CN113257456A - Low-cost conductive paste for heterojunction solar cell and preparation method thereof - Google Patents
Low-cost conductive paste for heterojunction solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 122
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052709 silver Inorganic materials 0.000 claims abstract description 64
- 239000004332 silver Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001723 curing Methods 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- -1 anhydride compound Chemical class 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000013008 thixotropic agent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000011449 brick Substances 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000758 substrate Substances 0.000 description 14
- 230000000903 blocking effect Effects 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
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- 239000000853 adhesive Substances 0.000 description 6
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- 239000004411 aluminium Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 4
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- 238000005253 cladding Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002195 synergetic effect Effects 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
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
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- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—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
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The application relates to the field of heterojunction solar cells, and particularly discloses a low-cost conductive paste for a heterojunction solar cell and a preparation method thereof. The low-cost conductive paste for the heterojunction solar cell comprises the following raw materials: 60-90 parts of flake silver-coated aluminum powder, 1-10 parts of spherical silver powder, 1-10 parts of nano silver powder, 3-6 parts of resin, 1-3 parts of curing agent and 5-20 parts of auxiliary agent; the preparation method comprises the following steps: s1, preparing a mixed resin raw material; s2, mixing; and S3, preparing the conductive slurry. The low-cost conductive paste for the heterojunction solar cell adopts the flake silver-coated aluminum powder and the spherical silver powder, the flake silver-coated aluminum powder is favorable for improving the net-crossing performance of the conductive paste, the production cost of the conductive paste is reduced, the flake silver-coated aluminum powder is matched with the spherical silver powder for use, the net-crossing performance of the prepared conductive paste can be further improved, and the prepared conductive paste has good conductivity and has the characteristics of excellent net-crossing performance and good printing performance by adjusting the ratio of the flake silver-coated aluminum powder and the spherical silver powder.
Description
Technical Field
The application relates to the field of heterojunction solar cells, in particular to low-cost conductive paste for a heterojunction solar cell and a preparation method thereof.
Background
As the prevailing PERC battery technology in the market at present, due to the limitations of raw materials and production processes, the conversion efficiency of the battery is close to the bottleneck, and further improvement is difficult. The heterojunction battery has various natural advantages of high conversion efficiency, high double-sided rate, almost no light attenuation, good temperature characteristic, capability of using a thin silicon wafer, capability of superposing perovskite and the like due to the unique double-sided symmetrical structure and the excellent passivation effect of the amorphous silicon layer, and is considered as a mainstream battery technology in the post PERC age due to the short manufacturing process flow.
A heterojunction solar cell is a hybrid type solar cell made of a crystalline silicon substrate and an amorphous silicon thin film. The metallization of heterojunction cells usually employs a corresponding low-temperature curing conductive paste and curing is carried out at a temperature of around 200 ℃. The existing low-temperature slurry of the heterojunction battery mainly comprises silver powder, resin, a solvent and an additive.
The conductive paste mainly contains the flake silver powder, and compared with the spherical silver powder, the conductive paste mainly containing the flake silver powder has poorer net passing performance, so that the printing effect of subsequent screen printing is poorer, and the net passing performance of the conductive paste is more and more difficult along with the development of high-number narrow line width.
Meanwhile, the silver content in the low-temperature slurry of the heterojunction battery is generally higher, so that the production cost of the heterojunction battery is higher, the heterojunction battery has no cost advantage compared with other batteries, and the development of the heterojunction battery is hindered.
Disclosure of Invention
In order to solve the problems of poor mesh performance and high cost of the conductive paste, the application provides a low-cost conductive paste for a heterojunction solar cell and a preparation method thereof.
The application provides a low-cost conductive paste for a heterojunction solar cell and a preparation method thereof, and the preparation method adopts the following technical scheme:
in a first aspect, the present application provides a low-cost conductive paste for a heterojunction solar cell, which adopts the following technical scheme:
a low-cost conductive paste for a heterojunction solar cell comprises the following raw materials in parts by weight: 60-90 parts of flake silver-coated aluminum powder, 1-10 parts of spherical silver powder, 1-10 parts of nano silver powder, 3-6 parts of resin, 1-3 parts of curing agent and 5-20 parts of auxiliary agent.
