CN106229026B - Alloy silver powder and preparation method thereof and solar energy electrocondution slurry prepared therefrom - Google Patents
Alloy silver powder and preparation method thereof and solar energy electrocondution slurry prepared therefrom Download PDFInfo
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- CN106229026B CN106229026B CN201610545278.6A CN201610545278A CN106229026B CN 106229026 B CN106229026 B CN 106229026B CN 201610545278 A CN201610545278 A CN 201610545278A CN 106229026 B CN106229026 B CN 106229026B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 62
- 239000000956 alloy Substances 0.000 title claims abstract description 62
- 239000002002 slurry Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- 239000010946 fine silver Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000010944 silver (metal) Substances 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 16
- 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 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- 229940096017 silver fluoride Drugs 0.000 claims description 4
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 229960001516 silver nitrate Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- -1 lauryl alcohol ester Chemical class 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 31
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 abstract description 15
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 abstract description 15
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 abstract description 15
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 229910000679 solder Inorganic materials 0.000 abstract description 5
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- 230000009466 transformation Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 235000008216 herbs Nutrition 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000000967 suction filtration Methods 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- 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
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
Abstract
The invention discloses a kind of alloy silver powder and preparation method thereof and solar energy electrocondution slurries prepared therefrom, the alloy silver powder is made of Ag and one or more metals in Au, Pd, Cu, Ni, Al, Mn, Mg and Bi, one or more contents in wherein described Au, Pd, Cu, Ni, Al, Mn, Mg and Bi are 0.1 10wt%, remaining is silver；The alloy silver powder is prepared using liquid phase chemical reduction alloyage；The solar energy electrocondution slurry includes fine silver powder, alloy silver powder, unorganic glass and the organic carrier, the parts by weight of the fine silver powder are 50 85wt%, the parts by weight of the alloy silver powder are 5 40wt%, the parts by weight of the unorganic glass powder are 1 10wt%, and the parts by weight of the organic carrier are 5 10wt%.The alloy silver powder of the present invention can make solar energy electrocondution slurry prepared therefrom at a relatively low sintering temperature, the solder attachment power of higher battery conversion efficiency, electrode of solar battery be obtained, particularly suitable for PERC solar cell sizes.
Description
Technical field
The present invention relates to technical field of solar batteries, more particularly to a kind of preparation method of alloy silver powder is used for PERC
Solar cell conductive paste.
Background technology
It is prepared currently, PERC silver paste of solar cells material are mostly used fine silver powder, the silver paste of solar cells prepared with fine silver powder
Material, sintering temperature height (900~930 DEG C), easily causes high-temperature damage to solar cell, influences battery conversion efficiency.Furthermore too
The phenomenon that positive energy welding battery electrode will produce silver ion migration under high current access, in silver electrode, electrode of solar battery
Adhesive force is gradually reduced with the extension of time, eventually forms open circuit.
Invention content
The object of the present invention is to provide a kind of alloy silver powder and preparation method thereof and solar energy electrocondution slurry prepared therefrom,
To reduce the high temperature sintering temperature of solar energy electrocondution slurry, harmful effect of the high temperature to solar cell is reduced, battery is improved
Transfer efficiency, and improve the solder attachment power of electrode of solar battery.
Technical scheme is as follows：
A kind of alloy silver powder, the alloy silver powder by Ag with it is one or more in Au, Pd, Cu, Ni, Al, Mn, Mg and Bi
Metal forms, based on the total weight of the alloy silver powder, one kind or more in described Au, Pd, Cu, Ni, Al, Mn, Mg and Bi
The content of kind is 0.1-10wt%, remaining is silver.Preferably, one kind or more in described Au, Pd, Cu, Ni, Al, Mn, Mg and Bi
The content of kind is 0.5-5%.It is further preferred that one or more in described Au, Pd, Cu, Ni, Al, Mn, Mg and Bi contain
Amount is 0.8-1.7%.
