CN114520065A - Lead-free composite powder for solar cell negative electrode, method for producing the composite powder, and silver paste for solar cell negative electrode - Google Patents
Lead-free composite powder for solar cell negative electrode, method for producing the composite powder, and silver paste for solar cell negative electrode Download PDFInfo
- Publication number
- CN114520065A CN114520065A CN202210315054.1A CN202210315054A CN114520065A CN 114520065 A CN114520065 A CN 114520065A CN 202210315054 A CN202210315054 A CN 202210315054A CN 114520065 A CN114520065 A CN 114520065A
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- Prior art keywords
- silver
- solar cell
- powder
- negative electrode
- lead
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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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a lead-free composite powder for a negative electrode of a solar cell, a method for manufacturing the composite powder and a 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 an 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 IVB group element Ti or Zr. According to the lead-free composite powder for the negative electrode of the solar cell, the glass core component of the lead-free composite powder is specially selected to replace the most common lithium element with sodium element with wider reserves so as to reduce the viscosity of glass and 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 formed on the shell of the composite powder in advance by adopting a coating technology, so that the complex chemical reaction of a silver crystal tunneling layer generated by depending on lead in the sintering process is avoided, and the electrode slurry is easier to achieve lead-free and 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 from the composite powder.
Background
Conventional solar cell structures are used as an external energy source for generating hole-electron pairs of 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 generated by the p-n semiconductor junction and the resulting current is collected by the conductive grid (grid lines) to flow to an external circuit. Conductive pastes (also referred to as inks) are commonly used to form conductive grids or metal contacts. To improve cell efficiency, the cell pieces are typically coated with an antireflective coating, such as silicon nitride, aluminum oxide, or silicon oxide, to promote light absorption. The conductive paste typically contains glass powder due to the insulating properties of the anti-reflective layer, and the anti-reflective layer is dissolved by a chemical reaction during sintering to be brought into contact with the battery sheet substrate.
However, due to the insulating property of glass, the high contact resistance caused by the glass layer remaining between the conductive grid line and the cell substrate is always a difficult point for improving the efficiency of the cell.
The glass frits currently used mainly contain lead and other low-melting components so that they attain a softening point of about 300 to 700 ℃. In the sintering process of the battery, lead and lead-containing substances firstly react with the antireflection coating to generate a lead simple substance, then the lead simple substance and silver powder generate a silver-lead alloy, the alloy phase splitting is carried out along with the temperature cooling, silver crystals with proper size are formed on the surface of the silicon substrate, and the conductive contact is formed. However, due to the inevitable aging and hydrolysis of the fillers of the battery pack, such as EVA, the decomposed acetic acid is very likely to react with lead in the electrode, and the lead is dissolved, thereby causing problems of grid line falling, battery pack failure, and the like.
It has been 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 seriously affects the fluidity of the glass frit during sintering and the formation of silver crystals, so that the addition amount thereof 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 a lead-free composite powder for a negative electrode of a solar cell, a method for manufacturing the composite powder and a 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 a surface of the inorganic powder; the inorganic powder has a composition comprising Te-Na-X-O, wherein X is at least one of Ti or Zr which are elements of group IVB.
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 preparing a lead-free composite powder for a negative electrode of a solar cell, comprising the steps of:
S1: adding an inorganic powder to the silver or silver complex solution, wherein the inorganic powder comprises the components of at least one of IVB group elements Ti or Zr, Te and Na;
S2: and adding a reducing agent to form a silver coating layer on the surface of the inorganic powder.
Preferably, step S1The silver complex solution is prepared in the following manner:
A1: dissolving a silver-containing compound in deionized water in a reactor with stirring;
B1: a compound that can complex with silver is added, thereby obtaining a silver complex solution.
Preferably, step S1The silver complex solution is prepared in the following manner:
A1: dissolving a silver-containing compound in deionized water in a reactor with stirring;
B1: adding a compound that can complex with silver, thereby forming a silver complex;
C1: a base is added to adjust the basicity of the solution, thereby obtaining a silver complex solution.
Preferably, step A1In (b), the silver-containing compound is silver nitrate.
Preferably, in step B1, the compound capable of complexing with silver is ammonia water or ethylenediamine tetraacetic acid.
Preferably, step S1The preparation composition of the inorganic powder comprises the following three powders:
oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powder containing Te element;
② oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powder containing Na element;
③ powders of oxides, peroxides, fluorides, chlorides, hydroxides, nitrates, phosphates, sulfates, chlorates or carbonates containing Ti and/or Zr, elements of group IVB.
Preferably, step S2In the above step, the reducing agent is any one of hydrazine hydrate, hydroxylamine sulfate, formaldehyde, glucose, sucrose and fructose.
Preferably, in step S2Then, the method also comprises a step S3: after silver is deposited on the surface of the inorganic powder, the processes of filtration, washing, drying and pulverization are performed.
