CN105858623A - Preparation method for silver tellurite, crystalline solar cell positive pole silver paste and preparation method therefor - Google Patents
Preparation method for silver tellurite, crystalline solar cell positive pole silver paste and preparation method therefor Download PDFInfo
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- CN105858623A CN105858623A CN201610191735.6A CN201610191735A CN105858623A CN 105858623 A CN105858623 A CN 105858623A CN 201610191735 A CN201610191735 A CN 201610191735A CN 105858623 A CN105858623 A CN 105858623A
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- Prior art keywords
- silver
- preparation
- tellurous acid
- tellurite
- tellurous
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 116
- 239000004332 silver Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 title claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- SITVSCPRJNYAGV-UHFFFAOYSA-N tellurous acid Chemical compound O[Te](O)=O SITVSCPRJNYAGV-UHFFFAOYSA-N 0.000 claims description 63
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000428 dust Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 8
- 239000001856 Ethyl cellulose Substances 0.000 claims description 8
- 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 8
- -1 alcohol ester Chemical class 0.000 claims description 8
- 229920001249 ethyl cellulose Polymers 0.000 claims description 8
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 8
- 235000011837 pasties Nutrition 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 239000013008 thixotropic agent Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 229910052714 tellurium Inorganic materials 0.000 claims description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229940083025 silver preparation Drugs 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 10
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910004273 TeO3 Inorganic materials 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229910017906 NH3H2O Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910017611 Ag(NH3)2 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/008—Salts of oxyacids of selenium or tellurium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a preparation method for preparing silver tellurite through subjecting a silver ammonia solution to a reaction with tellurite as well as provides novel crystalline solar cell positive pole silver paste by means of directly adding the silver tellurite prepared by the method and improved inorganic glass powder based on original raw materials and a method for preparing the crystalline solar cell positive pole silver paste. According to the invention, the design is ingenious; and through directly adding the silver tellurite and the high-selection-ratio corrosive inorganic glass powder, conditions are created for ohmic contact for silver and silicon, meanwhile, high-temperature conditions required for precipitating adequate silver tellurite from the glass powder are avoided, and the integrity of PN junctions cannot be affected by high temperatures, so that the contradiction is solved, and the window for sintering temperatures is widened.
Description
Technical field
The invention belongs to area of solar cell, be specifically related to the preparation method of a kind of tellurous acid silver, bag
Crystal solaode anode silver paste and the preparation method of silver paste containing above-mentioned tellurous acid silver.
Background technology
Solar energy is a kind of inexhaustible clean type energy, and solar electrical energy generation is direct
Solar radiant energy is converted to electric energy, be minimum to the conversion links of solar energy in all clean energy resourcies,
Utilize the most direct mode.
At present, crystal silicon solar energy battery is main solaode, and crystal silicon solar batteries is just
Face silver slurry, as the anelectrode of cell piece, is the important component part of cell piece, and its composition includes organic
Carrier, argentum powder and unorganic glass.Weigh at present the standard of silver slurry performance have adhesive force, series resistance,
Parallel resistance, printing performance etc..
The mechanism of action of cell piece positive silver paste is now: in sintering process, and first unorganic glass is heated
Decompose, by glass, the corrosion of silicon nitride and silicon penetrated silicon nitride, but penetrating silicon nitride
The most also to obtain the Ohmic contact of silver silicon.
The integrity of PN junction the most also should be kept not to be damaged, to ensure the height of cell piece as far as possible
Open-circuit voltage, and form the best silver-colored silicon contact surface, reduce the contact resistance of front electrode.
But in order to effectively ensure that ohm of silver silicon connects, crossing in punching at sintering, it is necessary for having and fills
The energy of foot, this is accomplished by the high temperature of nearly 800 DEG C, allows the integrity of PN junction not be damaged by the biggest
Challenge, i.e. high temperature has damage to PN junction, and generally temperature is the highest, and PN junction damage probability is the biggest,
The most how to solve the high temperature requirement of the Ohmic contact realizing silver silicon and the low temperature requirements of PN junction holding integrity
Between contradiction just become need research problem.
