CN111302638B - Glass powder composition, conductive silver paste containing glass powder composition and solar cell - Google Patents

Glass powder composition, conductive silver paste containing glass powder composition and solar cell Download PDF

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CN111302638B
CN111302638B CN201811509689.5A CN201811509689A CN111302638B CN 111302638 B CN111302638 B CN 111302638B CN 201811509689 A CN201811509689 A CN 201811509689A CN 111302638 B CN111302638 B CN 111302638B
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silver paste
parts
conductive silver
glass frit
frit composition
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CN111302638A (en
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周欣山
包娜
汪山
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Suzhou Jingyin New Material Technology Co ltd
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Suzhou Isilver Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • 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
    • 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

Abstract

The invention provides a glass powder composition, and a conductive silver paste and a solar cell containing the same. The glass powder composition is a Te-Pb-Ta-Zn based glass powder composition, wherein the glass powder composition comprises the following components in percentage by weight of corresponding oxides: te (5-95): pb (5-50): ta (1-20): zn (1-10). The conductive silver paste provided by the invention comprises the glass powder composition. The solar cell adopting the conductive silver paste has better corrosion capability on passivation layers such as silicon nitride, aluminum oxide, silicon oxide and the like, and has good infiltration capability on silver and silicon base.

Description

Glass powder composition, conductive silver paste containing glass powder composition and solar cell
Technical Field
The invention relates to a glass powder composition and conductive silver paste in a solar cell, and belongs to the technical field of materials of solar cells.
Background
Photovoltaic power generation is taken as an important branch of novel clean energy, and has been developed rapidly in recent years, and the whole industrial chain actively improves the conversion efficiency of photovoltaic cells and reduces the cost through technical innovation, and replaces the traditional high-pollution energy.
At present, the photovoltaic cell for large-scale industrialization is a crystalline silicon solar cell. In recent years, in order to improve conversion efficiency and reduce cost, high-efficiency solar cell technology is rapidly developed, and the fine classification is gradually increased, such as black silicon, PERC, double-sided alumina PERC, N-type, P-type and the like.
The solar cell electrode silver paste is used as a functional part for leading out cell current and has the characteristic of noble metal silver, and is particularly important in improving the efficiency of the cell and reducing the cost. The silver paste of the light receiving surface electrode of the solar cell mainly comprises silver powder, an inorganic glass powder composition and an organic carrier, wherein the silver powder is a main conductive base material; the inorganic glass powder composition can corrode SiO on the surface of the battery 2 、SiN x And Al 2 O 3 The passivation layer forms good ohmic contact with the silicon substrate, and the sintering effect between the passivation layer and the silver particles is improved; the organic carrier is mainly used for dispersing the silver powder and the inorganic glass powder composition, endows the slurry with certain rheological property, and is suitable for silk screenPrinting process, and forming fine electrodes.
The glass powder composition adopted at present mainly comprises a lead salt, tellurate and borosilicate glass powder composition. With the development of solar cell technology, new high-efficiency cells and new cell process technology are upgraded faster, requirements on electrode silver paste performance are higher and higher, wherein requirements on glass powder which is one of main components of the silver paste are correspondingly increased, and different electrode pastes, especially glass powder playing a core role, can be developed according to different cell technologies in general in the prior art.
Therefore, the development of a glass powder system with good adaptability, which can be applied to various types of crystalline silicon batteries, becomes one of the problems to be solved in the field.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a front electrode silver paste in a solar cell, which has a good corrosion capability on passivation layers such as silicon nitride, aluminum oxide, and silicon oxide, and has a good wetting capability on silver and silicon.
In order to achieve the above technical object, the present invention provides a glass frit composition, which is a Te-Pb-Ta-Zn based glass frit composition, wherein the composition of the glass frit composition comprises, based on the weight of the corresponding oxides: te (5-95): pb (5-50): ta (1-20): zn (1-10).
In one embodiment of the present invention, the composition of the glass frit composition is Te (10): pb (20): ta (9): zn (7).
In the glass frit composition of the present invention, the composition of the glass frit composition may further contain one or a combination of several of Li, Na, K, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, B, P, Bi, Si, Al, La, Ce, Nd, Eu, Er, Zr, Sn, Sb, Se, Mo and W in terms of oxide weight.