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 vehicle, 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: 50-99.5 wt% of conductive silver powder, 0.4-50 wt% of organic carrier and 0.1-15 wt% 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 lead-free composite powder for the negative electrode of the solar cell, the glass core component of the lead-free composite powder is specially selected to replace the most common lithium element with sodium element with wider reserves so as to reduce the viscosity of glass and increase the fluidity and the contact performance, 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 negative electrode of the solar cell, the silver layer is successfully formed on the shell of the composite powder in advance by adopting the coating technology, so that the complex chemical reaction of a silver crystal tunneling layer generated by depending on lead in the sintering process is avoided, and the electrode slurry is easier to achieve lead-free and environment-friendly.
3. According to the preparation method of the lead-free composite powder for the negative electrode of the solar cell, the silver coating technology is adopted to control and improve the final contact performance of the electrode slurry through the content of the silver layer, the design difficulty of the components of the core glass is greatly reduced, and a larger space is provided for improving various comprehensive performances of the electrode slurry, such as acid resistance, ageing resistance and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments and examples, and it should be understood that the described examples are a part of the examples of the present invention, but not all of the examples.
Thus, the following detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present 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 which are elements in IVB group, namely the lead-free composite powder for the negative electrode of the solar battery is formed by coating the surface of the inorganic powder of Te-Na-Ti-0, Te-Na-Zr-O or Te-Na-Ti-Zr-O with a silver coating layer.
In an alternative embodiment, in combination with the first aspect of the present invention, the inorganic powder is any one of glass frit, solid solution, and microcrystalline powder. More preferably, the inorganic powder is glass frit.
In a preferred embodiment in combination with the first aspect of the present invention, the lead-free composite powder for a negative electrode of a solar cell is formed by coating a silver coating layer on the surface of glass frit of Te-Na-Ti-O.
In a preferred embodiment in combination with the first aspect of the present invention, the lead-free composite powder for a negative electrode of a solar cell is formed by coating a silver coating layer on the surface of glass frit of Te — Na — Zr — O.
In an alternative embodiment, in combination with the first aspect of the present invention, the inorganic powder is a Te-Na-X- (M) -O glass powder, wherein X is at least one of Zr or Ti, a group IVB element, and M is any one or more cationic elements other than Te, Na, Ti, Zr, Bi, Li, and Pb, (M) meaning that any one or more cationic elements may or may not be present in the glass powder.
In an alternative embodiment In combination with the first aspect of the invention, the composition of the inorganic powder comprises, In addition to Te and Na, at least one of the group IVB elements Ti or Zr, 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 preparing a lead-free composite powder for a negative electrode of a solar cell, the method comprising the steps of:
S1: adding an inorganic powder to the silver or silver complex solution, wherein the inorganic powder comprises at least one of group IVB elements Ti or Zr, Te and Na;
S2: 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 invention, step S1The silver complex solution may be prepared by:
A1: dissolving a silver-containing compound, which may be any silver salt, preferably silver nitrate, in deionized water with stirring in a reactor;
B1: in step A1On the basis of (A), adding a compound capable of complexing with silverSo as to form a silver complex, wherein the compound capable of being complexed with silver can be organic amine such as ammonia water or ethylenediamine, and can also be Ethylene Diamine Tetraacetic Acid (EDTA), and preferably, the compound capable of being complexed with silver is ammonia water;
C1: in step B1On the basis of (a), a base is added to adjust the basicity of the solution, preferably, the base is sodium hydroxide, thereby obtaining a silver complex solution.
Here, it is worth mentioning that, in the above-described process for preparing the silver complex solution, step C1It is not essential, however, that applicants have found, after numerous experiments, that in step B1On the basis of the method, the silver can be more compact by adding the alkali, 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, comprising a step C1Is a more preferred embodiment of the present invention.
In an alternative embodiment, in combination with the second aspect of the invention, step S1The preparation composition of the inorganic powder comprises the following three powders:
oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powder containing Te element;
② oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powder containing Na element;
③ powders of oxides, peroxides, fluorides, chlorides, hydroxides, nitrates, phosphates, sulfates, chlorates or carbonates containing Ti and/or Zr, elements of group IVB.
For example, when the inorganic powder is an inorganic powder of Te-Na-Ti-O, the preparation composition may be a mixture of three powders: oxide powder containing Te element (e.g. TeO)2Powder), and Na element-containing carbonate powder (such as Na)2CO3Powder), oxide powder containing Ti element (e.g. TiO)2Powder).
In the same way, ifWhen the inorganic powder is Te-Na-Zr-0 inorganic powder, the preparation composition can be a mixture of the following three powders: oxide powder containing Te element (e.g. TeO)2Powder), and Na element-containing carbonate powder (such as Na)2CO3Powder), oxide powder containing Zr element (e.g. ZrO)2Powder).
Further, the inorganic powder can be prepared by the following method:
A2: preparing a mixture comprising the three powders as described above;
B2: heating the powder mixture in air or an oxygen-containing atmosphere to form a melt;
C2: quenching the melt, milling and ball or jet milling the quenched material, and screening the milled material to provide an inorganic powder having a desired particle size.
Wherein, step B2The powder mixture is sintered to a peak temperature of 600-1200 deg.C to form a melt. Step C2The melt is quenched on a stainless steel platen or between counter-rotating stainless steel rollers or with water quenching to form flakes, which can be milled to form a powder. Preferably, the milled inorganic powder has a median particle size (D50) of 0.1 to 3.0 microns.