Summary of the invention
It is an object of the invention to the deficiency overcoming prior art to exist, by improving the component of silver slurry,
Directly add tellurous acid silver on the basis of original composition or improve the mode of unorganic glass powder and provide a kind of
New crystal solaode anode silver paste and preparation method thereof;Another object of the present invention is to: for
Prepare above-mentioned crystal solaode anode silver paste and the standby side of tellurous acid silvery of tellurous acid silver material is provided
Method.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of tellurous acid silver, comprises the steps,
S11, tellurite generation step: tellurium oxide and XOH solution reaction are produced tellurite, described
X is K or Na;
S12, silver ammino solution generation step: be added dropwise over ammonia in the silver nitrate solution specifying consumption,
Drip while vibrate, stop to the resolution of precipitate initially generated, obtain silver ammino solution;
S13, tellurous acid silver generation step: tellurite is generated tellurous acid with silver ammino solution hybrid reaction
Silver precipitation.
Preferably, the preparation method of described tellurous acid silver, wherein: the quality of described XOH solution is divided
Number is 2-5%.
Preferably, the preparation method of described tellurous acid silver, wherein: described tellurium oxide and sodium hydroxide
Or potassium hydroxide mol ratio is 1:2.
Preferably, the preparation method of described tellurous acid silver, wherein: the concentration of described silver nitrate solution
Being 0.05-0.12mol/L, the mass fraction of described ammonia spirit is 8-15%, described silver nitrate and ammonia
The mol ratio of water or weight ratio are 1:1.
Preferably, the preparation method of described tellurous acid silver, wherein: described silver ammino solution and tellurous acid
Salt solute ratio is 2:1.
Crystal silicon solar batteries anode silver paste, it includes above-mentioned tellurous acid silver, organic carrier, Gao Xuan
Selecting ratio corrosive inorganic glass dust and argentum powder, the percentage by weight of above-mentioned each composition is: tellurous acid silver:
0-4wt%, organic carrier: 7-11wt%, unorganic glass powder: 2-4wt%, argentum powder: 87-90wt%.
Preferably, described crystal silicon solar batteries anode silver paste, wherein: putting down of described tellurous acid silver
All particle diameters are 1-4 μm.
Preferably, described crystal silicon solar batteries anode silver paste, wherein: described high selectivity corrodes
Property unorganic glass powder is Pb-Te-O system unorganic glass.
Preferably, described crystal silicon solar batteries anode silver paste, wherein: described argentum powder is spherical shape
The spherical formula of formula, class, sheet form and the combination of one or more, the mean diameter of described argentum powder is
1-5μm。
The preparation method of crystal silicon solar batteries anode silver paste, it comprises the steps:
S1, tellurous acid silver preparation process: prepare tellurous acid according to above-mentioned tellurous acid silvery Preparation Method
Silver;
S2, organic carrier preparation process: by organic component alcohol ester 12, butyl carbitol acetate, fourth
Base carbitol, ethyl cellulose and thixotropic agent thixatrol st press specified wt than adding container, and
It is warming up to 75 DEG C, is incubated 2 hours, obtains organic carrier;
S3, silver slurry preparation process: according to specified wt ratio by tellurous acid silver, organic carrier, high selectivity
Corrosive inorganic glass dust and argentum powder mixing, adjust pasty state, is ground to fineness with three-roller rolling little
In 10 μm, viscosity is 200-250mpa s, is prepared into solar cell front side silver paste.
The substantive distinguishing features of technical solution of the present invention and progress are mainly reflected in:
Deft design the most of the present invention, by directly add tellurous acid silver and use high selectivity corrosivity without
Machine glass dust, forms Ohmic contact for silver silicon and creates condition, avoid simultaneously from simple glass powder
Separate out the hot conditions required for enough tellurous acid silver, thus ensure that the integrity of PN junction will not be subject to
The impact of high temperature, solves contradiction between the two, widens the window of sintering temperature.
2., by using high selectivity corrosive inorganic glass dust and tellurous acid silver, reach that positive electricity is extremely low to be connect
Get an electric shock and hinder purpose, it is ensured that the high conversion efficiency of battery.
3. the preparation method of the tellurous acid silver that the present invention provides is simple, and raw material obtains convenient, cost
Low, environmental hazard is little, and the preparation for silver slurry creates basic condition.
