CN114520065B - Lead-free composite powder for negative electrode of solar cell, method for producing the same, and silver paste for negative electrode of solar cell - Google Patents
Lead-free composite powder for negative electrode of solar cell, method for producing the same, and silver paste for negative electrode of solar cell Download PDFInfo
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- CN114520065B CN114520065B CN202210315054.1A CN202210315054A CN114520065B CN 114520065 B CN114520065 B CN 114520065B CN 202210315054 A CN202210315054 A CN 202210315054A CN 114520065 B CN114520065 B CN 114520065B
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- silver
- powder
- solar cell
- negative electrode
- composite powder
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- 229910000978 Pb alloy Inorganic materials 0.000 description 1
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- 239000012964 benzotriazole Substances 0.000 description 1
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- BNMYXGKEMMVHOX-UHFFFAOYSA-N dimethyl butanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC BNMYXGKEMMVHOX-UHFFFAOYSA-N 0.000 description 1
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- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
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- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
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- 239000003350 kerosene Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
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- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
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- 239000001103 potassium chloride Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- RLAQMYBFAVTHSC-UHFFFAOYSA-M potassium;acetic acid;chloride Chemical compound [Cl-].[K+].CC(O)=O RLAQMYBFAVTHSC-UHFFFAOYSA-M 0.000 description 1
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- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
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- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
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Classifications
-
- 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
- H01B1/14—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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Sustainable Energy (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Sustainable Development (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a lead-free composite powder for a negative electrode of a solar cell, a method for manufacturing the same and silver paste for the negative electrode of the solar cell, wherein the lead-free composite powder for the negative electrode of the solar cell comprises inorganic powder and a silver coating layer formed on the surface of the inorganic powder, and the inorganic powder comprises Te-Na-X-O, wherein X is at least one of Ti or Zr of IVB group elements. According to the leadless composite powder for the solar battery negative electrode, the sodium element with wider reserve is specially selected as the glass core component to replace the most commonly used lithium element so as to reduce the glass viscosity, increase the fluidity and the contact performance, and a feasible scheme is provided for reducing the material cost of the composite powder; in addition, the silver layer is successfully preformed on the shell of the composite powder by adopting the coating technology, so that complex chemical reaction of generating the silver crystal tunneling layer by virtue of lead in the sintering process is avoided, and the electrode slurry is easier to achieve leadless and is environment-friendly.
Description
Technical Field
The invention relates to the field of solar cells, in particular to lead-free composite powder for a negative electrode of a solar cell, a method for manufacturing the composite powder and silver paste for the negative electrode of the solar cell prepared by using the composite powder.
Background
Conventional solar cell structures are used as an external energy source for generating hole-electron pair charge carriers by radiation of a suitable wavelength incident on the p-n junction of the semiconductor. These electron-hole pair charge carriers migrate in the electric field created by the p-n semiconductor junction and collect the resulting current through the conductive grid (gate line) to the external circuit. Conductive pastes (also known as inks) are commonly used to form conductive grids or metal contacts. To improve cell efficiency, the cell sheet is typically coated with an anti-reflective coating such as silicon nitride, aluminum oxide, or silicon oxide, etc., to promote light absorption. Due to the insulating properties of the anti-reflective layer, the conductive paste typically contains glass powder, which is dissolved by chemical reaction during sintering to eliminate the anti-reflective coating for contact with the substrate of the battery.
However, the high contact resistance caused by the glass layer remaining between the conductive grid line and the battery substrate has been a difficulty in improving the efficiency of the battery sheet due to the insulating properties of the glass itself.
The glass frits currently in common use contain mainly lead and other low melting point components, which give them softening points of about 300 to 700 ℃. In the sintering process of the battery, lead and lead-containing substances firstly react with the anti-reflection coating to generate a lead simple substance, then the lead simple substance and silver powder generate silver-lead alloy, and silver crystals with proper size are formed on the surface of the silicon substrate along with the phase separation of the alloy by cooling at the temperature to form conductive contact. However, due to unavoidable aging and hydrolysis of the battery pack filler such as EVA and the like, the decomposed acetic acid is extremely likely to react with lead in the electrode, so that it is dissolved, thereby causing problems of falling off of the grid line, failure of the battery pack and the like.
Studies have shown that the addition of zirconia or titania can improve the acid resistance of the glass frit to some extent. However, the addition of these two oxides can seriously affect the fluidity of the glass frit and the formation of silver crystals during sintering, so that the addition amount is limited, and it is difficult to simultaneously achieve the performance requirements of low contact resistance, high conversion efficiency and strong acid resistance.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide lead-free composite powder for a negative electrode of a solar cell, a method for manufacturing the composite powder and silver paste for the negative electrode of the solar cell prepared by using the composite powder.
According to a first aspect of the present invention, there is provided a lead-free composite powder for a negative electrode of a solar cell, comprising an inorganic powder and a silver coating layer formed on the surface of the inorganic powder; the inorganic powder comprises Te-Na-X-O, wherein X is at least one of Ti or Zr of IVB group elements.
Preferably, the inorganic powder is any one of glass powder, solid solution, and microcrystal powder.
According to a second aspect of the present invention, there is provided a method for producing a lead-free composite powder for a negative electrode of a solar cell, comprising the steps of:
S 1: adding an inorganic powder to the silver or silver complex solution, the components of the inorganic powder comprising Te and Na and at least one of group IVB elements Ti or Zr;
S 2: and adding a reducing agent to form a silver coating layer on the surface of the inorganic powder.
Preferably, in step S 1, the silver complex solution is prepared as follows:
A 1: dissolving a silver-containing compound in deionized water in a reactor with stirring;
b 1: a compound capable of complexing with silver is added, thereby obtaining a silver complex solution.
Preferably, in step S 1, the silver complex solution is prepared as follows:
A 1: dissolving a silver-containing compound in deionized water in a reactor with stirring;
B 1: adding a compound capable of complexing with silver, thereby forming a silver complex;
C 1: a base is added to adjust the basicity of the solution, thereby obtaining a silver complex solution.
Preferably, in step a 1, the silver-containing compound is silver nitrate.
Preferably, in the step B1, the compound capable of complexing with silver is ammonia water or ethylenediamine tetraacetic acid.
Preferably, in step S 1, the preparation components of the inorganic powder include the following three powders:
① Oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powders containing Te element;
② Oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powders containing Na element;
③ Oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powders containing the group IVB element Ti and/or Zr.
Preferably, in step S 2, the reducing agent is any one of hydrazine hydrate, hydroxylamine sulfate, formaldehyde, glucose, sucrose or fructose.
