CN113880435A - Modified glass powder for PERC back silver paste and preparation method and application thereof - Google Patents
Modified glass powder for PERC back silver paste and preparation method and application thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 171
- 239000000843 powder Substances 0.000 title claims abstract description 142
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 title claims abstract description 59
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 title claims abstract description 59
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 title claims abstract description 59
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 56
- 239000004332 silver Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 238000010791 quenching Methods 0.000 claims abstract description 9
- 230000000171 quenching effect Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004031 devitrification Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 21
- 239000000853 adhesive Substances 0.000 abstract description 19
- 230000001070 adhesive effect Effects 0.000 abstract description 19
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 15
- 230000032683 aging Effects 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 230000008569 process Effects 0.000 description 11
- 239000001856 Ethyl cellulose Substances 0.000 description 10
- 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 description 10
- 229920001249 ethyl cellulose Polymers 0.000 description 10
- 235000019325 ethyl cellulose Nutrition 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 5
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229940116411 terpineol Drugs 0.000 description 5
- 101000579913 Homo sapiens Peroxisomal trans-2-enoyl-CoA reductase Proteins 0.000 description 4
- 102100027506 Peroxisomal trans-2-enoyl-CoA reductase Human genes 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- UWSYCPWEBZRZNJ-UHFFFAOYSA-N trimethoxy(2,4,4-trimethylpentyl)silane Chemical group CO[Si](OC)(OC)CC(C)CC(C)(C)C UWSYCPWEBZRZNJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/1005—Forming solid beads
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the field of PERC solar cells, and discloses modified glass powder for PERC back silver paste and a preparation method and application thereof. The modified glass powder comprises glass powder and a coupling agent grafted on the surface of the glass powder, and the preparation method comprises the following steps: uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material; smelting the uniformly mixed materials to prepare uniform glass liquid; water quenching is carried out on the glass liquid to prepare coarse glass powder; and mixing the coarse glass powder with a coupling agent, grinding, drying and sieving to obtain the modified glass powder for the PERC back silver paste. The modified glass powder disclosed by the invention can reduce the corrosion of the glass powder to a passivation layer to a certain extent under the condition of ensuring the adhesive force and the aging adhesive force of the back silver paste, so that the electrical property of the PERC battery is improved, and the preparation process is simple and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of PERC solar cells, in particular to modified glass powder for PERC back silver paste and a preparation method and application thereof.
Background
Solar energy is a renewable clean energy source. Solar power generation does not produce greenhouse gases as does other traditional energy sources. The application of the photovoltaic technology can not only relieve the energy problem at the present stage, but also relieve the environmental pollution problem. Therefore, it is a constant trend in photovoltaic development to improve the quality of photovoltaic modules and reduce the cost of photovoltaic power generation.
The concept of PERC solar cells (Passivated Emitter and Rear cells) with backside passivation and local aluminum contacts was first introduced in 1989. In recent years, PERC solar cells have been rapidly developed and become one of the most important high efficiency photovoltaic products. Unlike conventional crystalline silicon solar cells, PERC solar cells require back silver paste to SiN during sinteringx/Al2O3The passivation layer plays a protective role, and meanwhile, in order to guarantee the quality of the assembly, the back electrode needs to meet certain welding performance.
The PERC back silver paste consists of conductive phase silver powder, bonding phase glass powder, an organic carrier and other auxiliaries. The organic carrier mainly plays a role in providing dispersion and printing forming of silver powder and glass powder, the silver powder mainly provides a conductive function, the glass powder only accounts for 1-5% of the total weight of the whole slurry, but the glass powder plays a crucial role in electrical performance and welding performance of a back electrode, if the glass powder corrodes a back passivation layer in a sintering process, although a high adhesive force can be obtained, the electrical performance of the PERC battery is obviously reduced due to the fact that the back passivation layer is damaged.