In an alternative embodiment, in combination with the second aspect of the invention, the preparation composition of the inorganic powder further comprises one or more other metal compounds, suitable other metal compounds including 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、SeO2And CeO2Any one or more of them.
Thus, In the present application, the terms "Te-Na-Ti-O", "Te-Na-Zr-0", "Te-Na-Ti-Zr-O", the composition of which may also comprise other metal oxides, such As oxides comprising any one or more of 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 invention, step S2The reducing agent is any one of hydrazine hydrate, hydroxylamine sulfate, formaldehyde and saccharides (glucose, sucrose or fructose). Preferably, the reducing agent is hydrazine hydrate or sucrose. It is important to select a suitable reducing agent, which is critical to form a uniform silver coating layer on the surface of the inorganic powder, and it has been found through trial and error that the reducing agent described above is effective in forming a silver coating layer on the surface of the inorganic powder, rather than forming a mixture of the inorganic powder and the silver powder particles.
In an alternative embodiment, in combination with the second aspect of the invention, in step S2Then, the method also comprises a step S3: after silver is deposited on the surface of the inorganic powder, the processes of filtration, washing, drying and pulverization are performed.
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 a conductive silver powder, an organic vehicle, and the lead-free composite powder for a negative electrode of a solar cell, wherein the silver paste comprises the following components in percentage by weight based on the total weight of the silver paste for a negative electrode of a solar cell: 50-99.5 wt% of conductive silver powder, 0.4-50 wt% of organic carrier and 0.1-15 wt% 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 vehicle, and the following embodiments can be adopted:
conductive silver powder
In an alternative embodiment, in combination with the third aspect of the present invention, the conductive silver powder is in any one or more of a flake form, a spherical form, a granular form, a crystalline form, a powder form, or other irregular form. Preferably, the conductive silver powder is in the form of spheres.
In an alternative embodiment, in combination with the third aspect of the invention, the conductive silver powder is provided in the form of a colloidal suspension.
In an alternative embodiment, in combination with the third aspect of the present invention, the silver paste for a negative electrode of a solar cell provided by the present invention comprises 80 to 99.5 wt% of conductive silver powder in a spherical form.
In an alternative embodiment, in combination with the third aspect of the present invention, the silver paste for a negative electrode of a solar cell provided by the present invention comprises the conductive silver powder in a 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, and palmitate.
Organic vehicle
In an alternative embodiment, in combination with the third aspect of the present invention, the organic vehicle includes an organic binder, a surface dispersant, a thixotropic agent, and a diluent.
In an alternative embodiment, in combination with the third aspect of the present invention, the organic vehicle is a solution of one or more solvents comprising one or more polymers, wherein the polymers may be selected from the group consisting of ethyl cellulose, ethyl hydroxyethyl cellulose, wood rosin, a mixture of ethyl cellulose and phenolic resins, polymethacrylates of lower alcohols, and monobutyl ether of ethylene glycol monoacetate; the solvent may be a mixture comprising terpenes such as alpha-or beta-terpineol or their mixtures with other solvents such as kerosene, dibutyl phthalate, butyl carbitol acetate, hexylene glycol and alcohols and alcohol esters having a boiling point above 150 ℃.
In an alternative embodiment, in combination with the third aspect of the present invention, the organic vehicle further comprises the following ingredients: 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 epoxidised resinate, isotetradecanol and pentaerythritol ester of hydrogenated rosin.
In combination with the third aspect of the invention, in an alternative embodiment, the organic vehicle comprises a volatile liquid to promote rapid hardening of the solar cell negative electrode silver paste of the invention after application on the substrate.
In combination with the third aspect of the present invention, in an alternative embodiment, the organic carrier may comprise thickeners, stabilizers, surfactants and/or other common additives.
In an alternative embodiment, in combination with the third aspect of the present invention, the organic vehicle can be a plurality of inert viscous materials.
In making the silver paste for a negative electrode of a solar cell of the present invention, the inorganic components of the silver paste for a negative electrode of a solar cell of the present invention can be mixed with an organic vehicle to form a viscous paste having a consistency and rheology suitable for printing. Further, the inorganic components of the silver paste for the negative electrode of the solar cell may be dispersed in the organic vehicle with a suitable 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 the solids, suitable viscosity and thixotropy for screen printing, suitable wettability of the substrate and paste solids, good drying rate, and good sintering characteristics.
The silver paste for the negative electrode of the solar cell can be prepared by the following method:
S1: mixing a proper amount of lead-free composite powder for a solar cell negative electrode, an organic carrier and conductive silver powder to obtain a raw material mixture;
S2: grinding raw materials by a three-roller grinding machineMixing to obtain silver paste;
S3: the viscosity of the silver paste was measured using a brookfield viscometer and appropriate amounts of solvent and resin were added to adjust the paste viscosity to the 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 is applied to the preparation of the solar cell, and the preparation process of the solar cell and the printing process and the sintering process related to the preparation process are introduced below.