In one embodiment of the present invention, the glass frit composition may contain one or a combination of more of Li, Na, K, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, B, P, Bi, Si, Al, La, Ce, Nd, Eu, Er, Zr, Sn, Sb, Se, Mo and W in an amount of 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 14 parts, based on 100 parts by weight of the glass frit composition.
In a further embodiment of the present invention, the composition of the glass frit composition may further comprise one or a combination of Li, Si, Al, Mg, B, Cr, P and V.
In the glass frit composition of the present invention, the raw material composition of the glass frit composition includes oxides of Te, Pb, Ta, and Zn; or, a compound containing Te, Pb, Ta, and Zn; wherein the compound containing Te, Pb, Ta and Zn can be decomposed into oxides of Te, Pb, Ta and Zn.
In one embodiment of the present invention, the oxide of Te may be TeO 2 (ii) a The oxide of Pb may be PbO or Pb 2 O 3 (ii) a The oxide of Ta may be Ta 2 O 5 (ii) a The oxide of Zn may be ZnO.
In the glass frit composition of the present invention, the raw material composition of the glass frit composition comprises Te (5-95): pb (5-50): ta (1-20): zn (1-10).
In the glass frit composition of the present invention, the glass frit composition may be an amorphous glass frit, a crystalline glass frit, or a glass frit composition in which amorphous and crystalline are mixed.
The invention also provides a solar cell, and the glass powder composition of the solar cell.
In order to achieve the above technical objects, the present invention also provides a method for preparing the above glass frit composition, which may include the steps of:
mixing the raw materials of the glass powder composition, and heating and melting at 750-1000 ℃ for 30-120 min;
cooling to obtain glass powder composition fragments;
and further crushing the glass powder composition fragments and then carrying out ball milling to obtain the glass powder composition with the required particle size distribution.
In the production method of the present invention, the heating and melting may be performed in an electric resistance furnace.
In the preparation method of the invention, no special requirement is required for the cooling operation, and the cooling can be carried out by water quenching, steel plates or stainless steel double-roll machines.
In the production method of the present invention, the desired particle size may be obtained by ball milling, for example, by a planetary ball mill, and the Te — Pb-Ta-Zn based glass powder composition having the desired particle size distribution may be obtained.
In order to achieve the above technical object, the present invention further provides a conductive silver paste comprising the Te-Pb-Ta-Zn based glass frit composition of the present invention.
In the conductive silver paste of the present invention, the conductive silver paste may include, based on 100 parts by weight of the total mass of the conductive silver paste, the following raw materials: 70 to 90 portions of silver powder, 0.5 to 5 portions of glass powder composition, 8 to 30 portions of organic carrier and 0.5 to 5 portions of auxiliary agent.
In one embodiment of the present invention, the silver powder may be contained in an amount of 72 parts, 75 parts, 80 parts, 82 parts, 85 parts, 89 parts.
In one embodiment of the present invention, the content of the glass frit composition may be 0.7 parts, 1 part, 1.3 parts, 1.5 parts, 2 parts, 3 parts, 3.2 parts, 3.5 parts, 4 parts, 4.3 parts, 4.5 parts, 4.7 parts.
In one embodiment of the present invention, the content of the organic vehicle may be 9 parts, 10 parts, 12 parts, 15 parts, 20 parts, 22 parts, 27 parts, 29 parts.
In one embodiment of the present invention, the content of the auxiliary agent may be 0.9 parts, 1.2 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 2.5 parts, 4 parts, 4.2 parts, 4.5 parts.
In the conductive silver paste, the silver powder is modified. The dispersion stability of the silver powder in the conductive silver paste can be improved through modification.
In the conductive silver paste, the modifier comprises one or a combination of a plurality of oleic acid, linoleic acid, linolenic acid, a silane coupling agent, hard fatty acid, fatty acid amine, polyvinylpyrrolidone, fatty alcohol-polyoxyethylene ether and a block macromolecular surfactant.
In the conductive silver paste, the modifier is a block macromolecular surfactant.
In one embodiment of the present invention, the block macromolecular surfactant used comprises one or more of alkyl vinyl-amine (hydroxy) vinyl ether block copolymer, acrylamide-surface active macromonomer-ionic monomer copolymer, fluorine-containing acrylic block copolymer and hydroxyethyl methacrylate block copolymer.