Preferably, the D50 of the laser particle size of the alloy silver powder particles be 1.0 μm to 5.0 μm, tap density be 3.5~
6.5g/cm3, specific surface area is 0.2~0.5m2/g.Alloy silver powder particles with above-mentioned parameter, which can be good at meeting, to be prepared too
The requirement of positive energy electrocondution slurry.
A kind of preparation method of above-mentioned alloy silver powder, includes the following steps：
A, acid silver salt solution is prepared, the silver salt is selected from one kind or several of silver nitrate, silver fluoride, silver acetate
Kind, wherein silver salt concentrations control is in 0.5~2mol/L；
B, a kind of the water-soluble of acid metal salt including at least Au, Pd, Cu, Ni, Al, Mn, Mg, Bi element is prepared
Liquid, the metal salt are selected from the water soluble metallic compound containing the crystallization water or nodeless mesh water, and wherein metal salt concentrations control exists
0.1~1.0mol/L；
C, mixed solution is prepared, the mixed solution is that reducing agent and surface dispersant are dissolved in deionized water respectively
In, it is uniformly mixed；
D, by the silver salt solution of the acidity with it is described containing at least one of Au, Pd, Cu, Ni, Al, Mn, Mg, Bi salt
Aqueous solution and the mixed solution are uniformly mixed within the time no more than 20 seconds, and the pH for adjusting reaction solution is held 3~6
Continuous stirring and ultrasound 5-10min, detach alloy silver powder particle obtained in final mixed solution and are such as taken out by depressurizing
Filter method, cleaning and drying obtain the particle of the alloy silver powder.Wherein cleaning can be that deionized water is cleaned, and drying can be
Vacuum drying, but cleaning and dry above-mentioned enumerate are not intended as limiting.
Preferably, the reducing agent is selected from the glucose, ascorbic acid and their mixing being dissolved in deionized water
Object, the surface dispersant are selected from polyethylene glycol, gum arabic, oleic acid and their any mixture.
The alloy silver powder is prepared using liquid phase chemical reduction alloyage, and the method that liquid phase chemical reduction prepares alloy has
The features such as process conditions are easily controllable, the alloyed powder narrow particle size distribution of reduction, good dispersion.
A kind of solar energy electrocondution slurry, including fine silver powder, above-mentioned alloy silver powder, unorganic glass and organic carrier, it is described
The parts by weight of fine silver powder are 50-85%, and the parts by weight of the alloy silver powder are 5-40%, the weight of the unorganic glass powder
Number is 1-10%, and the parts by weight of the organic carrier are 5-10%.Present invention alloy silver powder is prepared with fine silver powder compounding
Solar energy electrocondution slurry reduces the sintering temperature of solar energy electrocondution slurry using the characteristic of alloy silver powder, reaches and improves battery turn
It changes efficiency and improves the purpose of the solder attachment power of electrode.
Preferably, the alloy silver powder particle shape is spherical or spherical, and the D50 of granular laser particle size is 1.0 μm
To 5.0 μm, tap density is 3.5~6.5g/cm3, specific surface area is 0.2~0.5m2/g.Alloy silver powder with above-mentioned parameter
Particle can be good at the requirement that satisfaction prepares solar energy electrocondution slurry.
In a specific embodiment of the present invention, the unorganic glass be Bi-B-Si, Te-Bi-B system glass one kind or
Multiple combinations, the glass transition temperature of the unorganic glass between 200-500 DEG C, the D50 of granular laser particle size be 1.0 μm extremely
Between 2.0 μm.
In a specific embodiment of the present invention, the organic carrier is made of solvent, resin and dispersant, wherein described
Solvent is butyl carbitol, butyl carbitol acetate, one kind in lauryl alcohol ester and their any mixture, the resin
For one kind and their mixture in ethyl cellulose, acrylic resin, the dispersant is Span 85, oleic acid, stearic acid
One kind and their any mixture.