At present, reports of component blending, morphology control, particle size control and softening temperature control of glass powder are wide, and modification of the glass powder is less. Chinese patent CN109761504A discloses a glass powder activation silver plating process for silver paste on the back of a PERC battery, wherein a layer of nano silver particles is plated on the glass powder, so that on one hand, the high activity of the nano silver can be utilized to reduce the softening temperature of the glass powder in the sintering process, improve the fluidity of glass melt, promote electrodes to form a compact conductive network, reduce the series resistance of the battery and improve the filling factor of the battery; on the other hand, the mechanical strength of the contact between the electrode and the substrate can be improved by controlling the nano silver content of the silver @ glass powder composite powder, so that reliable contact can be obtained under the low-temperature sintering condition. However, the modification process is complicated and is not suitable for practical industrial production.
Disclosure of Invention
In order to solve the technical problems, the invention provides modified glass powder for PERC back silver paste and a preparation method and application thereof. The modified glass powder can improve the electrical property of the PERC battery under the condition of ensuring the adhesive force and the aging adhesive force of the back silver paste, and the preparation process is simple and is suitable for industrial production.
The specific technical scheme of the invention is as follows:
the modified glass powder for the silver paste on the back surface of the PERC comprises glass powder and a coupling agent grafted on the surface of the glass powder.
According to the invention, the coupling agent is grafted on the surface of the glass powder, so that the corrosion of the glass powder to the passivation layer of the PERC solar cell in the high-temperature sintering process can be reduced, and the specific mechanism is as follows: in the high-temperature sintering process, the groups grafted on the surface of the modified glass powder can be decomposed to absorb heat and take away a part of energy, so that the fluidity of the glass powder is reduced, and the corrosion of the glass powder to a passivation layer is reduced; meanwhile, the surface groups can also play a physical barrier role, and the contact between the glass powder and the passivation layer is reduced, so that the corrosion of the glass powder to the passivation layer is hindered. The modified glass powder has less corrosion to the passivation layer, so that the electrical property of the PERC solar cell can be improved (including improving open-circuit voltage, short-circuit current and filling factor, reducing series resistance and the like); moreover, because the grafting of the coupling agent does not change the components of the glass powder, when the grafting amount of the coupling agent is controlled within a certain range, the influence of the grafting amount on the adhesive force and the aging adhesive force of the back silver paste can be ignored.
In addition, the grafting of the coupling agent can be completed only by grinding, so that the industrial operation is easy, and the original technical equipment or process does not need to be replaced.
Preferably, the coupling agent comprises a silane coupling agent and/or a titanate coupling agent.
The glass powder modified window is wide, modified glass powder with different properties can be obtained by changing the type and the using amount of the coupling agent, and the controllability is high. When different back silver pastes, PERC solar cells and electrode sintering temperatures are used, the optimum type and amount of coupling agent can be determined through experiments.
Preferably, the coupling agent is a silane coupling agent containing an alkenyl group.
The alkenyl decomposition can absorb more heat, so that silane coupling agents (such as KH570 and the like) containing alkenyl can take away more heat in the sintering process, and are beneficial to reducing the fluidity of glass powder and reducing the corrosion of the glass powder to a passivation layer, thereby improving the electrical property of the battery.
When the coupling agent is adopted, the groups grafted to the surface of the glass powder are more easily decomposed and absorb heat (or absorb more heat), so that the effect of reducing the corrosion of the passivation layer can be better exerted, and the electrical property of the PERC solar cell is further improved.
Preferably, the glass powder comprises the following raw materials in parts by weight: bi2O330-45 parts of B2O35-20 parts of SiO220-30 parts of Al2O35-20 parts of CuO, 1-20 parts of MnO21-15 parts of ZnO, 1-10 parts of Na2CO31-5 parts of CaO and 1-5 parts of CaO, wherein the total weight part is 100 parts.
Preferably, D50 is 0.1-1.5 μm and D90 is 2-8 μm.
Preferably, the softening temperature is 600-800 ℃, and the crystallization temperature is 700-900 ℃.
A preparation method of the modified glass powder comprises the following steps:
(1) uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material;
(2) smelting the uniformly mixed materials to prepare uniform glass liquid;
(3) water quenching is carried out on the glass liquid to prepare coarse glass powder;
(4) and mixing the coarse glass powder with a coupling agent, grinding, drying and sieving to obtain the modified glass powder for the PERC back silver paste.