Preferably, after step S 2, step S 3 is further included: and (3) filtering, cleaning, drying and crushing the silver after the silver is precipitated on the surface of the inorganic powder.
According to a third aspect of the present invention, there is provided a silver paste for a negative electrode of a solar cell, comprising a conductive silver powder, an organic carrier, and the lead-free composite powder for a negative electrode of a solar cell described in any one of the above;
based on the total weight of the silver paste for the negative electrode of the solar cell, the silver paste comprises the following components in percentage by weight: 50 to 99.5 weight percent of conductive silver powder, 0.4 to 50 weight percent of organic carrier and 0.1 to 15 weight percent of lead-free composite powder for a negative electrode of a solar cell.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the leadless composite powder for the solar battery negative electrode, the sodium element with wider reserve is specially selected as the glass core component to replace the most commonly used lithium element, so that the glass viscosity is reduced, the fluidity and the contact performance are increased, and a feasible scheme is provided for reducing the material cost of the composite powder.
2. According to the preparation method of the lead-free composite powder for the solar cell negative electrode, disclosed by the invention, the silver layer is successfully formed on the shell of the composite powder in advance by adopting a coating technology, so that the complex chemical reaction of generating a silver crystal tunneling layer by virtue of lead in the sintering process is avoided, and the lead-free environment-friendly electrode slurry is easier to achieve.
3. According to the preparation method of the lead-free composite powder for the solar cell negative electrode, provided by the invention, the final contact performance of the electrode paste can be controlled and improved through the silver layer content by adopting the silver coating technology, so that the design difficulty of the inner core glass component is greatly reduced, and a larger space is provided for improving various comprehensive performances of the electrode paste, such as acid resistance, ageing resistance and the like.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below with reference to specific embodiments and examples, and it is apparent that the described examples are some examples of the present application, but not all examples.
Thus, the following detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
According to a first aspect of the present invention, there is provided a lead-free composite powder for a negative electrode of a solar cell, the lead-free composite powder comprising an inorganic powder and a silver coating layer formed on a surface of the inorganic powder; the inorganic powder comprises Te-Na-X-O, wherein X is at least one of Ti or Zr of IVB group elements, namely the lead-free composite powder for the negative electrode of the solar cell is formed by coating a silver coating layer on the surface of the inorganic powder of Te-Na-Ti-0 or Te-Na-Zr-O or Te-Na-Ti-Zr-O.
In combination with the first aspect of the present invention, in an alternative embodiment, the inorganic powder is any one of glass powder, solid solution, and microcrystal powder. More preferably, the inorganic powder is a glass frit.
In combination with the first aspect of the present invention, in a preferred embodiment, the present invention provides a lead-free composite powder for a negative electrode of a solar cell, which is formed by coating a silver coating layer on the surface of a glass frit of Te-Na-Ti-O.
In combination with the first aspect of the present invention, in a preferred embodiment, the present invention provides a lead-free composite powder for a negative electrode of a solar cell, which is formed by coating a silver coating layer on the surface of a glass frit of Te-Na-Zr-O.
In combination with the first aspect of the present invention, in an alternative embodiment, the inorganic powder is a Te-Na-X- (M) -O glass powder, wherein X is at least one of the group IVB elements Zr or Ti, M is any other cationic element or elements than Te, na, ti, zr, bi, li and Pb, and (M) means that the cationic element or elements may or may not be present in the glass powder.
In combination with the first aspect of the present invention, in an alternative embodiment, the composition of the inorganic powder comprises, in addition to at least one of the group IVB elements Ti or Zr, and Te and Na, any one or more of Sn、Al、Ce、Cs、Cu、Fe、K、Rb、Si、W、Zn、Ge、Ga、In、Ni、Ca、Mg、Sr、Ba、Se、Mo、W、Y、As、La、Nd、Co、Pr、Gd、Sm、Dy、Eu、Ho、Yb、Lu、Ta、V、Hf、Cr、Cd、Sb、F、Mn、P、Nb、B and Ru.
According to a second aspect of the present invention, there is provided a method for producing a lead-free composite powder for a negative electrode of a solar cell, the method comprising the steps of:
S 1: adding an inorganic powder to the silver or silver complex solution, the components of the inorganic powder comprising Te and Na and at least one of group IVB elements Ti or Zr;
s 2: a reducing agent is added to form a coating layer containing silver as a main component on the surface of the inorganic powder.
In an alternative embodiment, in combination with the second aspect of the present invention, in step S 1, the silver complex solution may be prepared by:
a 1: dissolving a silver-containing compound in deionized water in a reactor with agitation, the silver-containing compound being any silver salt, preferably silver nitrate;
B 1: adding a compound capable of complexing with silver on the basis of the step A 1 to form a silver complex, wherein the compound capable of complexing with silver can be ammonia water, organic amine such as ethylenediamine, ethylene Diamine Tetraacetic Acid (EDTA) or the like, and preferably the compound capable of complexing with silver is ammonia water;
C 1: on the basis of step B 1, a base is added to adjust the basicity of the solution, preferably sodium hydroxide, thereby obtaining a silver complex solution.
It should be noted that, in the process of preparing the silver complex solution, the step C 1 is not necessary, but the applicant has found through many experiments that, based on the step B 1, the addition of the alkali can make the silver more compact, so that the finally obtained silver coating layer of the lead-free composite powder for the negative electrode of the solar cell is less prone to falling off. Thus, the embodiment comprising step C 1 is a more preferred embodiment of the present invention.
In an alternative embodiment, in combination with the second aspect of the present invention, in step S 1, the preparation ingredients of the inorganic powder comprise the following three powders:
① Oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powders containing Te element;
② Oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powders containing Na element;
③ Oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powders containing the group IVB element Ti and/or Zr.
For example, when the inorganic powder is an inorganic powder of Te-Na-Ti-O, the preparation composition thereof may be a mixture of three powders: oxide powder containing Te element (such as TeO 2 powder), carbonate powder containing Na element (such as Na 2CO3 powder), oxide powder containing Ti element (such as TiO 2 powder).
Similarly, if the inorganic powder is an inorganic powder of Te-Na-Zr-0, the preparation component thereof may be a mixture of the following three powders: oxide powder containing Te element (such as TeO 2 powder), carbonate powder containing Na element (such as Na 2CO3 powder), oxide powder containing Zr element (such as ZrO 2 powder).
Further, the inorganic powder can be prepared by the following method:
A 2: preparing a mixture comprising three powders as described above;
B 2: heating the powder mixture under air or an oxygen-containing atmosphere to form a melt;
C 2: quenching the melt, milling and ball milling or air milling the quenched material, and screening the milled material to provide an inorganic powder having a desired particle size.