A kind of preparation method of above-mentioned solar energy electrocondution slurry, by alloy silver powder, fine silver powder, glass powder, organic carrier
Stir evenly to be placed on three-roller and roll, when its fineness is such as 10-14 μm with the fineness that Hegman grind gage measures to get to
The solar energy electrocondution slurry.The solar energy electrocondution slurry is conductive slurry for front electrode of solar battery.
Compared with prior art, beneficial effects of the present invention are as follows：
First, the present invention provides a kind of alloy silver powder and preparation method thereof, are prepared using liquid phase chemical reduction alloyage
Alloy silver powder metallic silver activity is improved by way of silver alloy, and it is conductive by the way that solar energy is added in the alloy silver powder
In slurry, reduce electrocondution slurry in PERC solar cell sintering processes from sintering temperature, alloy using the present invention
Slurry prepared by silver powder can make PERC solar cell sintering temperatures reduce by 20~50 DEG C, thus reduce high temperature to PERC
The influence of solar cell, and improve the transformation efficiency of battery；
Second, alloy silver powder of the invention also improves the solder attachment power of the electrode of solar battery thus prepared, closes
Metal powder can effectively reduce migration of the silver ion under high current, to extend the service life of solar cell.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Specific implementation mode
The present invention provides a kind of alloy silver powder.Since the sintering activity of fine silver powder is low, and silver point is high, and silver-colored is molten
Point temperature is 960.8 DEG C, easily causes high-temperature damage to PERC solar cells, influences battery conversion efficiency.The alloy of the present invention
Silver powder improves metallic silver activity by way of silver alloy, and reduces electrocondution slurry in PERC solar cell sintering processes
From sintering temperature, avoid causing high-temperature damage to PERC solar cells.The alloy approach of the alloy silver powder uses liquid phase
Reduction alloyage is learned, different ionizable metal salts is added in silver powder reduction process and is reduced into alloy silver powder together.
The present invention also provides a kind of solar energy electrocondution slurry containing above-mentioned alloy silver powder, the PERC solar cell conductives
The preparation method of each raw material of slurry and the electrocondution slurry is as follows：
1. glass powder, preparation method thereof：After glass dust raw material is placed in 800-1300 DEG C of Muffle furnace to complete melt, heat preservation
0.5-2h is poured on water quenching on stainless steel roller and rolls flakiness, then it is 0.1-2 μm to be milled to granularity D50.
2. organic carrier preparation method：Organic carrier each component is pre-mixed in a reservoir, then in 70-95 DEG C of water-bath
In until keeping the temperature 2-4h after completely fused, 200 mesh screen postcoolings of filtering are spare.
3. silver paste preparation method：Alloy silver powder, fine silver powder, glass powder, organic carrier are stirred evenly and be placed on three-roller
On roll, measured when fineness is 10-14 μm to get to conductive slurry for front electrode of solar battery with Hegman grind gage.
Battery preparation method is：Slurry obtained above is printed onto plated film system respectively using Bacinni screen processes press
On suede polysilicon chip front, after the sintering of infrared Fast Sintering stove, solar battery sheet is made.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit protection scope of the present invention.Technical staff is according to the improvement of the invention made and tune in practical applications
It is whole, still fall within protection scope of the present invention.
Embodiment
The preparation method of the alloy silver powder of the present embodiment is as follows：
A, acid silver salt solution is prepared, the silver salt is selected from one kind or several of silver nitrate, silver fluoride, silver acetate
Kind, wherein silver salt concentrations control is in 0.5~2mol/L；
B, the water-soluble of the acid metal salt for including at least a kind of element in Au, Pd, Cu, Ni, Al, Mn, Mg, Bi is prepared
Liquid, the metal salt are selected from the water soluble metallic compound containing the crystallization water or nodeless mesh water, wherein aqueous metal salt concentration
Control is in 0.1~1.0mol/L；
C, mixed solution is prepared, the mixed solution is that reducing agent and surface dispersant are dissolved in deionized water respectively
In, it is uniformly mixed；
D, the silver salt solution of the acidity is contained at least one of Au, Pd, Cu, Ni, Al, Mn, Mg, Bi metals with described
The aqueous solution of salt and the mixed solution are uniformly mixed within the time no more than 20 seconds, and adjust the pH of reaction solution 3~
6, it is lasting to stir simultaneously ultrasound 5-10min, decompression suction filtration, cleaning are carried out to alloy silver powder particle obtained in final mixed solution
And drying, obtain the particle of the alloy silver powder.