Detailed description of the invention
The most just the present invention program is described further:
The present invention is by promoting silver silicon again by corroding silicon nitride by unorganic glass powder in sintering process
The process that ohm connects separates, i.e. by high selectivity corrosive inorganic glass dust corroding silicon nitride
Layer, and separate out Asia at relatively low temperatures by directly adding tellurous acid silver and Pb-Te-O system
The mode of telluric acid silver, facilitates silver silicon to form Ohmic contact, thus solves unorganic glass in prior art
Separating out tellurous acid silver in powder needs the stability of high temperature and PN junction to need the contradiction of relatively low temperature.
The present invention specifically provides a kind of crystal silicon solar batteries anode silver paste, including tellurous acid silver, has
Airborne body, high selectivity corrosive inorganic glass dust and argentum powder, the percentage by weight of above-mentioned each composition
Composition: tellurous acid silver: 0-4wt%, organic carrier: 7-11wt%, unorganic glass powder: 2-4wt%, silver
Powder: 87-90wt%.
Further, the mean diameter of described tellurous acid silver is 1-4 μm, owing to unorganic glass is insulator,
Too much interpolation can increase solaode series resistance, by the way of directly adding tellurous acid silver, and can
Largely to reduce the addition of unorganic glass, to promote the performance of solaode.
Described organic carrier has after mixing inorganic component and organic media, is formed and is applicable to silk screen printing
Ink, this is because ink has certain denseness and a rheological property, and have what silk screen printing was suitable for
Viscosity, thixotropy, yield value etc., and possess good calcination performance.
Described high selectivity corrosive inorganic glass dust refers to that the corrosion rate difference to SiNx and Si is big
Unorganic glass powder, has a good corrosive nature to the silicon nitride as reflecting layer, but the corrosivity to Si
Can be the lowest;Described high selectivity corrosive inorganic glass dust is preferably the inorganic glass of Pb-Te-O system
Glass powder, wherein Pb-Te-O system refers to that material of main part is Te, and Pb, O form, and Pb-Te-O body
Tie up to sintering process has the formation of tellurous acid silver, be conducive to increasing further the tellurous acid in reaction
The total amount of silver, promotes the Ohmic contact of silver silicon.
Described argentum powder be balled form, the spherical formula of class, sheet form and the combination of one or more, institute
The mean diameter stating argentum powder is 1-5 μm.
Further, present invention further teaches the preparation method of a kind of crystal silicon solar batteries anode silver paste, its
Comprise the steps:
S1, tellurous acid silver preparation process: prepare tellurous acid according to following steps silver-colored:
S11, tellurite generation step: tellurium oxide and XOH solution reaction are produced tellurite, described
X is K or Na;The mass fraction of described XOH solution is 2-5%, preferably 4%, described tellurium oxide and
Sodium hydroxide or potassium hydroxide mol ratio are 1:2.
As a example by NaOH, its reaction equation is as follows:
TeO2+ 2NaOH==Na2TeO3+H2O。
S12, silver ammino solution generation step:
First first injecting a small amount of sodium hydroxide solution in test tube, vibration, then heated and boiled, hydrogen-oxygen
After change sodium goes, then clean standby with distilled water.