Wherein in step B 2, the powder mixture is sintered to a peak temperature of 600-1200 ℃ to form a melt. In step C 2, the melt is quenched on a stainless steel platen or between counter-rotating stainless steel rolls or by water quenching to form flakes, which can be ground to form a powder. Preferably, the milled inorganic powder has a median particle size (D50) of 0.1 to 3.0 microns.
In combination with the second aspect of the present invention, in an alternative embodiment, the preparation ingredients of the inorganic powder further comprise one or more other metal compounds, suitably other metal compounds comprising any one or more of B2O3、SiO2、WO3、K2O、Rb2O、Cs2O、Al2O3、MgO、CaO、SrO、BaO、V2O5、MoO3、Y2O3、Mn2O3、Ag2O、ZnO、Ga2O3、GeO2、In2O3、SnO2、Sb2O3、P2O5、CuO、NiO、Cr2O3、FeO、Fe3O4、Fe2O3、CoO、Co2O3、SeO2 and CeO 2.
Thus, in the present application, the terms "Te-Na-Ti-O", "Te-Na-Zr-0", "Te-Na-Ti-Zr-O" may also comprise other metal oxides, such as oxides comprising any one or more of the elements Sn、Al、Ce、Cs、Cu、Fe、K、Rb、Si、Zn、Ge、Ga、In、Ni、Ca、Mg、Sr、Ba、Se、Mo、W、Y、As、La、Nd、Co、Pr、Gd、Sm、Dy、Eu、Ho、Yb、Lu、Ta、V、Hf、Cr、Cd、Sb、F、Mn、P、Nb、B and Ru.
In an alternative embodiment in combination with the second aspect of the present invention, in step S 2, the reducing agent is any one of hydrazine hydrate, hydroxylamine sulfate, formaldehyde, saccharides (glucose, sucrose or fructose). Preferably, the reducing agent is hydrated diamine or sucrose. The selection of a suitable reducing agent is critical to forming a uniform silver coating on the surface of the inorganic powder, and the invention has been found through trial and error that the reducing agent can effectively form a silver coating on the surface of the inorganic powder rather than forming a mixture of the inorganic powder and silver powder particles.
In an alternative embodiment, in combination with the second aspect of the present invention, after step S 2, step S 3 is further included: and (3) filtering, cleaning, drying and crushing the silver after the silver is precipitated on the surface of the inorganic powder.
According to a third aspect of the present invention, there is provided a silver paste for a negative electrode of a solar cell, the silver paste comprising conductive silver powder, an organic carrier, and the lead-free composite powder for a negative electrode of a solar cell described above, the weight percentages of the components being based on the total weight of the silver paste for a negative electrode of a solar cell: 50 to 99.5 weight percent of conductive silver powder, 0.4 to 50 weight percent of organic carrier and 0.1 to 15 weight percent of lead-free composite powder for a negative electrode of a solar cell.
Further, the silver paste for the negative electrode of the solar cell, provided by the invention, comprises the conductive silver powder and the organic carrier, and can be prepared by adopting the following embodiments:
Conductive silver powder
In combination with the third aspect of the present invention, in an alternative embodiment, the conductive silver powder is in any one or more of flake form, spherical form, granular form, crystalline form, powder form, or other irregular form. Preferably, the conductive silver powder is in spherical form.
In combination with the third aspect of the invention, in an alternative embodiment, the conductive silver powder is provided in the form of a colloidal suspension.
In combination with the third aspect of the present invention, in an alternative embodiment, the silver paste for a negative electrode of a solar cell provided by the present invention contains 80 to 99.5wt% of the conductive silver powder in a spherical form.
In combination with the third aspect of the present invention, in an alternative embodiment, the silver paste for a negative electrode of a solar cell provided by the present invention comprises a conductive silver powder in spherical form having a coating layer, and the coating layer may comprise a phosphate and a surfactant, wherein the surfactant may comprise any one or more of polyoxyethylene, polyethylene glycol, benzotriazole, poly (ethylene glycol) acetic acid, lauric acid, oleic acid, capric acid, myristic acid, linoleic acid, stearic acid, palmitic acid, stearate, palmitate.
Organic carrier
In combination with the third aspect of the invention, in an alternative embodiment, the organic carrier comprises an organic binder, a surface dispersant, a thixotropic agent and a diluent.
In combination with the third aspect of the invention, in an alternative embodiment, the organic carrier is a solution of one or more solvents comprising one or more polymers, wherein the polymers may be monobutyl ether comprising ethylcellulose, ethylhydroxyethyl cellulose, wood rosin, a mixture of ethylcellulose and phenolic resin, polymethacrylates of lower alcohols, and ethylene glycol monoacetate; the solvent may be a mixture comprising terpenes such as alpha-or beta-terpineol or their esters with other solvents such as kerosene, dibutyl phthalate, butyl carbitol acetate, hexylene glycol and alcohols having a boiling point above 150 ℃ and alcohol esters.
In combination with the third aspect of the invention, in an alternative embodiment, the organic carrier further comprises the following components: bis (2- (2-butoxyethoxy) ethyl adipate, dibasic esters such as DBE, DBE-2, DBE-3, DBE-4, DBE-5, DBE-6, DBE-9 and DBE 1B, octyl epoxide resin, isotetradecanol and pentaerythritol esters of hydrogenated rosin.
In combination with the third aspect of the invention, in an alternative embodiment, the organic carrier comprises a volatile liquid to promote rapid hardening of the solar cell negative electrode of the invention after application of the silver paste to a substrate.
In combination with the third aspect of the invention, in an alternative embodiment, the organic carrier may comprise a thickener, a stabilizer, a surfactant and/or other common additives.
In combination with the third aspect of the invention, in an alternative embodiment, the organic carrier may be a plurality of inert viscous materials.
In making the silver paste for a solar cell negative electrode of the present invention, the inorganic component of the silver paste for a solar cell negative electrode of the present invention may be mixed with an organic vehicle to form a viscous paste having a consistency and rheology suitable for printing. Further, the inorganic component of the silver paste for the negative electrode of the solar cell may be dispersed in the organic carrier with a proper degree of stability during the manufacture, shipment and storage of the silver paste, and may be dispersed on the printing screen during the screen printing process. Suitable organic carriers have rheological properties that provide stable dispersion of solids, suitable viscosity and thixotropy for screen printing, suitable wettability of the substrate and slurry solids, good drying rates and good sintering characteristics.