Preferably, in the step (2), the smelting temperature is 1100-1400 ℃, and the time is 30-60 min.
Preferably, in the step (4), the mass ratio of the coarse glass powder to the coupling agent is 100: 0.1-2.
When the relative dosage of the coupling agent is too small, the corrosion of the glass powder to the passivation layer can be effectively reduced, and the electrical property of the PECR battery is poor; when the relative dosage of the coupling agent is too large, the corrosion degree of the glass powder on the passivation layer is too low, and the adhesive force and the aging adhesive force of the back silver paste are obviously reduced. According to the invention, the dosage of the coarse glass powder and the coupling agent is controlled within the range of 100:0.1-2, so that the electrical property of the PECR battery can be greatly improved, and meanwhile, the adhesive force and the aging adhesive force of the back silver paste are almost kept unchanged.
Preferably, in the step (4), the grinding is carried out by ball milling, the rotating speed is 100-.
The PERC back silver paste comprises the following raw materials: silver powder, an organic carrier, an auxiliary agent and the modified glass powder.
Compared with the prior art, the invention has the following advantages:
(1) the modified glass powder can reduce the corrosion of the glass powder to a passivation layer to a certain extent under the condition of ensuring the adhesive force and the aging adhesive force of the back silver paste, so that the electrical property of the PERC battery is improved;
(2) the modified glass powder is simple and convenient to prepare, is easy to realize industrial operation, and does not need to replace the prior art equipment or process.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
The modified glass powder for the silver paste on the back surface of the PERC comprises glass powder and a coupling agent grafted on the surface of the glass powder. The coupling agent comprises a silane coupling agent and/or a titanate coupling agent, and is preferably a silane coupling agent containing alkenyl. The D50 of the modified glass powder is 0.1-1.5 μm, the D90 is 2-8 μm, the softening temperature is 600-800 ℃, and the crystallization temperature is 700-900 ℃.
The glass powder comprises the following raw materials in parts by weight: bi2O330-45 parts of B2O35-20 parts of SiO220-30 parts of Al2O35-20 parts of CuO, 1-20 parts of MnO21-15 parts of ZnO, 1-10 parts of Na2CO31-5 parts of CaO and 1-5 parts of CaO, wherein the total weight part is 100 parts.
A preparation method of the modified glass powder comprises the following steps:
(1) uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material;
(2) smelting the mixed material at 1100-1400 ℃ for 30-60min to prepare uniform glass liquid;
(3) water quenching is carried out on the glass liquid to prepare coarse glass powder;
(4) mixing the crude glass powder and a coupling agent according to a mass ratio of 100:0.1-2, ball-milling at a rotating speed of 100-.
The PERC back silver paste comprises the following raw materials: silver powder, an organic carrier, an auxiliary agent and the modified glass powder.
Example 1
The modified glass powder for the PERC back silver paste comprises glass powder and a silane coupling agent KH570 grafted on the surface of the glass powder. The D50 of the modified glass powder is 0.8-0.9 μm, the D90 is 3-5 μm, the softening temperature is 650-700 ℃, and the crystallization temperature is 800-850 ℃.
The glass powder comprises the following raw materials in parts by weight: bi2O336 parts of, B2O36 parts of SiO222 parts of Al2O36 parts of CuO, 10 parts of MnO212 parts of ZnO, 1 part of Na2CO32 parts and 5 parts of CaO.
A preparation method of the modified glass powder comprises the following steps:
(1) uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material;
(2) putting the uniformly mixed materials into a quartz crucible, then putting the quartz crucible into a muffle furnace, and smelting at 1250 ℃ for 40min to prepare uniform glass liquid;
(3) rapidly quenching the glass liquid with deionized water to obtain coarse glass powder;
(4) adding 100g of coarse glass powder and 1g of silane coupling agent KH570 into a ball milling tank, carrying out ball milling for 18h at the rotating speed of 200r/min, drying and sieving to obtain the modified glass powder for the PERC back silver paste.