By adopting the technical scheme, the relative molecular mass of silver is much larger than that of aluminum, and the specific surface area of the flaky silver coated aluminum powder is larger than that of the flaky silver powder under the same mass, so that the dispersibility is better, the dispersion in the conductive paste is more uniform, the agglomeration phenomenon among silver particles is reduced, the improvement of the screening performance of the conductive paste is facilitated, the use of noble metal silver powder is reduced, the production cost of the conductive paste is reduced, and the practical production and application are facilitated.
The aluminum is more active than silver and can be reduced before silver, so that the formation of silver ions is reduced, the migration of the silver ions is inhibited, the situation that the heterojunction solar cell prepared from the conductive paste is short-circuited is reduced, the potential safety hazard is reduced, and the product obtained after the aluminum is reduced is adhered to the surface of the aluminum, so that the further oxidation of the aluminum is inhibited, and the oxidation resistance of the aluminum is improved.
The spherical silver powder has better net passing performance, and the net passing performance of the prepared conductive paste can be further improved by matching with the flaky silver-coated aluminum powder. The contact of the spherical silver powder in the conductive paste is point contact, and the flaky silver-coated aluminum powder is in surface-to-surface contact besides the point contact, so that the contact resistance of the whole conductive paste can be reduced compared with the spherical silver powder, and the conductivity of the whole conductive paste is improved.
By adjusting the proportion of the spherical silver powder and the flaky silver-coated aluminum powder, the prepared conductive paste has good conductivity and has the characteristics of excellent screening performance and good printing performance.
The nano silver powder has the characteristic of low-temperature sintering, can be used as an auxiliary bonding phase after sintering and curing, has a synergistic effect with resin, improves the adhesive force between the conductive paste and the heterojunction solar cell substrate, ensures that the conductive paste is more firmly connected with the heterojunction solar cell substrate after curing, reduces the damage of high-temperature sintering to the cell structure, consumes less energy, has simple process, and is beneficial to actual production.
The conductive paste can meet the requirements of printing performance and good aspect ratio required by front silver paste.
Preferably, the average particle diameter of the silver-coated flaky aluminum powder is 1.5 to 3 μm, and the amount of silver particles coated on the surface of aluminum particles attached is 20 to 80 parts by weight with respect to 100 parts by weight of the aluminum powder.
Preferably, the preparation method of the flaky silver-coated aluminum powder comprises the following steps: mixing 8-10g of anhydrous copper sulfate, 20-25g of potassium sodium tartrate and 1000ml of water, stirring and dissolving to obtain a copper plating solution, then adding 25-30g of aluminum powder, stirring and reacting for 5-8min until the color of the solution changes from blue to colorless and the color of the aluminum powder changes from gray to brick red, filtering, washing and drying in vacuum to obtain copper-coated aluminum powder; and putting the copper-coated aluminum powder into a 10g/L ammonium sulfate solution, magnetically stirring for 10min, filtering, washing, adding a silver-ammonia solution, stirring for reaction for 10-15min, filtering, washing by deionized water and ethanol, and drying at 60-70 ℃ to obtain the flaky silver-coated aluminum powder.
Through adopting above-mentioned technical scheme, replace copper with the aluminium powder earlier for the even cladding of copper is on the aluminium powder surface, and the copper that utilizes the aluminium powder surface replaces the silver in the silver ammonia solution after that, thereby obtains silver-coated aluminium powder of flake, and in the preparation process, through the introduction of copper, can indirectly reduce the reaction potential who prepares silver cladding aluminium powder, and then reduces the deposition rate of silver cladding material, is favorable to obtaining better silver coating.
Preferably, the spherical silver powder has an average particle diameter of 1 to 2 μm.