The silver paste for the negative electrode of the solar cell provided by the invention can be prepared by the following method:
S 1: mixing a proper amount of lead-free composite powder for a negative electrode of a solar cell, an organic carrier and conductive silver powder to obtain a raw material mixture;
S 2: rolling the raw material mixture by a three-roller grinder to preliminarily prepare silver paste;
S 3: the viscosity of the silver paste was measured using a brookfield viscometer and an appropriate amount of solvent and resin were added to adjust the paste viscosity to a target viscosity to obtain the silver paste for a negative electrode of a solar cell of the present invention.
The silver paste for the negative electrode of the solar cell provided by the invention can be applied to the preparation of the solar cell, and the preparation process of the solar cell, the printing process and the sintering process related to the preparation process are described in the field.
In terms of the preparation process of the solar cell, the preparation process at least comprises the following two process steps:
S 1: providing a crystalline silicon solar cell silicon wafer;
S 2: and sintering the solar cell silicon wafer to obtain the solar cell.
In the process of preparing the solar cell, the conductive paste can be sintered on the front surface of the P-type PERC-SE cell, or on the back surface of the N-type TOPCon cell. In terms of the printing process of the conductive paste, it is preferable that the front surface, the back surface, and the embedded electrode are each applied by applying the conductive paste, and then sintering the conductive paste to obtain a sintered body. The conductive paste may be applied in a manner known to those of ordinary skill in the art including, but not limited to, dipping, pouring, dripping, injecting, spraying, doctor blading, curtain coating, brushing, printing, or a combination of at least two thereof, wherein the preferred printing technique is inkjet printing, screen printing, pad printing, lithographic printing, letterpress printing, stencil printing, or a combination of at least two thereof. Preferably, the conductive paste is applied by printing, more preferably, by screen printing. In a preferred embodiment, the conductive paste is applied to the N-side by screen printing. In the case of a sintering process of the conductive paste, after the conductive paste is applied, the conductive paste is sintered to obtain a solid electrode body to form an electrode. Sintering is carried out in a manner known to the person skilled in the art.
In an alternative embodiment, the sintering step meets at least one of the following criteria:
① The sintering is maintained at a temperature of about 700 to 900 ℃, preferably about 730 to 800 ℃;
② The sintering holding time at the holding temperature is about 1 to 10 seconds.
In an alternative embodiment, the sintering is performed at a holding time of about 10 seconds to about 2 minutes, more preferably about 25 to 90 seconds, and most preferably about 40 seconds to about 1 minute.
The sintering of the conductive paste on the front and back sides of the battery cell may be performed simultaneously or sequentially. Simultaneous sintering is suitable if the conductive pastes applied to both sides are similar, preferably the same optimum sintering conditions, in which case sintering is preferably carried out simultaneously. When sintering is performed sequentially, it is preferable to first apply the back side conductive paste and sinter, and then apply the conductive paste to the front side for sintering.
The following describes the advantageous effects of the embodiments of the present invention compared to the prior art with specific experimental data. In the following, for convenience of description, the term "composite powder" refers to "lead-free composite powder for a negative electrode of a solar cell", that is, when reference is made to composite powder hereinafter, it refers to "lead-free composite powder for a negative electrode of a solar cell".
Example 1
(1) Preparation of glass frit
Referring to table 1, 100g of glass frit raw materials are weighed, which includes: 73g of TeO 2, 1g of B 2O3, 1.6g of SiO 2, 2.5g of Na 2 O, 2.6g of MgO, 1g of Al 2O3, 1.3g of WO 3, 13.5g of ZnO and 3.5g of TiO 2, uniformly mixing the raw materials of the glass powder, pouring the raw materials into a crucible, then placing the crucible into a muffle furnace, heating to 1000 ℃, preserving heat for 40 minutes, pouring the molten glass melt between reversing stainless steel rollers for quenching, then placing the glass powder into a ball mill, and performing ball milling for 24 hours to obtain glass powder A 2 with the granularity of 2 um.
(2) Preparation of composite powder containing 10% silver coating
Referring to Table 2, 500ml of deionized water was added to a beaker, 9.6g of silver nitrate was dissolved with stirring, then 10ml of concentrated aqueous ammonia was added to form a clear solution of silver-containing ammonia complex, followed by 0.5g of sodium hydroxide. 60g of glass frit A 2 was added, and under stirring, 400 ml of a solution containing 18g of sucrose was added and stirred for 20 minutes. Washing with deionized water, and drying to obtain composite powder CA 2 containing 10% silver coating.
(3) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder, 30g of composite powder CA 2 and 100g of an organic vehicle were weighed, wherein the organic vehicle comprised 46.4g of 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, 1.5g of ethylcellulose, 8.4g of N-tallow-1, 3-diaminopropane dioleate, 4g of hydrogenated castor oil, 10.4g of pentaerythritol tetraester of perhydrogenated abietic acid, 26.3g of dimethyl adipate and 3g of dimethyl glutarate.
Firstly, putting weighed composite powder CA 2 and an organic carrier into a wide-mouth bottle of a planetary stirrer, then adding conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; the mixture was then mixed with a planetary mixer at 800rpm for 3 minutes to obtain a sample slurry. And grinding the sample slurry for 5 times by using a three-roller grinder, and testing that the grinding fineness is less than 10 mu m and the Brookfield viscosity is between 300 and 350Pa.s to obtain the silver slurry PCA 2 for the negative electrode of the solar cell.
Example 2
(1) Preparation of glass frit
Referring to table 1, 100g of glass frit raw materials are weighed, which includes: 73g of TeO 2, 1g of B 2O3, 1.4g of SiO 2, 2.5g of Na 2 O, 2.6g of MgO, 1g of Al 2O3, 13.5g of ZnO and 5g of ZrO 2, uniformly mixing the raw materials of the glass powder, pouring the raw materials into a crucible, then placing the crucible into a muffle furnace, heating to 1000 ℃, preserving heat for 40 minutes, pouring the molten glass material between reversing stainless steel rollers for quenching, then placing the glass powder into a ball mill, and ball milling for 24 hours to obtain glass powder A 3 with the granularity of 2 um.
(2) Preparation of composite powder containing 20% silver coating
Referring to Table 2, 500ml deionized water was added to the beaker and 19.2g of silver nitrate was dissolved with stirring. Then, 20ml of concentrated aqueous ammonia was added to form a transparent solution of an ammonia complex containing silver, and 0.5g of sodium hydroxide was added. 60 g of glass frit A 3 were added, and 400ml of a solution containing 36g of hydrazine hydrate was added with stirring. Stirring for 20 minutes. Washing with deionized water, and drying to obtain composite powder CA 3 containing 20% silver coating.