Preparation solution: in clean test tube, injects 1mL silver nitrate solution, is then added dropwise over ammonia,
Dripping while vibrate, until the precipitation initially generated just is dissolved, its concrete course of reaction is as follows:
After dropwise dripping ammonia in silver nitrate solution, silver nitrate and ammonia are according to chemical reaction
AgNO3+NH3H2O==AgOH ↓+NH4NO3First reaction separates out AgOH;Owing under room temperature, AgOH pole is not
Stable, according to reaction equation: 2AgOH==Ag2O↓+H2O is decomposed into Ag2O burgundy precipitates;Continue dropping
Ammonia, Ag2O precipitates according to reaction equation: Ag2O+4NH3·H2O=2Ag (NH3)2 ++2OH-+3H2O dissolves: with
Time, the OH of generation-With the NH above reacting generation4 +(AgNO3+NH3H2O==AgOH ↓+NH4NO3)
Reaction: OH-+NH4 +==NH3·H2O。
Therefore, to AgNO3In solution, addition weak ammonia to total ionic equation of resolution of precipitate is:
Ag+Containing only NO in+2NH3 H2O==Ag (NH3) 2++2H2O now solution3 -With Ag (NH3)2+, i.e. obtain
Ag(NH3)2NO3。
During the generation of silver ammino solution, the concentration of described silver nitrate solution is 0.05-0.12mol/L,
The mass fraction of described ammonia spirit is 8-15%, and the concentration of the most described silver nitrate solution is
0.1mol/L, the mass fraction of described ammonia spirit is 15%, and the mol ratio of described silver nitrate and ammonia is
1:1。
S13, tellurous acid silver generation step: tellurite is generated tellurous acid with silver ammino solution hybrid reaction
Silver precipitation, wherein, the mol ratio of described silver ammino solution and tellurite is 2:1, and they are according to following anti-
Equation is answered to react: Na2TeO3+2Ag(NH3)2NO3==Ag2TeO3↓+2NaNO3。
For the ease of the application of crystal silicon solar batteries anode silver paste in the present invention, the tellurous acid silver that will generate
Utilize ball milling method, mean diameter is controlled in 1-4 μm, with applicable silk screen printing.
S2, organic carrier preparation process: by organic component alcohol ester 12, butyl carbitol acetate, fourth
Base carbitol, ethyl cellulose and thixotropic agent thixatrol st press specified wt than adding container, and
It is warming up to 75 DEG C, is incubated 2 hours, obtains organic carrier;
S3, silver slurry preparation process: according to tellurous acid silver: 0-4wt%, organic carrier: 7-11wt%, nothing
Machine glass dust: 2-4wt%, raw material is mixed by the proportioning of argentum powder: 87-90wt%, adjusts pasty state, uses
Three-roller rolling is ground to fineness and is less than 10 μm, and viscosity is 200-250mpa s, is prepared into the sun
Can cell front side silver paste.
Certainly, above-mentioned tellurous acid silver generation step, organic carrier preparation process and the mistake prepared without glass dust
The sequencing of journey does not has strict restriction, as long as will complete above-mentioned three before silver slurry preparation process
Raw material corresponding to individual step makes.
Embodiment 1:
Prepare organic carrier: according to component ratio: ethyl cellulose 3wt%, thixotropic agent thixatrol st5
Wt%, alcohol ester 12 60wt%, butyl carbitol acetate 20wt%, butyl carbitol 12wt%'s
Ratio, adds stirring in container and is warming up to and 75 DEG C, be incubated 2 hours.
By argentum powder 87wt%, organic carrier 10wt%, high selectivity etching glass powder 2wt%, tellurious
The ratio mix homogeneously of acid silver 1wt%, furnishing pasty state, it is ground to fineness less than 10 μ with three-roller rolling
M, viscosity is 200-250mpa s, is prepared into solar cell front side silver paste slurry as a comparison.
Embodiment 2:
Prepare organic carrier: according to component ratio: ethyl cellulose 3wt%, thixotropic agent thixatrol st5
Wt%, alcohol ester 12 60wt%, butyl carbitol acetate 20wt%, butyl carbitol 12wt%'s
Ratio, adds stirring in container and is warming up to and 75 DEG C, be incubated 2 hours.
By argentum powder 88wt%, organic carrier 10wt%, the ratio of high selectivity etching glass powder 2wt%
Mix homogeneously, furnishing pasty state, it is ground to fineness with three-roller rolling and is less than 10 μm, viscosity is 200-250
Mpa s, is prepared into solar cell front side silver paste slurry as a comparison.
Embodiment 3:
Prepare organic carrier: according to component ratio: ethyl cellulose 3wt%, thixotropic agent thixatrol st5
Wt%, alcohol ester 12 60wt%, butyl carbitol acetate 20wt%, butyl carbitol 12wt%'s
Ratio, adds stirring in container and is warming up to and 75 DEG C, be incubated 2 hours.
By argentum powder 87wt%, organic carrier 9wt%, high selectivity etching glass powder 2wt%, tellurous acid
The ratio mix homogeneously of silver 2wt%, furnishing pasty state, it is ground to fineness less than 10 μ with three-roller rolling
M, viscosity is 200-250mpa s, is prepared into solar cell front side silver paste slurry as a comparison.
