CN112489851B - N-type efficient battery front silver-aluminum paste - Google Patents
N-type efficient battery front silver-aluminum paste Download PDFInfo
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- CN112489851B CN112489851B CN202011242618.0A CN202011242618A CN112489851B CN 112489851 B CN112489851 B CN 112489851B CN 202011242618 A CN202011242618 A CN 202011242618A CN 112489851 B CN112489851 B CN 112489851B
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- -1 silver-aluminum Chemical compound 0.000 title claims abstract description 89
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 54
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011521 glass Substances 0.000 claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 32
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000013008 thixotropic agent Substances 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- KAHDRIJVYBCDNO-UHFFFAOYSA-N C(CCC)OCCCC.C(C(=O)O)(=O)O Chemical compound C(CCC)OCCCC.C(C(=O)O)(=O)O KAHDRIJVYBCDNO-UHFFFAOYSA-N 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- 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 6
- 229910020826 NaAlF6 Inorganic materials 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000004147 Sorbitan trioleate Substances 0.000 claims description 5
- 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 5
- 235000019337 sorbitan trioleate Nutrition 0.000 claims description 5
- 229960000391 sorbitan trioleate Drugs 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000005245 sintering Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000002161 passivation Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 23
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 2
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 2
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229940023462 paste product Drugs 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
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- 238000004448 titration Methods 0.000 description 1
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- 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
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- 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
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- 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
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- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an N-type efficient battery front silver-aluminum paste, which belongs to the field of materials and comprises the following components in parts by weight: 83-95 parts of silver-aluminum powder mixture, 2-8 parts of glass frit, 0.01-0.2 part of metal oxide, 4-12 parts of organic carrier, 1-10 parts of AlB alloy and 0-1 part of boron powder; the silver-aluminum powder mixture comprises silver powder and aluminum powder, and the mass ratio of the silver powder to the aluminum powder is 1: 78-85; the activity degree of the aluminum powder is 98-99.8%. By adding a certain amount of silver powder into the aluminum powder and limiting the high activity of the aluminum powder, the conductivity of the silver-aluminum paste can be improved, and the contact resistance value can be reduced; by adding the glass material into the components, the passive film on the surface of the battery can be effectively corroded; the addition of the metal oxide can balance the reaction degree of the silver-aluminum powder, the passivation film and the silicon; the addition of the AlB alloy and the boron powder can ensure that the B element in the silver-aluminum paste is uniformly dispersed to promote the contact performance, and the P + structure is prepared by sintering to improve the conductivity. The invention also provides a preparation method of the product and an N-type high-efficiency battery prepared from the product.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a front silver-aluminum paste of an N-type efficient battery
Background
Crystalline silicon solar cells have evolved over the years, with performance escalating, from the earliest crystalline silicon conventional solar cells (no passivation on the back) to the back passivated PERC cells. In the PERC cell, the metal electrode is still in direct contact with the silicon substrate, the contact interface between the metal and the semiconductor can generate band bending due to work function adaptation, and a large number of minority carrier recombination centers are generated, which has a negative effect on the efficiency of the solar cell, so that it has been proposed for a long time to use a thin film to separate the metal from the silicon to reduce recombination, but the cell based on the structural principle has not been industrialized until recently, and the existing products have the following disadvantages: (1) the electrical property is unstable, and the electrical property difference among batches reaches 0.2%; (2) the overall electrical performance is not high enough, the mass production efficiency is 23.8 percent averagely, and the open-circuit voltage is lower than 700 mv; (3) poor printing performance, and false printing often occurs; (4) the contact resistance is large.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide the front silver-aluminum paste of the N-type efficient battery with high open-circuit voltage, good printing performance and small contact resistance.
In order to achieve the purpose, the invention adopts the technical scheme that:
the N-type efficient battery front silver-aluminum paste comprises the following components in parts by weight: 83-95 parts of silver-aluminum powder mixture, 2-8 parts of glass frit, 0.01-0.2 part of metal oxide, 1-10 parts of organic carrier, 1-10 parts of AlB alloy and 0-1 part of boron powder; the silver-aluminum powder mixture comprises silver powder and aluminum powder, and the mass ratio of the silver powder to the aluminum powder is 1: 78-85; the oxygen content of the aluminum powder is 0.9-1.3%.