(3) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder, 30g of composite powder CA 3, 100g of an organic vehicle comprising 46.4g of 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, 1.5g of ethylcellulose, 8.4g of N-tallow-1, 3-diaminopropane dioleate, 4g of hydrogenated castor oil, 10.4g of pentaerythritol tetraester of perhydrogenated abietic acid, 26.3g of dimethyl adipate and 3g of dimethyl glutarate were weighed.
Firstly, putting weighed composite powder CA 3 and an organic carrier into a wide-mouth bottle of a planetary stirrer, then adding conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; the mixture was then mixed with a planetary mixer at 800rpm for 3 minutes to obtain a sample slurry. And grinding the sample slurry for 5 times by using a three-roller grinder, and testing that the grinding fineness is less than 10 mu m and the Brookfield viscosity is between 300 and 350Pa.s to obtain the silver slurry PCA 3 for the negative electrode of the solar cell.
Comparative example 1
(1) Preparation of glass frit
Referring to table 1, 100g of glass frit raw materials are weighed, which includes: 73g of TeO 2, 1g of B 2O3, 1.6g of SiO 2, 1.5g of Li 2 O, 1.5g of Na 2 O, 2.6g of MgO, 1g of Al 2O3, 4.3g of WO 3 and 13.5g of ZnO, uniformly mixing the raw materials of the glass powder, pouring the raw materials into a crucible, then placing the crucible into a muffle furnace, heating to 1000 ℃, preserving heat for 40 minutes, pouring the molten glass melt between reversing stainless steel rollers for quenching, then placing the glass powder into a ball mill, and ball milling for 24 hours to obtain glass powder A 1 with the granularity of 2 um.
(2) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder, 30g of glass frit A 1 and 100g of an organic vehicle were weighed, wherein the organic vehicle comprised 46.4g of 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, 1.5g of ethylcellulose, 8.4g of N-tallow-1, 3-diaminopropane dioleate, 4g of hydrogenated castor oil, 10.4g of pentaerythritol tetraester of perhydrogenated abietic acid, 26.3g of dimethyl adipate and 3g of dimethyl glutarate.
Firstly, putting weighed glass powder A 1 and an organic carrier into a wide-mouth bottle of a planetary stirrer, then adding conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; the mixture was then mixed with a planetary mixer at 800rpm for 3 minutes to obtain a sample slurry. And grinding the sample slurry for 5 times by using a three-roller grinder, and testing that the grinding fineness is less than 10 mu m and the Brookfield viscosity is between 300 and 350Pa.s to prepare the silver slurry PA 1 for the negative electrode of the solar cell.
Comparative example 2
(1) Preparation of glass frit
The glass powder used in this example is glass powder A 2 prepared in example 1.
(2) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder, 30g of glass frit A 2 and 100g of an organic vehicle were weighed, wherein the organic vehicle comprised 46.4g of 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, 1.5g of ethylcellulose, 8.4g of N-tallow-1, 3-diaminopropane dioleate, 4g of hydrogenated castor oil, 10.4g of pentaerythritol tetraester of perhydrogenated abietic acid, 26.3g of dimethyl adipate and 3g of dimethyl glutarate.
Firstly, putting weighed glass powder A 2 and an organic carrier into a wide-mouth bottle of a planetary stirrer, then adding conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; the mixture was then mixed with a planetary mixer at 800rpm for 3 minutes to obtain a sample slurry. And grinding the sample slurry for 5 times by using a three-roller grinder, and testing that the grinding fineness is less than 10 mu m and the Brookfield viscosity is between 300 and 350Pa.s to prepare the silver slurry PA 2 for the negative electrode of the solar cell.
Comparative example 3
(1) Preparation of glass frit
The glass powder used in this example is glass powder A 3 prepared in example 2.
(2) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder, 30g of glass frit A 3 and 100g of an organic vehicle were weighed, wherein the organic vehicle comprised 46.4g of 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, 1.5g of ethylcellulose, 8.4g of N-tallow-1, 3-diaminopropane dioleate, 4g of hydrogenated castor oil, 10.4g of pentaerythritol tetraester of perhydrogenated abietic acid, 26.3g of dimethyl adipate and 3g of dimethyl glutarate.
Firstly, putting weighed glass powder A 3 and an organic carrier into a wide-mouth bottle of a planetary stirrer, then adding conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; the mixture was then mixed with a planetary mixer at 800rpm for 3 minutes to obtain a sample slurry. And grinding the sample slurry for 5 times by using a three-roller grinder, and testing that the grinding fineness is less than 10 mu m and the Brookfield viscosity is between 300 and 350Pa.s to prepare the silver slurry PA 3 for the negative electrode of the solar cell.
Table 1 shows the composition formulations of the glass frits described in the above examples and comparative examples, wherein glass frit A 1 is a Te-Na-O component system glass frit, glass frit A 2 is a Te-Na-Ti-O component system glass frit, and glass frit A 3 is a Te-Na-Zr-O component system glass frit.
Table 2 shows the composition formulation of the composite powder described in the above examples, wherein the glass frit used in the composite powder CA 2 is a Te-Na-Ti-O component system glass frit, and the silver content in the silver coating layer is 10%; the glass powder adopted by the composite powder CA 3 is Te-Na-Zr-O component system glass powder, and the silver content in the silver coating layer is 20 percent.
Table 3 shows the composition formulations of the silver pastes for negative electrodes of solar cells described in the above examples and comparative examples, each of which contains the same contents of the conductive silver powder and the organic vehicle, except that comparative example 1 (PA 1) was prepared using glass frit a 1, comparative example 2 (PA 2) was prepared using glass frit a 2, and comparative example 3 (PA 3) was prepared using glass frit a 3; example 1 (PCA 2) was prepared using composite powder CA 2 and example 2 (PCA 3) was prepared using composite powder CA 3, and it is worth noting that the conductive silver powder in table 3 was spherical conductive silver powder using oleic acid as a surfactant.