In the case of a solar cell production process, it comprises at least the following two process steps:
S1: providing a crystalline silicon solar cell silicon wafer;
S2: 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 prepared by sintering on the front surface of a P-type PERC-SE cell piece, and can also be prepared by sintering on the back surface of an N-type TOPCon cell piece. In the case of a 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 ink-jet printing, screen printing, pad printing, lithography, 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 the sintering process of the electroconductive paste, after the electroconductive paste is applied, the electroconductive 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:
keeping the sintering temperature at about 700-900 ℃, preferably about 730-800 ℃;
and the sintering holding time at the holding temperature is about 1 to 10 seconds.
In an alternative embodiment, a sintering is performed with a hold 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 pastes on the front and back sides of the cell sheet may be performed simultaneously or sequentially. Simultaneous sintering is suitable if the conductive pastes applied to both sides are similar, preferably the same optimal sintering conditions, in which case sintering is preferably performed simultaneously. When sintering is performed sequentially, it is preferable that the back side conductive paste is first applied and sintered, and then the conductive paste is applied onto the front side and sintered.
The following experimental data illustrate the advantageous effects of the embodiments of the present invention compared to the prior art. It is to be noted that, for the sake of convenience, in the following, the "composite powder" is referred to as "lead-free composite powder for a negative electrode of a solar cell", that is, the composite powder, which is referred to as "lead-free composite powder for a negative electrode of a solar cell", will be referred to hereinafter.
Example 1
(1) Preparation of glass powder
Referring to table 1, 100g of glass frit raw materials were weighed, including: 73g of TeO21g of B2O31.6g of SiO22.5g of Na2O, 2.6g of MgO, 1g of Al2O31.3g of WO313.5g of ZnO, 3.5g of TiO2Uniformly mixing the glass powder raw materials, pouring the mixture into a crucible, putting the crucible into a muffle furnace, heating to 1000 ℃, preserving heat for 40 minutes, pouring the molten glass material between counter-rotating stainless steel rollers for quenching, putting the mixture into a ball mill, and performing ball milling for 24 hours to obtain glass powder A with the particle size of 2um2。
(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, and then 10ml of concentrated aqueous ammonia was added to form a transparent solution containing a silver-ammonia complex, followed by addition of 0.5g of sodium hydroxide. 60g of glass powder A are added2400ml of a solution containing 18g of sucrose was added with stirring, and the mixture was stirred for 20 minutes. Washing with deionized water, and drying to obtain composite powder CA containing 10% silver coating layer2。
(3) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder and 30g of composite powder CA were weighed2And 100g of an organic carrier, wherein the organic carrier comprises 46.4g of 2,2, 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 perhydroabietic acid, 26.3g of dimethyl adipate, and 3g of dimethyl glutarate.
Firstly weighing composite powder CA2Putting the organic carrier and the organic carrier into a wide-mouth bottle of a planetary stirrer, adding the conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; followed by mixing with a planetary mixer at 800rpm for 3min to obtain a sample slurry. Grinding the sample slurry for 5 times by using a three-roll grinder, testing that the grinding fineness is less than 10um and the Brookfield viscosity is between 300 and 350Pa.s, and preparing the silver slurry PCA for the negative electrode of the solar cell2。
Example 2
(1) Preparation of glass powder
Referring to table 1, 100g of glass frit raw materials were weighed, including: 73g of TeO21g of B2O31.4g of SiO22.5g of Na2O, MgO 2.6g, Al 1g2O313.5g of ZnO, 5g of ZrO2Uniformly mixing the glass powder raw materials, pouring the mixture into a crucible, putting the crucible into a muffle furnace, heating to 1000 ℃, preserving heat for 40 minutes, pouring the molten glass material between counter-rotating stainless steel rollers for quenching, putting the mixture into a ball mill, and performing ball milling for 24 hours to obtain glass powder A with the particle size of 2um3。
(2) Preparation of composite powder containing 20% silver coating
Referring to Table 2, 500ml of deionized water was added to a beaker and 19.2g of silver nitrate was dissolved with stirring. Then, 20ml of concentrated aqueous ammonia was added to form a transparent solution containing the silver-ammonia complex, and 0.5g of sodium hydroxide was added. 60g of glass powder A are added3400ml of a solution containing 36g of hydrazine hydrate are added with stirring. Stirred for 20 minutes. Washing with deionized water, and drying to obtain composite powder CA containing 20% silver coating layer3。
(3) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder and 30g of composite powder CA were weighed3100g of an organic carrier, wherein the organic carrier comprises 46.4g of 2,2, 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 perhydroabietic acid, 26.3g of dimethyl adipate, and 3g of dimethyl glutarate.