According to the N-type efficient battery front silver-aluminum paste provided by the invention, the silver powder with specific content is added into the aluminum powder, so that the conductivity of the whole silver-aluminum paste is improved, and the contact resistance value of a finally prepared battery is reduced; and meanwhile, the low oxygen content (namely high purity) in the aluminum powder is limited, so that the aluminum powder is easy to break through the contact between the passivation film layer and silicon in the battery to form ohmic contact, and the current conduction capability of the silver-aluminum paste of the battery is ensured. The content of the added silver powder is moderate, and if the content of the silver powder is too much, the content of aluminum is easily reduced, the contact resistance is increased, and the performance of the battery is influenced; when the content is too small, electron-hole recombination is large, the open-circuit voltage of the battery is lowered, and the printability is poor. By adding the glass material and the metal oxide into the components, the application process window of the material can be effectively widened, the stability of the silver-aluminum paste is improved, and the phenomenon that the reaction of aluminum powder and silicon in the battery is too violent due to excessive corrosion of the glass material on a passivation film is avoided; the addition of the AlB alloy with specific content and the boron powder can ensure that the B element in the silver-aluminum paste is uniformly dispersed to promote the contact performance, and the P + structure is prepared by sintering to improve the conductivity. Through the coordination of the whole formula, the N-type efficient battery front silver-aluminum paste can ensure that the N-type efficient battery front silver-aluminum paste has high open-circuit voltage, wide application window, low contact resistance and excellent electrical property when applied to a battery.
Preferably, the silver powder has a median particle diameter0.5 to 3 μm and a specific surface area of 0.5 to 2m2(ii) a tap density of 4 to 6g/m3The burning loss rate is less than or equal to 1 percent. The particle size and the specific surface area of the silver powder are limited, so that the dispersibility of the silver powder can be effectively ensured, and the phenomenon that hard agglomerated silver particles are extruded into silver flakes when slurry is subjected to a grinding process, the silver flakes stay on a screen printing plate up and down during screen printing, and the accumulation of the silver flakes causes net blocking and forms virtual printing when more than thousands of silver flakes are printed is avoided; if the particle diameter of the silver powder is too large, insufficient sintering activity may be caused, leading to a problem of denseness, affecting the line resistance and even the electrical properties. The silver powder with proper tap density and low burning loss rate can ensure the shrinkage rate of the silver powder during sintering, the contact among the silver powders is compact, and the resistance is low.
Preferably, the median particle size of the aluminum powder is 1-5 mu m, and the maximum particle size D100Less than or equal to 12 mu m. Because the aluminum powder particles in the silver-aluminum paste are far larger than the silver powder particles, the large granularity of the aluminum powder can cause the phenomena of blocking or scraping a screen plate, and cause virtual printing or paste leakage; however, even if the median diameter of the powdery aluminum is appropriate, if the particle size distribution of the powdery aluminum is wide, the maximum particle diameter is large, which causes the above-mentioned problems. Therefore, similarly to the silver powder, the particle diameter of the aluminum powder is also required to be limited. The maximum grain diameter of the median grain diameter of the aluminum powder is limited, so that the phenomena of net blocking and virtual printing cannot be caused in the printing process.
Preferably, the glass frit comprises the following components in parts by weight: pb3(BO3)210 to 30 parts of Bi2O310-30 parts of SiO21 to 10 parts of Al2O31 to 10 parts of SnO210-30 parts of NaAlF60.1 to 3 parts of ZrO21 to 6 parts and 5 to 20 parts of SrO. Pb3(BO3)2The sintering can be promoted, and the ohmic metal aluminum is protected from being oxidized; bi2O3In which Bi is in Bi6O6In the 8-face body of (2), the covalent component of Bi-O bonds increases and Bi becomes Bi3+The coordination number of (2) is reduced, and the formation of a catalyst analogous to SbO3Configurational BiO3Radical of special structure, BiO3Radical filling in SiO4Between tetrahedrons, the glass structure is compact and in a stateStabilizing; SiO 22As the main skeleton of the frit, compact SiO is formed2A network structure; al (Al)2O3The addition of (3) can adjust the viscosity of the glass material and inhibit phase separation and crystallization; SnO2The addition of the compound can improve the chemical stability of the material, reduce the thermal expansion coefficient and improve the thermodynamic stability; ZrO (ZrO)2The sintering shrinkage of the glass particles is reduced by adding the glass particles, the physical and chemical stability of the glass frit is improved, the battery piece can endure outdoor severe environment, and the power generation capacity is not attenuated; SrO is used as a strong fusing agent, is not easy to melt at low temperature, can greatly reduce the viscosity of the glass material once melted at high temperature, is the best fusing agent for replacing lead oxide, and can effectively reduce the using amount of lead.