The PERC back silver paste comprises the following raw materials in parts by weight: 60 parts of silver powder, 37.5 parts of organic carrier, 1.5 parts of modified glass powder and 1 part of auxiliary agent. The preparation method of the PERC back silver paste comprises the following steps:
s1: adding ethyl cellulose into a mixed solvent of butyl carbitol, butyl carbitol acetate, terpineol and alcohol ester dodeca, stirring at constant temperature in a water bath environment at 85 ℃ until the ethyl cellulose is completely dissolved, and cooling to room temperature to obtain a stable and uniform organic carrier;
s2: and uniformly mixing the silver powder, the organic carrier, the modified glass powder and the auxiliary agent according to the proportion, grinding by a three-roll mill and filtering by a stainless steel filter screen to obtain the PERC back silver paste.
Example 2
The modified glass powder for the PERC back silver paste comprises glass powder and a silane coupling agent KH560 grafted on the surface of the glass powder. The D50 of the modified glass powder is 0.9-1.0 μm, the D90 is 2.5-4.5 μm, the softening temperature is 600-660 ℃, and the crystallization temperature is 720-790 ℃.
The glass powder comprises the following raw materials in parts by weight: bi2O344 parts of, B2O310 parts of SiO222 parts of Al2O35 parts of CuO, 10 parts of MnO24 parts of ZnO, 1 part of Na2CO32 parts of CaO and 2 parts of CaO.
A preparation method of the modified glass powder comprises the following steps:
(1) uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material;
(2) placing the uniformly mixed materials in a quartz crucible, then placing the quartz crucible in a muffle furnace, and smelting at 1300 ℃ for 35min to prepare uniform glass liquid;
(3) rapidly quenching the glass liquid with deionized water to obtain coarse glass powder;
(4) adding 250g of coarse glass powder and 1.5g of silane coupling agent KH560 into a ball milling tank, carrying out ball milling for 22h at the rotating speed of 150r/min, drying and sieving to obtain the modified glass powder for the PERC back silver paste.
The PERC back silver paste comprises the following raw materials in parts by weight: 55 parts of silver powder, 42 parts of organic carrier, 2 parts of modified glass powder and 1 part of assistant. The preparation method of the PERC back silver paste comprises the following steps:
s1: adding ethyl cellulose into a mixed solvent of butyl carbitol, butyl carbitol acetate, terpineol and alcohol ester dodeca, stirring at constant temperature in a water bath environment at 85 ℃ until the ethyl cellulose is completely dissolved, and cooling to room temperature to obtain a stable and uniform organic carrier;
s2: and uniformly mixing the silver powder, the organic carrier, the modified glass powder and the auxiliary agent according to the proportion, grinding by a three-roll mill and filtering by a stainless steel filter screen to obtain the PERC back silver paste.
Example 3
The modified glass powder for the PERC back silver paste comprises glass powder and a silane coupling agent KH550 grafted on the surface of the glass powder. The D50 of the modified glass powder is 0.6-0.8 μm, the D90 is 2.0-4.0 μm, the softening temperature is 650-720 ℃, and the crystallization temperature is 810-870 ℃.
The glass powder comprises the following raw materials in parts by weight: bi2O332 parts of, B2O38 parts of SiO223 parts of Al2O38 parts of CuO 20 parts of MnO23 parts of ZnO, 2 parts of Na2CO33 parts and 1 part of CaO.
A preparation method of the modified glass powder comprises the following steps:
(1) uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material;
(2) putting the uniformly mixed materials into a quartz crucible, then putting the quartz crucible into a muffle furnace, and smelting for 40min at 1150 ℃ to prepare uniform glass liquid;
(3) rapidly quenching the glass liquid with deionized water to obtain coarse glass powder;
(4) adding 200g of coarse glass powder and 0.5g of silane coupling agent KH550 into a ball milling tank, ball milling at the rotating speed of 200r/min for 20 hours, drying, and sieving to obtain the modified glass powder for the PERC back silver paste.