TABLE 1
| Composition of the components | A 1 (comparative example 1) | A 2 (example 1, comparative example 2) | A 3 (example 2, comparative example 3) |
| TeO2 | 73 | 73 | 73 |
| B2O3 | 1 | 1 | 1 |
| SiO2 | 1.6 | 1.6 | 1.4 |
| Li2O | 1.5 | 0 | 0 |
| Na2O | 1.5 | 2.5 | 2.5 |
| MgO | 2.6 | 2.6 | 2.6 |
| Al2O3 | 1 | 1 | 1 |
| WO3 | 4.3 | 1.3 | 0 |
| ZnO | 13.5 | 13.5 | 13.5 |
| TiO2 | 0 | 3.5 | 0 |
| ZrO2 | 0 | 0 | 5 |
TABLE 2
| Composition of the components | CA 2 (example 1) | CA 3 (example 2) |
| Glass powder | A2 | A3 |
| Silver coating layer | 10％ | 20％ |
TABLE 3 Table 3
| Component (wt%) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Example 1 | Example 2 |
| Conductive silver powder | 87％ | 87％ | 87％ | 87％ | 87％ |
| Composite powder | 0 | 0 | 0 | 3％CA2 | 3％CA3 |
| Glass powder | 3％A1 | 3％A2 | 3％A3 | 0 | 0 |
| Organic carrier | 10％ | 10％ | 10％ | 10％ | 10％ |
Performance testing
(1) Preparation of the cells used for the test:
N-type TOPCon solar cell
The silver paste for negative electrodes of solar cells prepared in example 1, comparative example 1 and comparative example 2 described above was used for the manufacture of N-type TOPCon solar cell sheets. The production process flow of the N-type TOPCon solar cell slice is generally divided into texturing the upper surface of N-type monocrystalline silicon, then forming a boron diffusion layer on the front surface, manufacturing PN junction and forming a P+ layer. And then sequentially forming a tunneling silicon oxide layer and a doped polysilicon layer on the back surface. An anti-reflective layer is then prepared on the back side and a passivation layer and an anti-reflective layer are prepared on the front side. Conductive silver paste and silver aluminum paste are then printed on the back and front sides by screen printing. The solar cell negative electrodes prepared in example 1, comparative example 1 and comparative example 2 were printed with silver paste on the back side anti-reflection layer, and the front side printed silver paste was typically silver paste which could burn through the passivation layer and form a point contact on the p+ diffusion layer, such as PV3N3 silver paste from dupont, or other commercially available silver paste.
The solar cell negative electrodes prepared in example 1, comparative example 1 and comparative example 2 above were screen printed on the back side (TOPCon side) of the cell (480 mesh 11um screen wire diameter, 17um screen thickness 15um latex thickness, 116 25um sub-grid wires and 5 main grids) using a semiautomatic screen printer from Asys Group, EKRA Automatisierungs systems Group with the following screen parameters. A commercial silver aluminum paste of PV3N3 from dupont was printed on the p+ doped front side of the cell using the same printer and screen parameters. After printing each side, the silicon wafer with the printed pattern was dried in an oven at 150 ℃ for 10 minutes. The cell was then fired with the p+ doped face up in a Centrotherm-300-FF strand sintering furnace for 1.5 minutes. For example 1, comparative example 1 and comparative example 2, sintering was performed at a maximum sintering temperature of 750 ℃.
P-type PERC-SE solar cell
The silver paste for negative electrodes of solar cells prepared in example 2, comparative example 1 and comparative example 3 described above was used for the manufacture of P-type PERC-SE solar cell sheets. The production process flow of the PERC-SE solar cell is generally divided into texturing the upper surface of the P-type monocrystalline silicon, and then forming a phosphorus diffusion layer on the front surface to manufacture a PN junction. And then carrying out region doping on the diffused silicon wafer by laser, and plating a layer of oxide film on the surface of the laser heavily doped silicon wafer. And then etching and polishing the back surface, and removing the phosphosilicate glass on the front and back surfaces. And annealing the battery piece to carry out integral passivation. And finally, depositing a passivation layer and an antireflection film on the surface of the battery piece, and carrying out laser grooving on the back surface.
The negative electrode of the solar cell prepared in the above example 2, comparative example 1 and comparative example 3 was printed with silver paste on the front anti-reflective film and passivation film, and the back-printed aluminum paste was generally used as a non-burn-through type aluminum paste product capable of performing thin-grid line printing and forming a back field, and RX (EFX 88C) aluminum paste of juxing company was used, and may be other commercially available aluminum paste. The printing process of the back side aluminum paste is completed before the adopted battery piece is purchased.
The battery cells have dimensions of 156x156mm 2 and a quasi-square shape. The paste of the examples was screen printed on the N-doped side of the cell sheet (480 mesh 11um screen wire diameter, 17um screen thickness 15um latex thickness, 116 25um secondary grid wires and 5 primary grids) using a semiautomatic screen printer from the Asys Group, EKRA Automatisierungs systems Group with the following screen parameters. After printing the front side, the silicon wafer with the printed pattern was dried in an oven at 150 ℃ for 10 minutes. The substrate was then fired in a Centrotherm-300-FF strand sintering furnace with the N-doped side up for 1.5 minutes. For example 2, comparative example 1 and comparative example 3 described above, sintering was performed at a maximum sintering temperature of 750 ℃.
(2) Performance testing
IV test
The solar cells were characterized using a commercially available IV tester "cetisPV-CTL1" from Halm Elektronik GmbH at 25 ℃ +/-1.0 ℃. Xe arc lamps simulate sunlight and are known to have an AM1.5 intensity of 1000W/m 2 on the cell surface. To have this intensity the lamp flashes several times in a short time until a steady level is reached, as monitored by the IV tester 'PVCTControl 4.313.0' software. The Halm IV tester uses a multi-point contact method to measure current (I) and voltage (V) to determine the IV curve of the battery. All values are automatically determined from the curve by means of the running software package. As a reference standard, calibrated solar cells obtained from ISE Freiburg and made of the same area size, the same cell sheet material and using the same front side pattern were tested and the data compared to certified values. At least 5 battery cells processed in very identical fashion were measured and the data was analyzed by calculating the average of the values. Software PVCTControl 4.313.0 provides the values of efficiency, fill factor, short circuit current, series resistance, and open circuit voltage.
Contact resistance
All equipment and materials were equilibrated in an air conditioning chamber at a temperature of 22+1 ℃ prior to measurement. To measure the contact resistance of the fired electrode on the doped front layer of a silicon solar cell, "GP4-Test Pro" from company GP solar GmbH equipped with "GP-4Test 1.6.6pro" software package was used. The device estimates the contact resistance by the Transfer Length Method (TLM) using the 4-point measurement principle. To measure the contact resistance, two strips 1cm wide were cut from the cell perpendicular to the printed grid line of the cell. Each strip was measured for its exact width with an accuracy of 0.05 mm. The width of the fired secondary grid line was measured at 3 different points on the bar using a digital microscope "VHX-600D" from company Keyence corp. The width was measured 10 times at each point in 2-point measurements. The gate line width value is the average of all 30 measurements. The contact resistance is calculated by the software package using the width of the gate lines, the width of the bars and the distance of the printed gate lines from each other. The measurement current was set to 14mA. A multi-contact measurement head adapted to contact 6 adjacent grid lines is mounted and in contact with the 6 adjacent grid lines. Measurements were made on 5 points equally spaced on each bar. After starting the measurement, the software determines the value of the contact resistance (mohm) for each point on the strip. The average of all 10 points is taken as the value of the contact resistance.