Preferably, the particle size of the glass frit is 0.5-5 μm. The glass frit can be controlled to have a proper softening point through the limitation of the grain size of the glass frit, so that the sintering temperature and the corrosion degree of the whole slurry can be controlled.
Preferably, the metal oxide includes at least one of PbO and SrO. The metal oxide is added outside the glass frit, so that the corrosion of the glass frit to a passivation film is better balanced, and the reaction of aluminum powder and silicon is not too violent, so that the sintering depth is too large, the too large compounding is generated, and the electrical property is reduced.
Preferably, the organic vehicle comprises the following components in parts by weight: 2-15 parts of a mixture of acrylic resin and ethyl cellulose, 10-30 parts of terpineol, 10-30 parts of butyl carbitol, 10-30 parts of decaglycol ester, 15-25 parts of diethyl phthalate, 1-10 parts of butyl ether diglycol acetate and 5-15 parts of butyl ether oxalate. The organic carrier composed of the components with the contents can effectively load silver-aluminum powder and other components, and simultaneously ensures the dispersion uniformity of the components.
Preferably, the mass content of B in the AlB alloy is 0.1-1%. Because of the structure of the front N-P of the N-type high-efficiency battery, the P layer is arranged on the front surface, the third main group element which lacks electrons on the periodic table of the elements is needed to be used as a front electrode, a P + structure is manufactured by sintering, and the use is consideredSuitability and price, Al element is preferred, and secondly, the sintering doping concentration of Al in Si (sintering process for mass production) is up to 1018And the sintering doping concentration of B can reach 1019Therefore, except aluminum, B element is selected as doping element; because B is a non-conductive substance, the doping of B is not necessary to be too much, but the adding of B is too little, so that the uniform distribution of B element in all positions is difficult to guarantee; the inventor finds out through experiments that the best effect is achieved by selecting the AlB alloy as the component, the AlB alloy can be used for replacing part of aluminum powder, the stability of the reaction between the aluminum powder and silicon in the battery can be guaranteed, and the content of the B element can be limited to guarantee that the addition amount of the AlB alloy is enough and can be uniformly distributed at all positions of an interface.
Preferably, the particle size of the boron powder is 10-100 nm, and the purity is more than or equal to 99.9%. Similar to the effect of AlB alloy, the boron powder can effectively ensure that the diffusion concentration is increased and the dispersion degree is high after the particle size is reduced and the purity is improved, and the electrical property of the finally prepared battery is improved.
Preferably, the components in the front-side silver-aluminum paste of the N-type high-efficiency battery further comprise a dispersing agent, a leveling agent and a thixotropic agent; the dispersant is sorbitan trioleate.
The invention also aims to provide a preparation method of the N-type efficient battery front silver-aluminum paste.
A preparation method of N-type efficient battery front silver-aluminum paste comprises the following steps:
(1) respectively adding the silver powder and the aluminum powder into an organic solvent, mixing and homogenizing, and then uniformly mixing to obtain a silver-aluminum powder mixture;
(2) and (2) mixing the silver-aluminum powder mixture obtained in the step (1), glass frit, metal oxide, organic carrier, AlB alloy and boron powder, uniformly stirring in vacuum, and dispersing to obtain the front silver-aluminum paste of the N-type efficient battery.
The preparation method of the N-type efficient battery front silver-aluminum paste has simple operation steps and can realize industrial large-scale production.
The invention further aims to provide an N-type efficient battery prepared from the front silver-aluminum paste of the N-type efficient battery. The cell not only has a high open circuit voltage, a wide application window, low contact resistance, and excellent electrical properties.