The preparation embodiment of electrocondution slurry is as follows in the present embodiment：
Embodiment 1
Weigh prepared Ag/Bi alloyed powders 10g (wherein Bi contents are 1.0%-1.3% by mass percentage), fine silver
Powder 80g, unorganic glass powder Bi-B-Si series 2.0g, organic carrier 8g is pre-mixed in a mixer, then mixed on three-roller
Conjunction rolls, and obtains positive conductive silver slurry.
Embodiment 2
Weigh prepared Ag/Ni alloyed powders 20g (wherein Ni contents are 1.5%-1.7% by mass percentage), fine silver
Powder 70g, unorganic glass powder Te-Bi-B series 2.0g, organic carrier 8g is pre-mixed in a mixer, then mixed on three-roller
Conjunction rolls, and obtains positive conductive silver slurry.
Embodiment 3
Weigh prepared Ag/Al alloyed powders 5g (wherein Al content is 1.2%-1.4% by mass percentage), fine silver powder
85g, unorganic glass powder Te-Bi-B series 2.0g, organic carrier 8g are pre-mixed, are then mixed on three-roller in a mixer
It rolls, obtains positive conductive silver slurry.
Embodiment 4
Weighing prepared Ag/Cu/Ni alloyed powders 10g, (wherein Cu/Ni contents are respectively 0.8%- by mass percentage
1.0%), fine silver powder 80g, unorganic glass powder Te-Bi-B series 2.0g, organic carrier 8g are pre-mixed, then exist in a mixer
Mixing rolls on three-roller, obtains positive conductive silver slurry.
Embodiment 5
Prepared Ag/Pd/Ni alloyed powder 15g are weighed, (wherein Pd contents are 0.3%-0.5%, Ni by mass percentage
Content is 0.8%-1.0%).Fine silver powder 80g, unorganic glass powder Te-Bi-B series 2.0g, organic carrier 8g, in a mixer
Premixing, then mixes on three-roller and rolls, obtain positive conductive silver slurry.
Comparative example 1
Weigh fine silver powder 90g, unorganic glass powder Te-Bi-B series 2.0g, organic phase carrier 8g are premixed in a mixer
It closes, then mixes and roll on three-roller, obtain positive conductive silver slurry.
Sintering process 1# battery performance test methods are as follows：The silicon chip after making herbs into wool, diffusion, PECVD is taken, is used
Bacinni screen processes press are respectively printed onto slurry on the polysilicon chip of plated film making herbs into wool front, use the infrared burnings of Despatch
Freezing of a furnace, according to the parameter setting sintering temperature of sintering process 1# shown in the following table 1, solar cell is made in sintering.
Table 1 (sintering temperature)
Its series resistance Rs, leakage current Irev1, fill factor FF, transformation efficiency Eff and welding is measured after sintering to draw
Power, result are as shown in table 2 below.
Wherein, series resistance Rs, fill factor FF, leakage current Irev1, transformation efficiency Eff and stripping electrode intensity
Definition and detection method, are described later in detail and report in document disclosed in related solar cell.