In the conductive silver paste of the present invention, the organic vehicle used includes a resin and an organic solvent.
In the conductive silver paste, the organic solvent comprises an organic solvent with the polarity of 2-5; further, the polarity of the organic solvent used is 2.5 to 4. For example, the polarity of the organic solvent used is 3, 3.5.
In the conductive silver paste, the organic solvent is one or a combination of more of terpineol, butyl carbitol acetate and glycol decahydrate.
In the conductive silver paste, the resin is one or more of cellulose, epoxy resin and acrylic resin.
In the conductive silver paste, the adopted auxiliary agent comprises one or more of a thixotropic agent, a dispersing agent, a lubricating agent, a humectant and a plasticizer.
In the conductive silver paste, the adopted dispersant is a macromolecular dispersant; further, the macromolecular dispersant used may be polyether, polyester, polyamide or polyorganosiloxane.
In the conductive silver paste of the present invention, the lubricant used may be a surfactant, silicone oil, or the like.
In the conductive silver paste of the present invention, the thixotropic agent used may be hydrogenated castor oil, polyamide, fumed silica, etc.
In the conductive silver paste of the present invention, the humectant used may be diethylene glycol, triethylene glycol, PEG400, glycerin, ethylene glycol, sorbitol, 1, 2-propylene glycol, diethylene glycol butyl ether, monoethylene glycol, polyethylene glycol, N-methyl-2-pyrrolidone, a condensate of polyhydric alcohol and ethylene oxide, xylitol, and the like.
In the conductive silver paste, the adopted plasticizer can be aliphatic dibasic acid ester, phthalic acid ester, terephthalic acid ester, benzene polyester ester, benzoate, polyol ester epoxy, citric acid ester, polyester and the like.
The conductive silver paste can be prepared by the following steps:
preparing an organic carrier: mixing the resin and the organic solvent in proportion, and stirring the mixture evenly at room temperature or under heating;
preparing slurry: and mixing the silver powder, the glass powder composition and the organic carrier, uniformly stirring, grinding and dispersing by a three-roller machine, and obtaining the conductive silver paste with the average scraper fineness of less than 10 micrometers, preferably less than 5 micrometers.
It should be noted here that the auxiliary agent may be added during the preparation of the organic vehicle; the organic vehicle can also be added during the preparation of the slurry, or partially during the preparation of the organic vehicle and partially during the preparation of the silver slurry.
The invention further provides a solar cell which comprises the conductive silver paste.
The glass powder composition and the silver paste formed by the glass powder composition can be used in crystalline silicon solar cells. The formed solar cell has good corrosion capability on passivation layers such as silicon nitride, aluminum oxide, silicon oxide and the like, can well infiltrate silver and silicon base, and has a proper amount of silver dissolving capability.
The conductive silver paste containing the Te-Pb-Ta-Zn based glass powder composition has higher sintering activity and better low-temperature sintering advantage, and is very suitable for preparing batteries with low sintering process temperature requirements, such as PERC batteries and the like.
The solar cell formed by the glass powder composition and the conductive silver paste has high photoelectric conversion efficiency, small series resistance, large short-circuit current and high welding tension.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention should not be construed as limiting the implementable scope of the present invention.
Solar cells are devices that directly convert light energy into electrical energy by the photoelectric or photochemical effect.
Example 1
This example provides a glass frit composition having a specific composition as shown in table 1.
TABLE 1
Figure BDA0001900379540000051
Figure BDA0001900379540000061
Example 2
This example provides a glass frit composition, which is prepared by the following steps:
weighing the Te-Pb-Ta-Zn based glass powder composition raw materials according to a certain proportion, mixing, and then placing in a resistance furnace for heating and melting at 900 ℃ for 50 min;
water quenching and steel plate cooling are carried out to obtain glass powder composition fragments;
the fragments were further crushed and then ball-milled by a planetary ball mill to obtain a Te-Pb-Ta-Zn based glass powder composition having a desired particle size distribution (D50: 0.1 to 5 μm).
Wherein the first Te-Pb-Ta-Zn base glass powder composition comprises the following raw materials in parts by weight: 10 parts of tellurium trioxide, 45 parts of lead monoxide, 20 parts of tantalum pentoxide, 1 part of aluminum trioxide, 3 parts of magnesium oxide, 2 parts of boron trioxide, 0.5 part of titanium dioxide, 10 parts of bismuth trioxide, 5 parts of molybdenum trioxide and 3.5 parts of zinc oxide.