The invention has the beneficial effects that the silver aluminum paste on the front surface of the N-type efficient battery is provided, and the silver powder with specific content is added into the aluminum powder, and meanwhile, the low oxygen content in the aluminum powder is limited, so that the conductivity of the whole silver aluminum paste is improved, the contact resistance value of the finally prepared battery is reduced, and the current conduction capability of the silver aluminum paste of the battery is ensured. By adding the glass material into the components, a passive film on the surface of the battery can be effectively corroded, and silver-aluminum powder is introduced into a contact interface; the addition of the metal oxide can well balance the reaction degree of the silver, the aluminum powder, the passivation film and the silicon; the addition of the AlB alloy with specific content and the boron powder can ensure that the B element in the silver-aluminum paste is uniformly dispersed to promote the contact performance, and the P + structure is prepared by sintering to improve the conductivity. Through the coordination of the whole formula, the positive silver-aluminum paste of the N-type efficient battery can ensure that the positive silver-aluminum paste has high open-circuit voltage, wide application window, low contact resistance and excellent photoelectric conversion efficiency when applied to the battery. The invention also provides a preparation method of the front silver-aluminum paste of the N-type efficient battery. The method has simple operation steps and can realize industrialized large-scale production. The invention also provides an N-type efficient battery prepared from the front silver-aluminum paste of the N-type efficient battery.
Drawings
Fig. 1 is a schematic structural diagram of an N-type efficient battery prepared from the silver-aluminum paste on the front surface of the N-type efficient battery.
Detailed Description
Unless otherwise specified, the raw materials used in the examples of the present invention and comparative examples were commercially available, and the production equipment used was a commercially available common model. The aluminum powder used in the invention is a product produced by Jinma corporation in Hunan, the test of the median particle size and the maximum particle size of the product is carried out by using a Dandongbaut particle size analyzer (BT-P300S), and the test of the activity is carried out by using an oxidation-reduction titration method; the silver powder used was a product produced by Suzhou silver Ray, and the median particle size of the product was measured by using a Malvern particle size analyzer (MS2000), the specific surface area was measured by using a Miro high-Bo specific surface area analyzer (JW-BK400), the tap density was measured by using a tap density instrument PT-20, and the burn-out rate was measured by using a drying densitometer method.
For better illustrating the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples, which are intended to be understood in detail, but not intended to limit the present invention.
Example 1
According to an embodiment of the front silver-aluminum paste for the N-type efficient battery, the front silver-aluminum paste for the N-type efficient battery comprises the following components in parts by weight: 90 parts of silver-aluminum powder mixture, 5 parts of glass frit, 0.1 part of metal oxide, 8 parts of organic carrier, 5 parts of AlB alloy, 0.5 part of boron powder, 0.5 part of dispersing agent, 0.5 part of flatting agent and 0.5 part of thixotropic agent; the silver-aluminum powder mixture comprises quasi-spherical silver powder and aluminum powder, and the mass ratio of the silver powder to the aluminum powder is 1: 80; the activity degree of the aluminum powder is 98.9%; the dispersant is sorbitan trioleate; the organic carrier comprises the following components in parts by weight: 8 parts of a mixture of acrylic resin and ethyl cellulose, 15 parts of terpineol, 20 parts of butyl carbitol, 20 parts of dodecanol ester, 19 parts of diethyl phthalate, 5 parts of butyl ether diglycol acetate and 10 parts of butyl ether oxalate; the AlB alloy is AlB alloy powder.
The median particle diameter of the sphere-like silver powder is 1 mu m, and the specific surface area is 1.5m2(ii)/g, tap density 5g/m3The burning loss rate is 0.5%; the median particle diameter of the aluminum powder is 3 mu m, and the maximum particle diameter D100Is 10 μm.
The glass frit comprises the following components in parts by weight: pb3(BO3)220 parts of Bi2O320 parts of SiO25 parts of Al2O35 parts of SnO220 parts of NaAlF62 parts of ZrO24 parts and 15 parts of SrO; the grain size of the glass frit is 2.5 mu m; and mixing the oxides, roughly mixing the mixed oxides by a V-shaped mixer, putting the mixed materials into a crucible, then smelting at high temperature, quenching, and grinding the obtained frit of the glass material to the particle size.
The metal oxide is a mixture of PbO and SrO, and the mass ratio of the PbO to the SrO is 1: 1.