Comparative example 1:
Prepare organic carrier: according to component ratio: ethyl cellulose 3wt%, thixotropic agent thixatrol st5
Wt%, alcohol ester 12 60wt%, butyl carbitol acetate 20wt%, butyl carbitol 12wt%'s
Ratio, adds stirring in container and is warming up to and 75 DEG C, be incubated 2 hours.
By argentum powder 87wt%, organic carrier 10wt%, PSGS-2014 tradition unorganic glass powder 3wt%
Ratio mix homogeneously, furnishing pasty state, be ground to fineness less than 10 μm with three-roller rolling, viscosity
For 200-250mpa s, it is prepared into solar cell front side silver paste slurry as a comparison.
Comparative example 2:
Prepare organic carrier: according to component ratio: ethyl cellulose 3wt%, thixotropic agent thixatrol st5
Wt%, alcohol ester 12 60wt%, butyl carbitol acetate 20wt%, butyl carbitol 12wt%'s
Ratio, adds stirring in container and is warming up to and 75 DEG C, be incubated 2 hours.
By argentum powder 87wt%, organic carrier 10wt%, tellurous acid silver 3wt%, furnishing pasty state, with three
The rolling of roller machine is ground to fineness and is less than 10 μm, and viscosity is 200-250mpa s, is prepared into solar energy
Cell front side silver paste slurry as a comparison.
After preparing anode silver paste by the above-mentioned preparation method of silver slurry and the embodiment of correspondence, and pass through silk
Net mode of printing is transferred on the polysilicon chip that square resistance is 90 Ω/;By peak temperature it is
The despatch sintering furnace of 770 DEG C, tests 156 × 156 polycrystalline cell pieces effect at different temperatures
Rate, it is as shown in the table that the silver slurry prepared with above-mentioned each example is compared test result:
Sintering peak value (DEG C) | Series resistance Rs (mohm) | Conversion efficiency (%) | |
Embodiment 1 | 770 | 3.57 | 15.45 |
Embodiment 1 | 700 | 3.42 | 15.21 |
Embodiment 2 | 770 | 6.22 | 13.25 |
Embodiment 3 | 700 | 3.01 | 16.01 |
Comparative example 1 | 770 | 2.43 | 17.44 |
Comparative example 1 | 700 | 25.28 | 9.66 |
Comparative example 2 | 770 | 132.08 | 1.12 |
Permissible in the data of 770 DEG C and the temperature conditions of 700 DEG C from upper table embodiment 1 and comparative example 1
Find out, under the window of non-constant width, add tellurous acid silver and high selectivity corrosive inorganic glass dust obtains
Each performance of the solaode arrived is the most unchanged, even if the most under cryogenic, it both met
The low temperature requirements that PN junction is stable, can effectively meet again the requirement of the Ohmic contact forming silver silicon;And pass
In system technique, although when 770 DEG C, the solar cell properties performance excellence that traditional handicraft obtains, but
Being as the reduction of sintering temperature, the performance of solaode drastically declines, series resistance and efficiency
Preferred values all can only show in less window, so traditional handicraft cannot effectively solve PN junction and stablize
Property low temperature requirements and from tradition unorganic glass, separate out tellurous acid silver to realize the Ohmic contact of silver silicon
Contradiction between high temperature requirement.
Data from embodiment 1 and embodiment 2 are it can be seen that directly adding of tellurous acid silver is permissible
Reduce solaode series resistance and conversion efficiency, i.e. tellurous acid silver take part in silver silicon contact, reduce
Ohmic contact resistance.
Data from embodiment 1 and embodiment 3 are it can be seen that when adding tellurous acid silver, permissible
Reduce the contact resistance of solar cell further and improve conversion efficiency, but, continue to increase at content
After, contact resistance fall is no longer obvious, and conversion efficiency increase rate is the least, and performance changes relatively
For steadily.
Data from comparative example 2 are it can be seen that tellurous acid silver not high temperature penetrates the energy of silicon nitride
Power, only on the premise of penetrating silicon nitride by unorganic glass, tellurous acid silver competence exertion promotes Europe
The function of nurse contact.