The PERC back silver paste comprises the following raw materials in parts by weight: 63 parts of silver powder, 34.5 parts of organic carrier, 1 part of modified glass powder and 1.5 parts of auxiliary agent. The preparation method of the PERC back silver paste comprises the following steps:
s1: adding ethyl cellulose into a mixed solvent of butyl carbitol, butyl carbitol acetate, terpineol and alcohol ester dodeca, stirring at constant temperature in a water bath environment at 85 ℃ until the ethyl cellulose is completely dissolved, and cooling to room temperature to obtain a stable and uniform organic carrier;
s2: and uniformly mixing the silver powder, the organic carrier, the modified glass powder and the auxiliary agent according to the proportion, grinding by a three-roll mill and filtering by a stainless steel filter screen to obtain the PERC back silver paste.
Example 4
The modified glass powder for the PERC back silver paste comprises glass powder and isopropyl triisostearoyl titanate grafted on the surface of the glass powder. The D50 of the modified glass powder is 0.7-1.0 μm, the D90 is 2.8-5.0 μm, the softening temperature is 650-720 ℃, and the crystallization temperature is 810-870 ℃.
The glass powder comprises the following raw materials in parts by weight: bi2O340 parts of, B2O35 parts of SiO220 parts of Al2O310 parts of CuO, 15 parts of MnO25 parts of ZnO, 1 part of Na2CO32 parts of CaO and 2 parts of CaO.
A preparation method of the modified glass powder comprises the following steps:
(1) uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material;
(2) placing the uniformly mixed materials in a quartz crucible, then placing the quartz crucible in a muffle furnace, and smelting at 1200 ℃ for 40min to prepare uniform glass liquid;
(3) rapidly quenching the glass liquid with deionized water to obtain coarse glass powder;
(4) adding 500g of crude glass powder and 1g of isopropyl triisostearoyl titanate into a ball milling tank, carrying out ball milling for 16h at the rotating speed of 180r/min, drying and sieving to obtain the modified glass powder for the PERC back silver paste.
The PERC back silver paste comprises the following raw materials in parts by weight: 56 parts of silver powder, 41 parts of organic carrier, 2.5 parts of modified glass powder and 0.5 part of assistant. The preparation method of the PERC back silver paste comprises the following steps:
s1: adding ethyl cellulose into a mixed solvent of butyl carbitol, butyl carbitol acetate, terpineol and alcohol ester dodeca, stirring at constant temperature in a water bath environment at 85 ℃ until the ethyl cellulose is completely dissolved, and cooling to room temperature to obtain a stable and uniform organic carrier;
s2: and uniformly mixing the silver powder, the organic carrier, the modified glass powder and the auxiliary agent according to the proportion, grinding by a three-roll mill and filtering by a stainless steel filter screen to obtain the PERC back silver paste.
Example 5
This example is different from example 1 in that in step (4), the amount of the silane coupling agent KH570 used was 0.1g, and the other raw materials and the preparation method were the same as those of example 1.
Example 6
This example is different from example 1 in that in step (4), the amount of the silane coupling agent KH570 used was 2g, and the other raw materials and the preparation method were the same as those of example 1.
Example 7
This example differs from example 1 in that the silane coupling agent KH570 was replaced with isooctyltrimethoxysilane.
Comparative example 1
The glass powder comprises the following raw materials in parts by weight: bi2O336 parts of, B2O36 parts of SiO222 parts of Al2O36 parts of CuO, 10 parts of MnO212 parts of ZnO, 1 part of Na2CO32 parts and 5 parts of CaO.
The preparation method of the glass powder comprises the following steps:
(1) uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material;
(2) putting the uniformly mixed materials into a quartz crucible, then putting the quartz crucible into a muffle furnace, and smelting at 1250 ℃ for 40min to prepare uniform glass liquid;
(3) rapidly quenching the glass liquid with deionized water to obtain coarse glass powder;
(4) adding 100g of coarse glass powder into a ball milling tank, carrying out ball milling for 18h at the rotating speed of 200r/min, drying and sieving to obtain the modified glass powder for the PERC back silver paste.