The organic carrier comprises the following components in parts by weight: 10 parts of a mixture of acrylic resin and ethyl cellulose, 20 parts of terpineol, 20 parts of butyl carbitol, 20 parts of dodecanol ester, 20 parts of diethyl phthalate, 5 parts of butyl ether diglycol acetate and 10 parts of butyl ether oxalate.
The mass content of B in the AlB alloy is 0.5%; the average particle size of the boron powder is 50 nm.
The preparation method of the front silver-aluminum paste of the N-type efficient battery comprises the following steps:
(1) respectively taking 50 parts of spheroidal silver powder and aluminum powder, respectively adding 8 parts of organic solvent, mixing, respectively homogenizing in a homogenizer, and uniformly mixing the two according to a proportion to obtain a silver-aluminum powder mixture;
(2) and (2) mixing the silver-aluminum powder mixture obtained in the step (1), glass frit, metal oxide, organic carrier, AlB alloy, boron powder, dispersant, leveling agent and thixotropic agent, stirring for 20min uniformly under vacuum, and introducing into a three-roll grinding machine for dispersing to obtain the N-type efficient battery front silver-aluminum paste.
Example 2
According to an embodiment of the front silver-aluminum paste for the N-type efficient battery, the front silver-aluminum paste for the N-type efficient battery comprises the following components in parts by weight: 95 parts of silver-aluminum powder mixture, 8 parts of glass frit, 0.2 part of metal oxide, 12 parts of organic carrier, 10 parts of AlB alloy, 0.5 part of boron powder, 1 part of dispersing agent, 0.5 part of flatting agent and 0.5 part of thixotropic agent; the silver-aluminum powder mixture comprises spherical-like silver powder and aluminum powder, and the mass ratio of the silver powder to the aluminum powder is 1: 78; the activity degree of the aluminum powder is 99%; the dispersant is sorbitan trioleate; the AlB alloy is AlB alloy powder.
The median particle diameter of the sphere-like silver powder is 2.5 mu m, and the specific surface area is 2m2(g) tap density of 4g/m3The burning loss rate is 0.5%; the median particle diameter of the aluminum powder is 4.5 mu m, and the maximum particle diameter D100And 12 μm.
The glass frit comprises the following components in parts by weight: pb3(BO3)210 parts of Bi2O330 parts of SiO210 parts of Al2O32 parts of SnO210 parts of NaAlF63 parts of ZrO26 parts and 20 parts of SrO; the grain size of the glass frit is 2.5 mu m; and mixing the oxides, roughly mixing the mixed oxides by a V-shaped mixer, putting the mixed materials into a crucible, then smelting at high temperature, quenching, and grinding the obtained frit of the glass material to the particle size.
The metal oxide is a mixture of PbO and SrO, and the mass ratio of the PbO to the SrO is 1: 1.
The organic carrier comprises the following components in parts by weight: 15 parts of a mixture of acrylic resin and ethyl cellulose, 10 parts of terpineol, 30 parts of butyl carbitol, 10 parts of dodecyl glycol ester, 25 parts of diethyl phthalate, 1 part of butyl ether diglycol acetate and 15 parts of butyl ether oxalate.
The mass content of B in the AlB alloy is 0.5%; the average particle size of the boron powder is 50 nm.
The preparation method of the silver-aluminum paste for the front surface of the N-type high-efficiency battery in the embodiment is the same as that in the embodiment 1.
Example 3
According to an embodiment of the front silver-aluminum paste for the N-type efficient battery, the front silver-aluminum paste for the N-type efficient battery comprises the following components in parts by weight: 83 parts of silver-aluminum powder mixture, 3 parts of glass frit, 0.05 part of metal oxide, 4 parts of organic carrier, 2 parts of AlB alloy, 0.5 part of boron powder, 0.5 part of dispersing agent, 0.5 part of flatting agent and 0.5 part of thixotropic agent; the silver-aluminum powder mixture comprises quasi-spherical silver powder and aluminum powder, and the mass ratio of the silver powder to the aluminum powder is 1: 85; the activity degree of the aluminum powder is 99%; the dispersant is sorbitan trioleate; the AlB alloy is AlB alloy powder.
The median particle diameter of the sphere-like silver powder is 0.5 mu m, and the specific surface area is 1m2(ii)/g, tap density of 6g/m3The burning loss rate is 0.5%; the median particle diameter of the aluminum powder is 2 mu m, and the maximum particle diameter D100Is 10 μm.