Table 2 (uses sintering process 1#)
Sintering process 2# battery performance test methods are as follows：Take making herbs into wool, diffusion, PECVD, the PERC for making back of the body passivation
Solar silicon wafers are respectively printed onto slurry on the polysilicon chip of plated film making herbs into wool front using Bacinni screen processes press, use
Despatch infrared sintering furnaces, according to the parameter setting sintering temperature of sintering process 2# shown in table 1, PERC solar energy is made in sintering
Battery.
Its series resistance Rs, leakage current Irev1, fill factor FF, transformation efficiency Eff and welding is measured after sintering to draw
Power, result are as shown in table 3 below.
Wherein, series resistance Rs, fill factor FF, leakage current Irev1, transformation efficiency Eff and stripping electrode intensity
Definition and detection method, are described later in detail and report in document disclosed in related solar cell.
Table 3 (uses sintering process 2#)
As seen from Table 3, the embodiment of Ag/Bi, Ag/Ni, Ag/Al, Ag/Cu/Ni, Ag/Pd/Ni are reduced in PERC batteries
After sintering temperature, properties Rs, Irev1, FF, Eff and pulling force are compared with comparative example 1 based on embodiment in table 2 compared to having
Certain raising illustrates that the alloy silver powder system of the present invention is more suitably applied to PERC batteries, is suitble to lower sintering temperature,
Also preferable Rs, Irev1, FF, Eff and pulling force characteristic can be obtained under lower sintering temperature.Using solution phase chemical reduction system
Standby alloy silver powder, and the electrocondution slurry thus prepared, reduce solar cell sintering temperature, relatively low in PERC batteries
Sintering temperature under the obtained contact resistance Rs of battery reduce, to improve FF, and then improve the transfer efficiency of battery
Eff；And improve the solder attachment power of electrode.
Under the introduction of the present invention and above-described embodiment, those skilled in the art are easy to it is envisioned that cited by the present invention
Or each raw material enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (10)
1. a kind of alloy silver powder for solar energy electrocondution slurry, which is characterized in that the alloy silver powder by Ag and Au, Pd, Cu,
One or more metals composition in Ni, Al, Mn, Mg and Bi, based on the total weight of the alloy silver powder, the Au, Pd,
One or more contents in Cu, Ni, Al, Mn, Mg and Bi are 0.1-10 wt%, remaining is silver；Of the alloy silver powder
The laser particle size D50 of grain is 1.0 μm to 2.0 μm；
The alloy silver powder is prepared by the following method：
A, acid silver salt solution is prepared, the silver salt is selected from the one or more of silver nitrate, silver fluoride, silver acetate,
Middle silver salt concentrations control is in 0.5 ~ 2mol/L；
B, a kind of aqueous solution of acid metal salt including at least Au, Pd, Cu, Ni, Al, Mn, Mg, Bi element, institute are prepared
State metal salt and be selected from the water soluble metallic compound containing the crystallization water or nodeless mesh water, wherein metal salt concentrations control 0.1 ~
1.0mol/L；
C, mixed solution is prepared, the mixed solution is to be dissolved in reducing agent and surface dispersant in deionized water respectively, is stirred
It mixes uniformly mixed；
D, by the silver salt solution of the acidity and the water containing at least one of Au, Pd, Cu, Ni, Al, Mn, Mg, Bi salt
Solution and the mixed solution are uniformly mixed within the time no more than 20 seconds, and the pH for adjusting reaction solution is persistently stirred 3 ~ 6
Simultaneously ultrasound 5-10min is mixed, alloy silver powder particle obtained in final mixed solution is detached, cleaned and dried, is obtained
The particle of the alloy silver powder.
2. alloy silver powder as described in claim 1, which is characterized in that one in described Au, Pd, Cu, Ni, Al, Mn, Mg and Bi
Kind or a variety of contents are 0.5-5%.
3. alloy silver powder as described in claim 1, which is characterized in that one in described Au, Pd, Cu, Ni, Al, Mn, Mg and Bi
Kind or a variety of contents are 0.8-1.7%.