The PERC back silver paste comprises the following raw materials in parts by weight: 60 parts of silver powder, 37.5 parts of organic carrier, 1.5 parts of glass powder and 1 part of assistant. The preparation method of the PERC back silver paste comprises the following steps:
s1: adding ethyl cellulose into a mixed solvent of butyl carbitol, butyl carbitol acetate, terpineol and alcohol ester dodeca, stirring at constant temperature in a water bath environment at 60 ℃ until the ethyl cellulose is completely dissolved, and cooling to room temperature to obtain a stable and uniform organic carrier;
s2: and uniformly mixing the silver powder, the organic carrier, the glass powder and the auxiliary agent according to the proportion, grinding by a three-roll mill and filtering by a stainless steel filter screen to obtain the PERC back silver paste.
Comparative example 2
This comparative example is different from example 1 in that in step (4), the amount of the silane coupling agent KH570 used was 0.05g, and the remaining raw materials and the preparation method were the same as those of example 1.
Comparative example 3
This comparative example is different from example 1 in that in step (4), the amount of the silane coupling agent KH570 used was 2.5g, and the remaining raw materials and the preparation method were the same as those of example 1.
Test example
The PERC back silver paste prepared in the examples 1-7 and the comparative examples 1-3 is adopted to prepare a solar cell piece according to a conventional method, namely the back silver paste is printed on a rear electrode of the PERC crystalline silicon solar cell through silk screen printing, dried and co-fired with the PERC back aluminum paste and the PERC front silver paste to form the rear electrode. And carrying out electrical property test, welding tension test and aging tension test on the sintered solar cell, wherein the electrical property test comprises open circuit voltage (Uoc), Fill Factor (FF), photoelectric conversion efficiency (Eta) and series resistance (Rs). The test results are shown in table 1.
TABLE 1
| Uoc/mV | FF/％ | Eta/％ | Rs/mΩ | Welding tension/N | Aged tensile force/N | |
| Example 1 | 687.1 | 80.88 | 22.82 | 2.48 | 6.0 | 4.8 |
| Example 2 | 686.3 | 80.87 | 22.79 | 2.51 | 5.9 | 4.6 |
| Example 3 | 687.0 | 80.92 | 22.85 | 2.45 | 6.3 | 5.0 |
| Example 4 | 686.7 | 80.89 | 22.80 | 2.49 | 5.6 | 4.4 |
| Example 5 | 686.7 | 80.83 | 22.80 | 2.50 | 6.0 | 5.0 |
| Example 6 | 687.0 | 80.88 | 22.83 | 2.48 | 5.7 | 4.9 |
| Example 7 | 686.4 | 80.85 | 22.79 | 2.50 | 5.9 | 4.8 |
| Comparative example 1 | 685.8 | 80.72 | 22.75 | 2.52 | 5.8 | 4.7 |
| Comparative example 2 | 686.1 | 80.80 | 22.78 | 2.51 | 5.9 | 4.7 |
| Comparative example 3 | 686.8 | 80.84 | 22.83 | 2.48 | 5.2 | 4.0 |
| Existing products | 685.7 | 80.85 | 22.76 | 2.54 | 5.4 | 2.8 |
As can be seen from table 1, compared with the existing commercial products, the modified glass frit of the present invention in examples 1 to 7 significantly improves the electrical properties of the cell (for PERC solar cells, the difficulty of improving the electrical properties is high, Uoc is improved by about 0.5mV, FF and Eta are improved by about 0.02%, Rs is reduced by about 0.02m Ω, i.e., there is a significant effect), and the aging adhesion is also improved.
Example 1 differs from comparative example 1 in that example 1 uses a coupling agent modified glass frit, whereas comparative example 1 uses an unmodified glass frit. As can be seen from table 1, the electrical properties of the battery of example 1 were significantly improved without significant changes in adhesion and aged adhesion, as compared to comparative example 1. The reason is presumed to be: in the high-temperature sintering process, the groups grafted on the surface of the modified glass powder can be decomposed and absorb heat to take away part of energy, so that the fluidity of the glass powder is reduced, the corrosion of the glass powder to a passivation layer is reduced, meanwhile, the surface groups can also play a physical blocking role, and the contact between the glass powder and the passivation layer is reduced, so that the corrosion of the glass powder to the passivation layer is hindered, and the electrical property of the PERC solar cell is improved; moreover, because the grafting of the coupling agent does not change the components of the glass powder, when the grafting amount of the coupling agent is controlled within a certain range, the influence on the adhesive force and the aging adhesive force of the back silver paste can be ignored.