Below it is only presently preferred embodiments of the present invention, not the present invention is made any pro forma limit
System, any simple modification that above example is made by every technical spirit according to the present invention, equivalent
Change and modification, all still fall within the range of technical solution of the present invention.
Claims (10)
1. the preparation method of tellurous acid silver, it is characterised in that: comprise the steps,
S11, tellurite generation step: with XOH solution reaction, tellurium oxide is produced tellurite, and described X is K or Na;
S12, silver ammino solution generation step: be added dropwise over ammonia in the silver nitrate solution specifying consumption, drip while vibrate, stop to the resolution of precipitate initially generated, obtain silver ammino solution;
S13, tellurous acid silver generation step: tellurite and silver ammino solution hybrid reaction are generated tellurous acid silver precipitation.
The preparation method of tellurous acid the most according to claim 1 silver, it is characterised in that: the mass fraction of described XOH solution is 2-5%.
The preparation method of tellurous acid the most according to claim 1 silver, it is characterised in that: described tellurium oxide and sodium hydroxide or potassium hydroxide mol ratio are 1:2.
The preparation method of tellurous acid the most according to claim 1 silver, it is characterised in that: the concentration of described silver nitrate solution is 0.05-0.12mol/L, and the mass fraction of described ammonia spirit is 8-15%, and the mol ratio of described silver nitrate and ammonia is 1:1.
The preparation method of tellurous acid the most according to claim 1 silver, it is characterised in that: the mol ratio of described silver ammino solution and tellurite is 2:1.
6. crystal silicon solar batteries anode silver paste, it is characterized in that: include claim 1-5 arbitrary described tellurous acid silver, organic carrier, high selectivity corrosive inorganic glass dust and argentum powder, the percentage by weight of above-mentioned each composition is: tellurous acid silver: 0-4 wt%, organic carrier: 7-11wt%, high selectivity corrosive inorganic glass dust: 2-4 wt%, argentum powder: 87-90 wt%.
Crystal silicon solar batteries anode silver paste the most according to claim 6, it is characterised in that: the mean diameter of described tellurous acid silver is 1-4 μm.
Crystal silicon solar batteries anode silver paste the most according to claim 6, it is characterised in that: described high selectivity corrosive inorganic glass dust is Pb-Te-O system unorganic glass.
Crystal silicon solar batteries anode silver paste the most according to claim 6, it is characterised in that: described argentum powder be balled form, the spherical formula of class, sheet form and the combination of one or more, the mean diameter of described argentum powder is 1-5 μm.
10. the preparation method of crystal silicon solar batteries anode silver paste, it is characterised in that: comprise the steps:
S1, tellurous acid silver preparation process: prepare tellurous acid silver according to the arbitrary described tellurous acid silvery Preparation Method of claim 1-5;
S2, organic carrier preparation process: organic component alcohol ester 12, butyl carbitol acetate, butyl carbitol, ethyl cellulose and thixotropic agent thixatrol st are pressed specified wt than adding container, and be warming up to 75 DEG C, be incubated 2 hours, obtain organic carrier;
S3, silver slurry preparation process: mix than by tellurous acid silver, organic carrier, high selectivity corrosive inorganic glass dust and argentum powder according to specified wt, adjust pasty state, is ground to fineness less than 10 μm with three-roller rolling, viscosity is 200-250 mpa s, is prepared into solar cell front side silver paste.
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CN109807346A (en) * | 2019-02-18 | 2019-05-28 | 贵州理工学院 | A kind of glass flour complexes and preparation method thereof of silver tellurium cladding |
CN109961870A (en) * | 2019-03-01 | 2019-07-02 | 泰州中来光电科技有限公司 | A kind of crystal-silicon solar cell black silver paste and preparation method thereof |
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CN109807346A (en) * | 2019-02-18 | 2019-05-28 | 贵州理工学院 | A kind of glass flour complexes and preparation method thereof of silver tellurium cladding |
CN109961870A (en) * | 2019-03-01 | 2019-07-02 | 泰州中来光电科技有限公司 | A kind of crystal-silicon solar cell black silver paste and preparation method thereof |
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