4. alloy silver powder as described in claim 1, which is characterized in that the tap density of the particle of the alloy silver powder be 4.5 ~
6.5 g/cm3, specific surface area is 0.2 ~ 0.5 m2/g。
5. any alloy silver powder preparation method for solar energy electrocondution slurry, feature in a kind of claim 1-4
It is, includes the following steps：
A, acid silver salt solution is prepared, the silver salt is selected from the one or more of silver nitrate, silver fluoride, silver acetate,
Middle silver salt concentrations control is in 0.5 ~ 2mol/L；
B, a kind of aqueous solution of acid metal salt including at least Au, Pd, Cu, Ni, Al, Mn, Mg, Bi element, institute are prepared
State metal salt and be selected from the water soluble metallic compound containing the crystallization water or nodeless mesh water, wherein metal salt concentrations control 0.1 ~
1.0mol/L；
C, mixed solution is prepared, the mixed solution is to be dissolved in reducing agent and surface dispersant in deionized water respectively, is stirred
It mixes uniformly mixed；
D, by the silver salt solution of the acidity and the water containing at least one of Au, Pd, Cu, Ni, Al, Mn, Mg, Bi salt
Solution and the mixed solution are uniformly mixed within the time no more than 20 seconds, and the pH for adjusting reaction solution is persistently stirred 3 ~ 6
Simultaneously ultrasound 5-10min is mixed, alloy silver powder particle obtained in final mixed solution is detached, cleaned and dried, is obtained
The particle of the alloy silver powder.
6. a kind of solar energy electrocondution slurry, which is characterized in that including any alloy silver in fine silver powder, claim 1-4
The parts by weight of powder, unorganic glass and organic carrier, the fine silver powder are 50-85%, and the parts by weight of the alloy silver powder are 5-
40%, the parts by weight of the unorganic glass powder are 1-10%, and the parts by weight of the organic carrier are 5-10%.
7. solar energy electrocondution slurry as claimed in claim 6, which is characterized in that the alloy silver powder particle shape be it is spherical or
Spherical, the D50 of granular laser particle size is 1.0 μm to 2.0 μm, and tap density is 4.5 ~ 6.5 g/cm3, specific surface area is
0.2~0.5 m2/g。
8. solar energy electrocondution slurry as claimed in claim 6, which is characterized in that the unorganic glass is Bi-B-Si, Te-Bi-
One or more combinations of B system glass, the glass transition temperature of the unorganic glass is between 200-500 DEG C, particle laser
Between the D50 of granularity is 1.0 μm to 2.0 μm.
9. solar energy electrocondution slurry as claimed in claim 6, which is characterized in that the organic carrier is by solvent, resin and divides
Powder form, wherein the solvent be butyl carbitol, butyl carbitol acetate, one kind in lauryl alcohol ester and they
Any mixture, the resin are ethyl cellulose, one kind in acrylic resin and their mixture, and the dispersant is
Span 85, oleic acid, stearic a kind of and their any mixture.
10. a kind of preparation method of the solar energy electrocondution slurry described in claim 6, it is characterised in that；By fine silver powder, alloy silver
Powder, glass powder, organic carrier are stirred evenly to be placed on three-roller and be rolled, when its fineness be 10-14 μm when to get to it is described too
Positive energy electrocondution slurry.
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| CN112071468B (en) * | 2020-09-11 | 2022-11-22 | 南京苏煜新能源科技有限公司 | Conductive slurry for HJT battery and preparation method thereof |
| CN114530280A (en) * | 2022-04-21 | 2022-05-24 | 西安宏星电子浆料科技股份有限公司 | Low-cost thick-film conductor paste |
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| US20090211626A1 (en) * | 2008-02-26 | 2009-08-27 | Hideki Akimoto | Conductive paste and grid electrode for silicon solar cells |
| US20110180139A1 (en) * | 2010-01-25 | 2011-07-28 | Hitachi Chemical Company, Ltd. | Paste composition for electrode and photovoltaic cell |
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