The Te-Pb-Ta-Zn base glass powder composition of the second class comprises the following raw materials in parts by weight: 30 parts of tellurium trioxide, 40 parts of lead monoxide, 4.5 parts of tantalum dioxide, 1 part of magnesium oxide, 1 part of boron oxide, 5 parts of bismuth trioxide, 6 parts of tungsten trioxide, 5 parts of zinc oxide and 7.5 parts of lithium oxide.
The third Te-Pb-Ta-Zn base glass powder composition comprises the following raw materials in parts by weight: 38 parts of tellurium dioxide, 31 parts of lead dioxide, 5 parts of tantalum pentoxide, 4.5 parts of magnesium hydroxide, 2 parts of chromium sesquioxide, 3.5 parts of sodium carbonate, 5 parts of molybdenum trioxide, 3 parts of silicon dioxide and 8 parts of zinc oxide.
The fourth Te-Pb-Ta-Zn base glass powder composition comprises the following raw materials in parts by weight: 45 parts of tellurium trioxide, 30 parts of lead monoxide, 12 parts of tantalum pentoxide, 1.5 parts of aluminum oxide, 2 parts of boric acid, 3 parts of chromium trioxide, 0.5 part of titanium dioxide, 1 part of sodium oxide, 1 part of vanadium pentoxide and 4 parts of zinc molybdate.
Example 3
The embodiment provides a conductive silver paste, which is prepared through the following steps:
preparing an organic carrier: weighing and mixing the organic matters in proportion, and stirring the mixture at room temperature or under heating;
85 parts by weight of silver powder, 3 parts by weight of the glass frit composition No. 10 in Table 1, and 12 parts by weight of an organic vehicle were mixed and stirred uniformly in a ratio, and the mixture was ground and dispersed by a three-roll mill to have an average plate fineness of 10 μm or less, preferably 5 μm or less.
Example 4
The embodiment provides a solar cell, which is prepared by the following steps:
the method comprises the following steps that a boron-doped P-type silicon substrate is selected as a semiconductor substrate, wherein the P-type silicon substrate is a silicon wafer which is 180-250 mu m thick and is 125mm multiplied by 125mm or 156mm multiplied by 156mm or other typical sizes;
firstly, etching one side of a silicon substrate by using an alkali solution, wherein the etching is called a pyramid (monocrystal) or uneven (polycrystal) antireflection suede, and a black silicon nanometer suede can be prepared by using a wet method or a dry method black silicon technology;
secondly, forming an N-type diffusion layer on the other side of the P-type silicon substrate to prepare a PN junction, wherein the N-type diffusion layer can be prepared by a gas-phase thermal diffusion method taking gaseous phosphorus oxychloride as a diffusion source, or a phosphorus ion injection method, or a slurry coating thermal diffusion method containing phosphorus pentoxide, and the like;
thirdly, depositing a SiNx anti-reflection layer on one side of the suede surface of the silicon substrate, or adding a layer of Al 2 O 3 The passivation layer can also be other similar coatings with good antireflection effect;
fourthly, printing or coating an Al electrode layer and a main grid silver electrode layer on one side of the P or N type silicon substrate, and in addition, SiNx and Al can also be utilized 2 O 3 A passivation layer is formed on the back of the cell to act as a back reflector to increase the absorption of long wavelength light.
Fifthly, forming vertical and horizontal main grids and fine grids on the antireflection film on one side of the N-type silicon substrate by the conductive silver paste in the table 2 through screen printing, coating or ink-jet printing and the like, and co-firing at a certain sintering temperature to form the electrode body. The sintering peak temperature is 600-900 ℃.
And (3) carrying out an electrical property test on the solar cell, specifically:
the solar energy is used for simulating the electric efficiency tester to test under standard conditions (the atmospheric quality AM1.5, the illumination intensity 1000W/m) 2 Test temperature 25 ℃ C.), the results are shown in Table 2.
The method for testing the welding tension of the solar cell specifically comprises the following steps:
selecting a welding rod with the diameter of 1.2 multiplied by 0.25mm, setting the temperature of an electric iron to be 350 ℃, testing at a constant speed of 180 ℃ by using a tension tester, and taking the average value as the tension value of the test. 5 cells were tested per formulation and then averaged, with the results shown in table 2.