The glass frit comprises the following components in parts by weight: pb3(BO3)230 parts of Bi2O310 parts of SiO22 parts of Al2O310 parts of SnO230 parts of NaAlF60.5 part of ZrO22 parts and 5 parts of SrO; the grain size of the glass frit is 2.5 mu m; and mixing the oxides, roughly mixing the mixed oxides by a V-shaped mixer, putting the mixed materials into a crucible, then smelting at high temperature, quenching, and grinding the obtained frit of the glass material to the particle size.
The metal oxide is a mixture of PbO and SrO, and the mass ratio of the PbO to the SrO is 1: 1.
The organic carrier comprises the following components in parts by weight: 5 parts of a mixture of acrylic resin and ethyl cellulose, 30 parts of terpineol, 10 parts of butyl carbitol, 30 parts of dodecanol ester, 15 parts of diethyl phthalate, 10 parts of butyl ether diglycol acetate and 5 parts of butyl ether oxalate.
The mass content of B in the AlB alloy is 0.5%; the average particle size of the boron powder is 50 nm.
The preparation method of the silver-aluminum paste for the front surface of the N-type high-efficiency battery in the embodiment is the same as that in the embodiment 1.
Comparative example 1
The comparative example only differs from example 1 in that the battery silver-aluminum paste comprises the following components in parts by weight: 90 parts of silver-aluminum powder mixture, 5 parts of glass material, 8 parts of organic carrier, 0.5 part of dispersing agent, 0.5 part of flatting agent and 0.5 part of thixotropic agent.
Comparative example 2
The comparative example only differs from example 1 in that the battery silver-aluminum paste comprises the following components in parts by weight: 80 parts of silver-aluminum powder mixture, 10 parts of glass frit, 0.1 part of metal oxide, 15 parts of organic carrier, 5 parts of AlB alloy, 0.5 part of boron powder, 0.5 part of dispersing agent, 0.5 part of flatting agent and 0.5 part of thixotropic agent; the AlB alloy is AlB alloy powder.
Comparative example 3
The comparative example only differs from example 1 in that the battery silver-aluminum paste comprises the following components in parts by weight: 90 parts of silver-aluminum powder mixture, 1 part of glass frit, 0.1 part of metal oxide, 8 parts of organic carrier, 15 parts of AlB alloy, 0.5 part of boron powder, 0.5 part of dispersing agent, 0.5 part of flatting agent and 0.5 part of thixotropic agent; the AlB alloy is AlB alloy powder.
Comparative example 4
The comparative example is different from example 1 only in that the silver-aluminum powder mixture in the silver-aluminum paste of the battery comprises spherical-like silver powder and aluminum powder, and the mass ratio of the silver powder to the aluminum powder is 1: 75.
Comparative example 5
The comparative example is different from example 1 only in that the silver-aluminum powder mixture in the battery silver-aluminum paste comprises spherical-like silver powder and aluminum powder, and the mass ratio of the silver powder to the aluminum powder is 1: 90.
Comparative example 6
The comparative example only differs from example 1 in that the activity degree of the aluminum powder in the silver-aluminum paste of the battery is 95%.
Comparative example 7
The difference between the comparative example and the example 1 is that in the silver-aluminum paste on the front surface of the N-type high-efficiency battery, the median particle size of the aluminum powder is 8 mu m, and the maximum particle size D100Is 15 μm; the median particle size of the spherical silver powder is 5 mu m.
Comparative example 8
The difference between the comparative example and the example 1 is that in the front-side silver-aluminum paste of the N-type high-efficiency battery, the glass frit comprises the following components in parts by weight: pb3(BO3)235 parts of Bi2O35 parts of SiO25 parts of Al2O315 parts of SnO25 parts of NaAlF62 parts of ZrO28 parts and SrO 3 parts.
Comparative example 9
The comparative example differs from example 1 only in that the glass frit has an average particle size of 6 μm.
Comparative example 10
The comparative example is different from example 1 only in that the mass content of B in the AlB alloy in the front silver-aluminum paste of the N-type high-efficiency battery is 1.5%.