Firstly weighing composite powder CA3Putting the organic carrier and the organic carrier into a wide-mouth bottle of a planetary stirrer, adding the conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; followed by mixing with a planetary mixer at 800rpm for 3min to obtain a sample slurry. Grinding the sample slurry for 5 times by using a three-roll grinder, testing that the grinding fineness is less than 10um and the Brookfield viscosity is between 300 and 350Pa.s, and preparing the silver slurry PCA for the negative electrode of the solar cell3。
Comparative example 1
(1) Preparation of glass powder
Referring to table 1, 100g of glass frit raw materials were weighed, including: 73g of TeO21g of B2O31.6g of SiO21.5g of Li2O, 1.5g of Na2O, 2.6g of MgO, 1g of Al2O34.3g of WO313.5g ZnO, mixing the above glass powder raw materials uniformly, pouring into a crucible, placing into a muffle furnace, heating to 1000 deg.C, keeping the temperature for 40 minutes, pouring the melted glass melt between counter-rotating stainless steel rollers, and quenchingThen putting the mixture into a ball mill for ball milling for 24 hours to prepare glass powder A with the particle size of 2um1。
(2) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder and 30g of glass frit A were weighed1And 100g of an organic carrier, wherein the organic carrier comprises 46.4g of 2,2, 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 perhydroabietic acid, 26.3g of dimethyl adipate, and 3g of dimethyl glutarate.
Firstly, weighing the glass powder A1Putting the organic carrier and the conductive silver powder into a wide-mouth bottle of a planetary stirrer, adding the conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; followed by mixing with a planetary mixer at 800rpm for 3min to obtain a sample slurry. Grinding the sample slurry for 5 times by using a three-roll grinder, testing that the grinding fineness is less than 10um and the Brookfield viscosity is between 300 and 350Pa.s, and preparing the silver slurry PA for the negative electrode of the solar cell1。
Comparative example 2
(1) Preparation of glass powder
The glass frit used in this example was the glass frit A prepared in example 12。
(2) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder and 30g of glass frit A were weighed2And 100g of an organic carrier, wherein the organic carrier comprises 46.4g of 2,2, 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 perhydroabietic acid, 26.3g of dimethyl adipate, and 3g of dimethyl glutarate.
Firstly, weighing the glass powder A2Putting the organic carrier and the organic carrier into a wide-mouth bottle of a planetary stirrer, adding the conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; followed by a planetary mixer at 800rAnd mixing for 3min at the rotating speed of pm to obtain sample slurry. Grinding the sample slurry for 5 times by using a three-roll grinder, testing that the grinding fineness is less than 10um and the Brookfield viscosity is between 300 and 350Pa.s, and preparing the silver slurry PA for the negative electrode of the solar cell2。
Comparative example 3
(1) Preparation of glass powder
The glass frit used in this example is the glass frit A prepared in example 23。
(2) Preparation of silver paste for negative electrode of solar cell
Referring to Table 3, 870g of conductive silver powder and 30g of glass frit A were weighed3And 100g of an organic carrier, wherein the organic carrier comprises 46.4g of 2,2, 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 perhydroabietic acid, 26.3g of dimethyl adipate, and 3g of dimethyl glutarate.
Firstly, weighing the glass powder A3Putting the organic carrier and the organic carrier into a wide-mouth bottle of a planetary stirrer, adding the conductive silver powder into the wide-mouth bottle for three times according to 250g, 250g and 370g, and uniformly stirring by using a scraper; followed by mixing with a planetary mixer at 800rpm for 3min to obtain a sample slurry. Grinding the sample slurry for 5 times by using a three-roll grinder, testing that the grinding fineness is less than 10um and the Brookfield viscosity is between 300 and 350Pa.s, and preparing the silver slurry PA for the negative electrode of the solar cell3。
Table 1 shows the component formulations of the glass frits described in the above examples and comparative examples, wherein glass frit A1Is Te-Na-O component system glass powder, glass powder A2Is Te-Na-Ti-O component system glass powder, glass powder A3Is Te-Na-Zr-O component system glass powder.
Table 2 shows the composition of the composite powder according to the above examples, wherein the composite powder CA2The adopted glass powder is Te-Na-Ti-O component system glass powder, and the silver content in the silver coating layer is 10 percent; composite powder CA3The glass powder is Te-Na-Zr-O component glass powder and silver bag thereofThe silver content in the coating was 20%.
Table 3 shows the composition formulas of the silver pastes for negative electrodes of solar cells described in the above examples and comparative examples, each example and each comparative example including the same contents of the conductive silver powder and the organic vehicle, except for comparative example 1 (PA)1) Adopts glass powder A1Preparation, comparative example 2 (PA)2) Adopts glass powder A2Preparation, comparative example 3 (PA)3) Adopts glass powder A3Preparing; example 1 (PCA)2) Using composite powder CA2Preparation, example 2 (PCA)3) Using composite powder CA3It is worth noting that the conductive silver powders in table 3 are spherical conductive silver powders with oleic acid as a surfactant.
TABLE 1
| Composition (I) | A1Comparative example 1 | A2(example 1, comparative example 2) | A3(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 (I) | CA2(example 1) | CA3(example 2) |
| Glass powder | A2 | A3 |
| Silver coating | 10％ | 20％ |
TABLE 3
| Ingredient (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 vehicle | 10％ | 10％ | 10％ | 10％ | 10％ |
Performance testing
(1) Preparation of the cells used for testing:
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 production of N-type TOPCon solar cell sheets. The production process flow of the N-type TOPCon solar cell is generally divided into the steps of texturing the upper surface of N-type monocrystalline silicon, then forming a boron diffusion layer on the front surface, manufacturing a PN junction and forming a P + layer. And then sequentially forming a tunneling silicon oxide layer and a doped polycrystalline silicon layer on the back surface. And then preparing an antireflection layer on the back surface, and preparing a passivation layer and an antireflection layer on the front surface. And then printing conductive silver paste and silver aluminum paste on the back surface and the front surface by screen printing. The negative electrodes of the solar cells prepared in the above example 1, comparative example 1 and comparative example 2 are printed on the back antireflection layer by using silver paste, and the silver-aluminum paste printed on the front surface can be silver-aluminum paste which can burn through the passivation layer and form point contact at the P + diffusion layer, such as PV3N3 silver-aluminum paste from dupont, and can be other commercially available silver-aluminum paste.