Electrical performance data and weld pull force are shown in table 2, using a single crystal PERC cell as an example.
TABLE 2
Figure BDA0001900379540000071
Figure BDA0001900379540000081
As can be seen from Table 2, the solar cell has low series resistance, large short-circuit current, high photoelectric conversion efficiency and large welding tension. The reason is that the glass powder component in the silver paste can moderately corrode a passivation layer, such as silicon nitride or aluminum oxide, in the sintering process, and the glass powder component forms good ohmic contact with the silicon substrate, has good wettability with the silver and the silicon substrate, and improves the electrode density after sintering, thereby improving the conductive capacity and the welding tension.

Claims (22)

1. A glass frit composition, wherein the glass frit composition is a Te-Pb-Ta-Zn based glass frit composition, wherein the glass frit composition has a composition, based on the weight of the corresponding oxides: te (50): pb (28): ta (11): zn (8): li (3).
2. The glass frit composition according to claim 1, wherein the raw material composition of the glass frit composition comprises oxides of Te, Pb, Ta, and Zn; or, a compound containing Te, Pb, Ta, and Zn, which can be decomposed into oxides of Te, Pb, Ta, and Zn.
3. The glass frit composition of claim 2, wherein the oxide of Te is TeO 2 。
4. The glass frit composition of claim 2, wherein the oxide of Pb is PbO or Pb 2 O 3 。
5. The glass frit composition of claim 2, wherein the oxide of Ta is Ta 2 O 5 。
6. The glass frit composition of claim 2, wherein the oxide of Zn is ZnO.
7. The glass frit composition according to any one of claims 1 to 6, wherein the glass frit composition is an amorphous glass frit composition and/or a crystalline glass frit composition.
8. A method of making a glass frit composition according to any of claims 1 to 7, comprising the steps of:
mixing the raw materials of the glass powder composition, and melting at 750-1000 ℃ for 30-120 min;
cooling to obtain glass powder composition fragments;
and further crushing the glass powder composition fragments and then carrying out ball milling to obtain the glass powder composition with the required particle size distribution.
9. A conductive silver paste comprising the glass frit composition of any one of claims 1 to 7.
10. The conductive silver paste of claim 9, wherein the conductive silver paste comprises the following raw materials, based on 100 parts by weight of the total mass of the conductive silver paste: 70 parts to 90 parts of silver powder, 0.5 parts to 5 parts of the glass frit composition according to any one of claims 1 to 7, 8 parts to 30 parts of an organic vehicle, and 0.5 parts to 5 parts of an assistant.
11. The conductive silver paste of claim 10, wherein the silver powder is a modified silver powder.
12. The conductive silver paste of claim 11, wherein the modifier used for modification comprises one or a combination of oleic acid, linoleic acid, linolenic acid, a silane coupling agent, a stearic acid, a fatty acid amine, polyvinylpyrrolidone, fatty alcohol-polyoxyethylene ether, and a block macromolecular surfactant.
13. The conductive silver paste of claim 12, wherein the modifier used for modification is a block macromolecular surfactant.
14. The conductive silver paste of claim 10, wherein the organic vehicle comprises a resin and an organic solvent.
15. The conductive silver paste of claim 14, wherein the organic solvent is an organic solvent with a polarity of 2-5.
16. The conductive silver paste of claim 15, wherein the organic solvent is an organic solvent with a polarity of 2.5-4.
17. The conductive silver paste of claim 15, wherein the organic solvent is one or a combination of terpineol, butyl carbitol acetate and glycol decaester.
18. The conductive silver paste of claim 14, wherein the resin is a combination of one or more of cellulose, epoxy and acrylic resins.
19. The conductive silver paste of claim 10, wherein the auxiliary agent comprises one or a combination of thixotropic agent, dispersant, humectant, lubricant and plasticizer.
20. The conductive silver paste of claim 19, wherein the dispersant is a macromolecular dispersant.
21. The conductive silver paste of claim 20, wherein the macromolecular dispersant is polyether, polyester, polyamide or polyorganosiloxane.
22. A solar cell comprising the glass frit composition according to any one of claims 1 to 7 and/or the conductive silver paste according to any one of claims 9 to 21.
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