The front silver-aluminum paste product of the N-type high-efficiency battery prepared in the embodiment 1-3 is used for preparing the N-type high-efficiency battery, and the structural schematic diagram of the N-type high-efficiency battery is shown in fig. 1. Meanwhile, the products obtained in comparative examples 1-10 are also used for preparing N-type batteries, and the batteries are subjected to electrical property tests, wherein the test results are shown in Table 1.
TABLE 1
As can be seen from the table, compared with the products prepared in comparative examples 1-10, when the front-side silver-aluminum paste product of the N-type efficient battery prepared in the optimal technical parameter range is applied to the preparation of the N-type efficient battery, the battery has higher open-circuit voltage, lower resistance and excellent photoelectric conversion efficiency.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. The N-type efficient battery front silver-aluminum paste is characterized by comprising the following components in parts by weight: 83-95 parts of silver-aluminum powder mixture, 2-8 parts of glass frit, 0.01-0.2 part of metal oxide, 4-12 parts of organic carrier, 1-10 parts of AlB alloy and 0-1 part of boron powder;
the silver-aluminum powder mixture comprises silver powder and aluminum powder, and the mass ratio of the silver powder to the aluminum powder is 1: 78-85; the oxygen content of the aluminum powder is 0.9-1.3%; the median particle diameter of the aluminum powder is 1-5 mu m, and the maximum particle diameter D100Less than or equal to 12 mu m; the silver powder has a median particle diameter of 0.5-3 μm and a specific surface area of 0.5-2 m2(ii) a tap density of 4 to 6g/m3The burning loss rate is less than or equal to 1 percent;
the glass frit comprises the following components in parts by weight: pb3(BO3)210 to 30 parts of Bi2O310-30 parts of SiO21 to 10 parts of Al2O31 to 10 parts of SnO210-30 parts of NaAlF60.1 to 3 parts of ZrO21-6 parts and 5-20 parts of SrO; the particle size of the glass frit is 0.5-5 mu m;
the metal oxide is a mixture of PbO and SrO, and the mass ratio of the PbO to the SrO is 1: 1; the mass content of B in the AlB alloy is 0.1-1%.
2. The N-type high-efficiency battery front silver-aluminum paste as claimed in claim 1, wherein the organic vehicle comprises the following components in parts by weight: 2-15 parts of a mixture of acrylic resin and ethyl cellulose, 10-30 parts of terpineol, 10-30 parts of butyl carbitol, 10-30 parts of decaglycol ester, 15-25 parts of diethyl phthalate, 1-10 parts of butyl ether diglycol acetate and 5-15 parts of butyl ether oxalate.
3. The N-type high efficiency battery front silver aluminum paste of claim 1, having at least one of the following characteristics:
(1) the particle size of the boron powder is 10-100 nm, and the purity is more than or equal to 99.9%;
(2) the components in the silver-aluminum paste on the front surface of the N-type efficient battery also comprise a dispersing agent, a leveling agent and a thixotropic agent; the dispersant is sorbitan trioleate.
4. The preparation method of the front silver-aluminum paste of the N-type high-efficiency battery as claimed in any one of claims 1 to 3, comprising the following steps:
(1) respectively adding the silver powder and the aluminum powder into an organic solvent, mixing and homogenizing, and then uniformly mixing to obtain a silver-aluminum powder mixture;
(2) and (2) mixing the silver-aluminum powder mixture obtained in the step (1), glass frit, metal oxide, organic carrier, AlB alloy and boron powder, uniformly stirring in vacuum, and dispersing to obtain the front silver-aluminum paste of the N-type efficient battery.
5. An N-type high-efficiency battery prepared from the front-side silver-aluminum paste of the N-type high-efficiency battery as claimed in any one of claims 1 to 3.
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| CN114203335A (en) * | 2021-11-30 | 2022-03-18 | 江苏正能电子科技有限公司 | Front aluminum paste suitable for N-type TOPCon battery and preparation method thereof |
| CN114360760B (en) * | 2021-12-31 | 2023-09-08 | 广东南海启明光大科技有限公司 | Conductive powder, thick film silver-aluminum paste, and preparation method and application thereof |
| CN116759134A (en) * | 2023-05-19 | 2023-09-15 | 南通艾盛新能源科技有限公司 | Aluminum powder material for N-type silver-aluminum paste and application thereof |
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