In examples 1, 5, and 6 and comparative examples 2 and 3, the mass ratios of the coarse glass frit to the coupling agent were 100:1, 100:0.1, 100:2, 100:0.05, and 100:2.5, respectively. As can be seen from table 1, the electrical properties of the cells of examples 1, 5, 6 are significantly better than those of comparative example 1, and the adhesion and aged adhesion are similar to those of comparative example 1; the cell of comparative example 2 had poor electrical properties, and the adhesion and aged adhesion of comparative example 3 were significantly lower than those of comparative example 1. The reason is presumed to be: when the relative dosage of the coupling agent is too small, the corrosion of the glass powder to the passivation layer is difficult to be effectively reduced, and the electrical property of the PECR battery is poor; when the relative dosage of the coupling agent is too large, the corrosion degree of the glass powder on the passivation layer is too low, and the adhesive force and the aging adhesive force of the back silver paste are obviously reduced. According to the invention, the dosage of the coarse glass powder and the coupling agent is controlled within the range of 100:0.1-2, so that the electrical property of the PECR battery can be greatly improved, and meanwhile, the adhesive force and the aging adhesive force of the back silver paste are almost kept unchanged.
Example 1 is different from example 7 in that a silane coupling agent KH570 containing an alkenyl group was used in example 1, and isooctyltrimethoxysilane was used in example 7. As can be seen from table 1, the battery of example 1 has higher electrical properties than that of example 7. The reason is presumed to be: the alkenyl decomposition can absorb more heat, so that the silane coupling agent containing the alkenyl can take away more heat in the sintering process, the fluidity of the glass powder is favorably reduced, the corrosion of the glass powder to a passivation layer is reduced, and the electrical property of the battery is improved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The modified glass powder for the silver paste on the back surface of the PERC is characterized by comprising glass powder and a coupling agent grafted on the surface of the glass powder.
2. The modified glass frit of claim 1, wherein the coupling agent comprises a silane coupling agent and/or a titanate coupling agent.
3. The modified glass frit of claim 2, wherein the coupling agent is a silane coupling agent comprising an alkenyl group.
4. The modified glass frit according to claim 1, wherein the glass frit comprises the following raw materials in parts by weight: bi2O330-45 parts of B2O3 5-20 parts of SiO2 20-30 parts of Al2O3 5-20 parts of CuO, 1-20 parts of MnO2 1-15 parts of ZnO, 1-10 parts of Na2CO3 1-5 parts of CaO and 1-5 parts of CaO, wherein the total weight part is 100 parts.
5. The modified glass frit of claim 1, wherein D50 is 0.1 to 1.5 μ ι η and D90 is 2 to 8 μ ι η.
6. The modified glass frit of claim 1, wherein the softening temperature is 600-800 ℃ and the devitrification temperature is 700-900 ℃.
7. A method for preparing a modified glass frit according to any of claims 1 to 6, comprising the steps of:
(1) uniformly mixing all the raw materials of the glass powder to prepare a uniform mixed material;
(2) smelting the uniformly mixed materials to prepare uniform glass liquid;
(3) water quenching is carried out on the glass liquid to prepare coarse glass powder;
(4) and mixing the coarse glass powder with a coupling agent, grinding, drying and sieving to obtain the modified glass powder for the PERC back silver paste.
8. The production method according to claim 7, wherein in the step (4), the mass ratio between the coarse glass frit and the coupling agent is 100: 0.1-2.
9. The method as claimed in claim 7, wherein in the step (4), the grinding is performed by ball milling at a rotation speed of 100 and 200r/min for a grinding time of 12-24 h.
10. The PERC back silver paste is characterized by comprising the following raw materials: silver powder, an organic vehicle, an auxiliary agent and the modified glass frit according to any one of claims 1 to 6.
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