The negative electrodes of the solar cells prepared in example 1, comparative example 1 and comparative example 2 above were screen-printed on the back side (TOPCon side) of the cell using a semi-automatic screen printing machine obtained from the Asys Group, EKRA automation systems Group with silver paste (480 mesh 11um screen diameter, 17um yarn thickness 15um latex thickness, 116 lines of 25um secondary grid and 5 primary grids) using the following screen parameters. A commercially available silver aluminum paste, PV3N3 from dupont, was printed on the P + doped front side of the cell sheet 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. Then, the cell piece was fired in a Centrotherm-300-FF band sintering furnace with the P + doping face up for 1.5 minutes. For example 1, comparative example 1 and comparative example 2, sintering was carried out at a maximum sintering temperature of 750 ℃.
P-type PERC-SE solar cellSheet
The silver pastes for negative electrodes of solar cells prepared in the above example 2, comparative example 1 and comparative example 3 were used for the manufacture of P-type PERC-SE solar cells. The production process flow of the PERC-SE solar cell is generally divided into the steps of 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 through laser, and plating an oxide film on the surface of the silicon wafer subjected to laser heavy doping. And then etching and polishing the back surface, and removing the phosphorosilicate glass on the front surface and the back surface. And annealing the battery piece to perform overall passivation. And finally, depositing a passivation layer and an antireflection film on the surface of the cell, and performing laser grooving on the back surface.
The silver paste for the negative electrode of the solar cell prepared in the above example 2, comparative example 1 and comparative example 3 is printed on the antireflection film and the passivation film on the front surface, and the aluminum paste printed on the back surface can be a non-fire through type aluminum paste product capable of performing fine grid line printing and forming a back surface field, RX (EFX88C) aluminum paste of juxing company can be used, and aluminum paste available in other markets can also be used. The printing process of the back aluminum paste is completed before the battery piece is purchased.
The battery piece has 156x156mm2The size of (d) and the shape of a quasi-square. The paste of the example was screen printed onto the N-doped side of the cell sheet using a semi-automatic screen printer from the Asys Group, EKRA automation systems Group, with the following screen parameters (480 mesh 11um screen gauge, 17um yarn thickness 15um latex thickness, 116 25um secondary grid lines and 5 main grids). After printing the front side, the silicon wafer with the printed pattern was dried in an oven at 150 ℃ for 10 minutes. Then, the substrate was fired in a Centrotherm-300-FF belt sintering furnace with the N-doped side up for 1.5 minutes. For example 2, comparative example 1 and comparative example 3 above, sintering was carried out at a maximum sintering temperature of 750 ℃.
(2) Performance testing
IV test
The solar cell was characterized using a commercial IV tester "cetiSPV-CTL 1" from Halm Elektronik GmbH at 25 ℃ +/-1.0 ℃. Xe arc lamp simulated sunLight, known to have an AM1.5 intensity of 1000W/m at the cell surface2. To make the simulator have this intensity, the lamp is flashed several times in a short time until reaching a plateau monitored by the "PVCTControl 4.313.0" software of the IV tester. The hall IV tester measures current (I) and voltage (V) using a multi-point contact method to determine the IV curve of the battery. All values are automatically determined from the curve by running the software package. As a reference standard, a calibration solar cell obtained from ISE Freiburg and made of the same area size, the same cell sheet material and using the same front side pattern was tested and the data compared to the certified values. At least 5 cells processed in the very same way were measured and the data were resolved by calculating the average of the values. The software PVCTControl 4.313.0 provides values for efficiency, fill factor, short circuit current, series resistance, and open circuit voltage.
Contact resistance
At a temperature of 22 deg.C before measurement+All equipment and materials were equilibrated in an air-conditioned room at 1 ℃. To measure the contact resistance of the fired electrodes on the doped front side layer of silicon solar cells, "GP 4-Test Pro" from the company GP solar GmbH, equipped with the software package "GP-4 Test 1.6.6 Pro" was used. The device estimates the contact resistance by the Transmission Length Method (TLM) using the 4-point measurement principle. To measure the contact resistance, two 1cm wide strips were cut from the cell sheet perpendicular to the printed grid lines of the cell sheet. Each strip was measured for its exact width with an accuracy of 0.05 mm. The width of the fired subline line was measured at 3 different points on the bar with a digital microscope "VHX-600D" from the company Keyence corp, equipped with a wide range zoom lens VH-Z100R. The width was measured 10 times at each point with 2 point measurements. The grating width value is the average of all 30 measurements. The software package calculates the contact resistance using the gate line width, strip width and the distance of the printed gate lines from each other. The measurement current was set to 14 mA. A multi-contact measuring head adapted to contact 6 adjacent grid lines is mounted and in contact with the 6 adjacent grid lines. Measurements were made at 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. All 10 areThe average of the points is taken as the value of the contact resistance.