Acetic acid test
1) Preparation of 3% potassium chloride acetate solution
Weigh 115gKCl in plastic box, lay flat at the bottom of box, ensure no more than 1cm of granule in KCl. 194ml of pure water were measured and added to a plastic box. 6g of acetic acid is measured and added into the plastic box, and the plastic base cushion is put into the plastic box after the acetic acid is evenly shaken slightly.
2) Preparation before testing
Before testing, the battery pieces are numbered and IV initial performance characterization is completed, the PVC glove is worn, the battery pieces to be tested are inserted into the flower basket in the following mode (one spacer is put), and the two pieces closest to the edge are put into the accompanying pieces. Placing the flower basket in the middle of the plastic box, covering the box cover and buckling, sealing by using a winding film, placing the plastic box with the battery piece to be tested and the fan wire on an electronic scale for weighing, and recording the reading.
3) Testing
After the fan power supply is switched on and the fan is checked to run well, the plastic box is placed in the oven, and after the position of the flower basket is detected to be not displaced again, the plastic box is kept for 20 hours in the oven with the temperature of 85 ℃; and closing the fan, taking out the plastic box, weighing the weight record data after the plastic box is cooled to room temperature, taking the plastic box out of the basket by taking the PVC gloves, and taking out the battery piece to be tested for testing IV performance.
Test results
Test example 1
According to the above method, silver paste PA 1 for negative electrode of solar cell prepared in comparative example 1, silver paste PA 2 for negative electrode of solar cell prepared in comparative example 2 and silver paste PCA 2 for negative electrode of solar cell prepared in example 1 were printed on the back surface (N surface) of N-type TOPCon cell sheet, and crystalline silicon solar cells were prepared by baking and sintering, and the electrical properties were tested, and the results were averaged, as shown in table 4-1, wherein Uoc indicates open circuit voltage value; FF refers to fill factor value; rc refers to the contact resistance value; ncell denotes a conversion efficiency value.
It can be seen from table 4-1 that the conversion efficiency of the solar cell prepared from the silver paste for negative electrode of solar cell (PCA 2) of example 1 was significantly higher than that of the solar cell prepared from the silver paste for negative electrode of solar cell (PA 2) of comparative example 2, and the contact resistance Rc of the former was also superior to the latter, and the conversion efficiency of the solar cell prepared from the silver paste for negative electrode of solar cell (PCA 2) of example 1 was the same as that of the solar cell prepared from the silver paste for negative electrode of solar cell (PA 1) of comparative example 1. This result demonstrates that, while comparative example 2 (PA 2) shows that the addition of Ti increases the contact resistance of the glass powder compared to comparative example 1 (PA 1), the test data shown in example 1 indicate that the silver coating process allows the composite powder using Te-Na-Ti-O to significantly reduce the contact resistance, improving the performance of N-type TOPCon cell and achieving comparable overall performance as compared to the conventional Te-Na-O glass powder sample (PA 1).
Further, the prepared solar cell was subjected to an acetic acid test, and then the electrical properties thereof were again tested, and the results were averaged, as shown in table 4-2, wherein Uoc indicates an open circuit voltage value; FF refers to fill factor value; ncell denotes a conversion efficiency value, Δ Ncell denotes a conversion efficiency value of relative gain or attenuation, and Δ Ncell is a positive value when the conversion efficiency is relative to the gain, and Δ Ncell is a negative value when the conversion efficiency is relative to the attenuation. The calculation formula of Δ Ncell is: (conversion efficiency value after acetic acid test-conversion efficiency value before acetic acid test)/conversion efficiency value before acetic acid test.
As can be seen from table 4-2, although the solar cell prepared with the silver paste for negative electrode of solar cell (PA 1) described in comparative example 1 also had higher conversion efficiency, only the solar cell prepared with the silver paste for negative electrode of solar cell (PCA 2) described in example 1 had a conversion efficiency value of less than 5% of the relative attenuation after acetic acid test. This result shows that the addition of Ti element can significantly improve the acid resistance of the electrode paste. Obviously, the Te-Na-Ti-O composite powder adopting the silver coating process flow is beneficial to improving the ageing resistance of the N-type TOPCon battery piece while ensuring the high conversion efficiency of the battery piece.
TABLE 4-1
| Sample of | Comparative example 1 | Comparative example 2 | Example 1 |
| Uoc(mV) | 680.594 | 683.805 | 681.538 |
| FF(％) | 76.3688 | 75.4587 | 76.2444 |
| Rc(mohm) | 0.84341 | 1.35149 | 1.09913 |
| Ncell(％) | 22.6386 | 22.387 | 22.6811 |
Table 4-2 (after acetic acid experiments)
| Sample of | Comparative example 1 | Comparative example 2 | Example 1 |
| Uoc(mV) | 680.064 | 682.705 | 681.038 |
| FF(％) | 55.9348 | 71.0587 | 73.1344 |
| Ncell(％) | 16.9196 | 21.057 | 21.7111 |
| ΔNcell(％) | -25.26％ | -5.94％ | -4.28％ |
Test example 2
According to the above method, silver paste PA 1 for negative electrode of solar cell prepared in comparative example 1, silver paste PA 3 for negative electrode of solar cell prepared in comparative example 3 and silver paste PCA 3 for negative electrode of solar cell prepared in example 2 were printed on the front side (N side) of P-type PERC-SE battery sheet, and crystalline silicon solar cells were prepared by baking and sintering, and the electrical properties were tested, and the results were averaged and listed in table 5-1, wherein Uoc indicates open circuit voltage value; FF refers to fill factor value; rc refers to the contact resistance value; ncell denotes a conversion efficiency value.
It can be seen from table 5-1 that the conversion efficiency of the solar cell prepared from the silver paste for negative electrode of solar cell (PCA 3) of example 2 was significantly higher than that of the solar cell prepared from the silver paste for negative electrode of solar cell (PA 3) of comparative example 3, and the contact resistance Rc of the former was also superior to that of the latter, and the conversion efficiency of the solar cell prepared from the silver paste for negative electrode of solar cell (PCA 2) of example 2 was the same as that of the solar cell prepared from the silver paste for negative electrode of solar cell (PA 1) of comparative example 1. This result demonstrates that, while comparative example 3 (PA 3) shows that the addition of Zr element increases the contact resistance of the glass powder compared to comparative example 1 (PA 1), the test data shown in example 2 indicate that the silver coating process allows the composite powder using Te-Na-Zr-O to significantly reduce the contact resistance, improving the performance of the P-type PERC-SE battery cell, and achieving comparable overall performance as compared to the conventional Te-Na-O glass powder sample (PA 1).