Acetic acid test
1) Preparation of 3% potassium chloride acetate solution
115g of KCl was weighed into a plastic box and laid flat on the bottom of the box to ensure that no particles larger than 1cm were in the KCl. 194ml of purified water were measured out and added to a plastic box. Weighing 6g of acetic acid, adding the acetic acid into a plastic box, and putting the plastic bottom pad after the acetic acid is shaken uniformly.
2) Preparation before testing
The battery pieces are numbered and IV initial performance characterization is completed before testing, the battery pieces to be tested are inserted into the flower basket in the following mode (placing the spacers) by wearing the PVC gloves, and the accompanying pieces are placed into the two pieces close to the edges. And placing the flower basket in the middle of a plastic box, covering a box cover, fastening, sealing by using a winding film, placing the plastic box with the battery piece to be measured and a fan lead on an electronic scale for weighing, and recording the reading.
3) Testing of
After a power supply of the fan is switched on and the fan is checked to run well, the plastic box is placed in an oven, and after the position of the flower basket is detected to be not displaced again, the plastic box is insulated in the oven at 85 ℃ for 20 hours; and (4) closing the fan, taking out the plastic box, weighing the weight record data after the plastic box is cooled to room temperature, taking the PVC gloves on the plastic box, taking out the flower basket, and taking out the battery piece to be tested to test the performance of the IV.
Test results
Test example 1
According to the method, the silver paste PA for the negative electrode of the solar cell prepared in the comparative example 1 is added1Silver paste PA for negative electrode of solar cell prepared in comparative example 22And silver paste PCA for negative electrode of solar cell prepared in example 12Printing on the back (N surface) of an N-type TOPCon battery piece, drying and sintering to obtain a crystalline silicon solar battery, testing the electrical performance, averaging the results, and listing the results in Table 4-1, wherein Uoc refers to an open-circuit voltage value; FF refers to the fill factor value; rc means contact resistance; ncell refers to the conversion efficiency value.
From Table 4-1, it can be seen that silver Paste (PCA) for negative electrode of solar cell described in example 12) Prepared ofThe conversion efficiency of the solar cell is obviously higher than that of the silver Paste (PA) for the negative electrode of the solar cell in the comparative example 22) The contact resistance Rc of the solar cell prepared is better than that of the solar cell prepared, and the silver Paste (PCA) for the negative electrode of the solar cell described in example 12) Conversion efficiency of the solar cell obtained was compared with silver Paste (PA) for negative electrode of solar cell described in comparative example 11) The prepared solar cell is flat. This result illustrates comparison to comparative example 1 (PA)1) Though comparative example 2 (PA)2) It is shown that the addition of Ti element increases the contact resistance of the glass powder, but the detection data shown in example 1 indicate that the silver coating process enables the composite powder using Te-Na-Ti-O to significantly reduce the contact resistance and improve the performance of the N-type TOPCon cell, compared with the conventional Te-Na-O glass powder sample (PA-Na-O glass powder sample)1) Achieving equivalent overall performance.
Further, the manufactured solar cell was subjected to an acetic acid test, and then the electrical properties thereof were tested again, and the results were averaged and listed in table 4-2, wherein Uoc means an open circuit voltage value; FF refers to the fill factor value; ncell refers to a conversion efficiency value, Δ Ncell refers to a conversion efficiency value with respect to gain or attenuation, Δ Ncell is a positive value when conversion efficiency is with respect to gain, and Δ Ncell is a negative value when conversion efficiency is with respect to attenuation. The formula for 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 tables 4-2, although the silver Paste (PA) for the negative electrode of the solar cell described in comparative example 11) The prepared solar cell also has higher conversion efficiency, but after the acetic acid experiment, only the silver Paste (PCA) for the negative electrode of the solar cell described in example 12) The conversion efficiency value of the prepared solar cell relative attenuation is less than 5%. This result indicates that the addition of Ti element can significantly improve the acid resistance of the electrode slurry. Obviously, the composite powder of Te-Na-Ti-O 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(s) | 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 experiment)
| Sample(s) | 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 method, the silver paste PA for the negative electrode of the solar cell prepared in the comparative example 1 is added1Silver paste PA for negative electrode of solar cell prepared in comparative example 33And silver paste PCA for negative electrode of solar cell prepared in example 23Printing on the front surface (N surface) of a P-type PERC-SE cell, drying, and sintering to obtain crystalline silicon solar cellThe solar cell was tested for electrical performance, and the results were averaged and are listed in table 5-1, wherein Uoc means open circuit voltage value; FF refers to the fill factor value; rc means contact resistance; ncell refers to the conversion efficiency value.