Further, the prepared solar cell was subjected to an acetic acid test, and then the electrical properties thereof were again tested, and the results were averaged, as shown in table 5-2, wherein Uoc indicates an open circuit voltage value; FF refers to fill factor value; ncell denotes a conversion efficiency value, Δ Ncell denotes a conversion efficiency value of relative gain or attenuation, and Δ Ncell is a positive value when the conversion efficiency is relative to the gain, and Δ Ncell is a negative value when the conversion efficiency is relative to the attenuation. The calculation formula of Δ Ncell is: (conversion efficiency value after acetic acid test-conversion efficiency value before acetic acid test)/conversion efficiency value before acetic acid test.
As can be seen from table 5-2, although the solar cell prepared with the silver paste for negative electrode of solar cell (PA 1) described in comparative example 1 also had higher conversion efficiency, only the solar cell prepared with the silver paste for negative electrode of solar cell (PCA 2) described in example 2 had a conversion efficiency value of less than 5% with respect to attenuation after acetic acid test. This result shows that the addition of Zr element can obviously raise the acid-resisting property of electrode paste. Obviously, the composite powder of Te-Na-Zr-O adopting the silver coating process flow is beneficial to improving the ageing resistance of the P-type PERC-SE battery piece while ensuring the high conversion efficiency of the battery piece.
TABLE 5-1
| Sample of | Comparative example 1 | Comparative example 3 | Example 2 |
| Uoc(mV) | 666.329 | 667.288 | 666.413 |
| FF(％) | 80.0586 | 79.4702 | 80.0027 |
| Rc(mohm) | 1.61468 | 5.38914 | 0.930533 |
| Ncell(％) | 21.7787 | 21.6582 | 21.7682 |
Table 5-2 (after acetic acid experiments)
| Sample of | Comparative example 1 | Comparative example 3 | Example 2 |
| Uoc(mV) | 665.499 | 666.678 | 665.813 |
| FF(％) | 63.8066 | 76.8602 | 77.7627 |
| Ncell(％) | 17.2307 | 20.9082 | 21.1382 |
| ΔNcell(％) | -20.88％ | -3.46％ | -2.89％ |
While the present invention has been described with reference to the above embodiments, it is apparent to those skilled in the art from this disclosure that various changes and modifications can be made without departing from the spirit of the invention.
Claims (4)
1. A lead-free composite powder for a negative electrode of a solar cell, which is characterized by comprising an inorganic powder and a silver coating layer formed on the surface of the inorganic powder; the inorganic powder comprises Te-Na-X-O, wherein X is Zr of IVB group elements;
The inorganic powder is glass powder, and each 100g of glass powder raw material comprises the following components: 73g of TeO 2, 1g of B 2O3, 1.4g of SiO 2, 2.5g of Na 2 O, 2.6g of MgO, 1g of Al 2O3, 13.5g of ZnO and 5g of ZrO 2;
The composite powder is composite powder containing 20% of silver coating layer, and the preparation method comprises the following steps: dissolve 19.2g silver nitrate in 500ml deionized water; then adding 20ml of concentrated ammonia water to form a transparent solution of silver-containing ammonia complex, and adding 0.5g of sodium hydroxide; 60g of the glass frit was added, and 400ml of a solution containing 36g of hydrazine hydrate was added to prepare a composite powder containing 20% silver coating.
2. The preparation method of the lead-free composite powder for the negative electrode of the solar cell is characterized by comprising the following steps of:
S 1: weighing 100g of glass powder raw materials to prepare glass powder, wherein the glass powder raw materials comprise 73g of TeO 2, 1g of B 2O3, 1.4g of SiO 2, 2.5g of Na 2 O, 2.6g of MgO, 1g of Al 2O3, 13.5g of ZnO and 5g of ZrO 2;
S 2: dissolve 19.2g silver nitrate in 500ml deionized water; then adding 20ml of concentrated ammonia water to form a transparent solution of silver-containing ammonia complex, and adding 0.5g of sodium hydroxide; 60 g of the glass frit was added, and 400ml of a solution containing 36g of hydrazine hydrate was added to prepare a composite powder containing 20% silver coating.
3. The method for producing a lead-free composite powder for a negative electrode of a solar cell according to claim 2, further comprising, after step S 2, step S 3: and (3) filtering, cleaning, drying and crushing the silver after the silver is precipitated on the surface of the inorganic powder.
4. A silver paste for a negative electrode of a solar cell, characterized by comprising a conductive silver powder, an organic carrier and the lead-free composite powder for a negative electrode of a solar cell of claim 1;
based on the total weight of the silver paste for the negative electrode of the solar cell, the silver paste comprises the following components in percentage by weight: 50 to 99.5 weight percent of conductive silver powder, 0.4 to 50 weight percent of organic carrier and 0.1 to 15 weight percent of lead-free composite powder for a negative electrode of a solar cell.
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| CN102653453A (en) * | 2011-03-01 | 2012-09-05 | 同和电子科技有限公司 | Silver-coated glass powder for conduction and manufacture method thereof and conductive paste |
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| CN106782754A (en) * | 2016-12-29 | 2017-05-31 | 武汉优乐光电科技有限公司 | A kind of inorganic composite materials additive solar cell positive silver paste |
| JP2019052080A (en) * | 2017-09-12 | 2019-04-04 | Ｄｏｗａエレクトロニクス株式会社 | Silver coated glass powder and method for producing the same |
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Patent Citations (6)
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| JP2011178634A (en) * | 2010-03-03 | 2011-09-15 | Okuno Chemical Industries Co Ltd | Lead-free low-melting-point glass having acid resistance |
| CN102479568A (en) * | 2010-11-30 | 2012-05-30 | 比亚迪股份有限公司 | Conductive paste for solar cell and preparation method thereof |
| CN102653453A (en) * | 2011-03-01 | 2012-09-05 | 同和电子科技有限公司 | Silver-coated glass powder for conduction and manufacture method thereof and conductive paste |
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| JP2019052080A (en) * | 2017-09-12 | 2019-04-04 | Ｄｏｗａエレクトロニクス株式会社 | Silver coated glass powder and method for producing the same |
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