As can be seen from Table 5-1, silver Paste (PCA) for negative electrode of solar cell described in example 23) The conversion efficiency of the prepared solar cell is obviously higher than that of the silver Paste (PA) for the negative electrode of the solar cell in the comparative example 33) The contact resistance Rc of the solar cell prepared is better than that of the solar cell prepared, and the silver Paste (PCA) for the negative electrode of the solar cell described in example 22) Conversion efficiency of the prepared solar cell and silver Paste (PA) for negative electrode of solar cell described in comparative example 11) The conversion efficiency of the prepared solar cell is even. This result illustrates comparison to comparative example 1 (PA)1) Though comparative example 3 (PA)3) The contact resistance of the glass powder is increased due to the addition of Zr element, but the detection data shown in example 2 show that the silver coating process enables the Te-Na-Zr-O composite powder to be used for remarkably reducing the contact resistance and improving the performance of the P-type PERC-SE battery piece, and compared with the conventional Te-Na-O glass powder sample (PA-Na-O glass powder sample)1) Achieving equivalent overall performance.
Further, the manufactured solar cell was subjected to an acetic acid test, and then the electrical properties thereof were tested again, and the results were averaged and listed in table 5-2, wherein Uoc means an open circuit voltage value; FF refers to the fill factor value; ncell refers to a conversion efficiency value, Δ Ncell refers to a conversion efficiency value with respect to gain or attenuation, Δ Ncell is a positive value when conversion efficiency is with respect to gain, and Δ Ncell is a negative value when conversion efficiency is with respect to attenuation. The formula for 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 tables 5-2, although the silver Paste (PA) for the negative electrode of the solar cell described in comparative example 11) The prepared solar cell also has high conversion efficiency, but after the acetic acid experiment, only the silver paste for the negative electrode of the solar cell (PCA) described in example 22) The conversion efficiency value of the prepared solar cell relative attenuation is less than 5%. This result indicates ZrThe addition of the elements can obviously improve the acid resistance of the electrode slurry. 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(s) | 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 experiment)
| Sample(s) | 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 embodiments of the present invention have been described, it is clear that various changes and modifications can be made by workers in the field without departing from the technical spirit of the present invention.
Claims (11)
1. 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 has a composition comprising Te-Na-X-O, wherein X is at least one of Ti or Zr which are elements of group IVB.
2. The lead-free composite powder for a negative electrode of a solar cell according to claim 1, wherein the inorganic powder is any one of glass powder, solid solution, and microcrystal powder.
3. A preparation method of lead-free composite powder for a negative electrode of a solar cell is characterized by comprising the following steps:
S1: adding an inorganic powder to the silver or silver complex solution, the inorganic powder having a composition comprising at least one of group IVB elements Ti or Zr, and Te and Na;
S2: and adding a reducing agent to form a silver coating layer on the surface of the inorganic powder.
4. The method for producing the lead-free composite powder for a negative electrode of a solar cell according to claim 3, characterized in that step S1The silver complex solution is prepared in the following manner:
A1: dissolving a silver-containing compound in deionized water in a reactor with stirring;
B1: a compound that can complex with silver is added, thereby obtaining a silver complex solution.
5. The method for producing a lead-free composite powder for a negative electrode of a solar cell according to claim 3, characterized in that step S1In (A), theThe silver complex solution was prepared as follows:
A1: dissolving a silver-containing compound in deionized water in a reactor with stirring;
B1: adding a compound that can complex with silver, thereby forming a silver complex;
C1: a base is added to adjust the basicity of the solution, thereby obtaining a silver complex solution.
6. The method for producing a lead-free composite powder for a negative electrode of a solar cell according to claim 4 or 5, characterized in that step A1In (b), the silver-containing compound is silver nitrate.
7. The method for producing a lead-free composite powder for a negative electrode of a solar cell according to claim 4 or 5, characterized in that step B1The compound capable of being complexed with silver is ammonia water, ethylenediamine or ethylenediamine tetraacetic acid.
8. The method for producing the lead-free composite powder for a negative electrode of a solar cell according to claim 3, characterized in that step S1The preparation composition of the inorganic powder comprises the following three powders:
oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powder containing Te element;
② oxide, peroxide, fluoride, chloride, hydroxide, nitrate, phosphate, sulfate, chlorate or carbonate powder containing Na element;
③ powders of oxides, peroxides, fluorides, chlorides, hydroxides, nitrates, phosphates, sulfates, chlorates or carbonates containing Ti and/or Zr, elements of group IVB.
9. The method for producing the lead-free composite powder for a negative electrode of a solar cell according to claim 3, characterized in thatStep S2In the above step, the reducing agent is any one of hydrazine hydrate, hydroxylamine sulfate, formaldehyde, glucose, sucrose and fructose.
10. The method for producing a lead-free composite powder for a negative electrode of a solar cell according to claim 3, characterized in that in step S2Then, the method also comprises a step S3: after silver is deposited on the surface of the inorganic powder, the processes of filtration, washing, drying and pulverization are performed.
11. A silver paste for a negative electrode of a solar cell, comprising a conductive silver powder, an organic vehicle, and the lead-free composite powder for a negative electrode of a solar cell according to any one of claims 1 to 2;
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: 50-99.5 wt% of conductive silver powder, 0.4-50 wt% of organic carrier and 0.1-15 wt% of lead-free composite powder for a negative electrode of a solar cell.
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