Preferably, the resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, saturated polyester resin, hydroxylated acrylic resin and novolac epoxy resin.
By adopting the technical scheme, the bisphenol A epoxy resin has strong adhesion to the substrate after being cured, high mechanical strength and good electrical insulation and chemical corrosion resistance.
Bisphenol F epoxy resin has slightly lower heat resistance and slightly better corrosion resistance than bisphenol a epoxy resin.
The saturated polyester resin has good adhesive force, strong universality and outstanding weather resistance and flexibility.
The hydroxylated acrylic resin can be subjected to heating curing reaction with the epoxy resin, and the prepared conductive paste can have good performances in the aspects of hardness, adhesive force, light resistance and the like after curing.
The phenolic epoxy resin has good temperature resistance and good weldability.
Preferably, the curing agent is one of blocked isocyanate, amine compound and anhydride compound.
By adopting the technical scheme, the curing agents such as blocked isocyanate, amine compounds, anhydride compounds and the like are used as latent curing agents, do not react with the resin part at room temperature, can quickly react with the functional group part of the resin when heated, and are beneficial to improving the printing effect of the conductive paste on the substrate.
Preferably, the auxiliary agent is at least one of a reducing agent, a thixotropic agent, a leveling agent and a solvent; the reducing agent is one of sodium hypophosphite, hydrazine hydrate, ascorbic acid and formaldehyde; the thixotropic agent is one of fumed silica, organic bentonite, hydrogenated castor oil and polyamide wax; the leveling agent is one of an organic silicon type and an acrylate type; the solvent is one or more of benzyl alcohol, diethylene glycol ethyl ether acetate and DBE.
By adopting the technical scheme, the reducing agent can reduce the exposed part of aluminum oxide into aluminum powder in the curing process, and is favorable for inhibiting the migration of silver ions.
The thixotropic agent can improve the thixotropy of the prepared conductive paste, so that the printed lines have good aspect ratio.
The leveling agent can reduce the surface tension between the conductive slurry and the substrate, so that the conductive slurry has good wettability on the substrate, and the fluidity of the conductive slurry is further improved.
The addition of the solvent is beneficial to improving the compatibility of each raw material component in the conductive paste, so that the prepared conductive paste is more uniform.
In a second aspect, the present application provides a method for preparing a low-cost conductive paste for a heterojunction solar cell, which adopts the following technical scheme:
a preparation method of low-cost conductive paste for a heterojunction solar cell comprises the following steps:
s1, preparing a mixed resin raw material: weighing resin and a solvent, adding the resin into the solvent, completely dissolving in a constant-temperature water bath at 50-80 ℃, filtering by using a filter screen with 200-400 meshes, cooling to room temperature, and adjusting the viscosity to be 1-20Pa to obtain an organic carrier;
s2, mixing: stirring and mixing the silver-coated aluminum powder, the spherical silver powder and the nano silver powder in proportion for 5-10min to obtain conductive powder;
s3, preparing conductive slurry: the organic carrier, the mixed conductive powder, the curing agent and the auxiliary agent are stirred and mixed uniformly according to a certain proportion, then are ground and dispersed until the fineness reaches below 7 mu m, and finally are filtered by a filter screen with 600 meshes of 400 meshes to obtain the conductive slurry.
In summary, the present application has the following beneficial effects:
1. the flaky silver-coated aluminum powder and the spherical silver powder are adopted, so that the use of the flaky silver-coated aluminum powder is beneficial to improving the screening performance of the conductive paste, the production cost of the conductive paste is reduced, the flaky silver-coated aluminum powder is matched with the spherical silver powder for use, the screening performance of the prepared conductive paste can be further improved, and the prepared conductive paste has good conductivity, and has the characteristics of excellent screening performance and good printing performance by adjusting the proportion of the flaky silver-coated aluminum powder and the spherical silver powder.
2. The nano silver powder is preferably adopted in the solar cell substrate, has the characteristic of low-temperature sintering, and has a synergistic effect with resin after sintering and curing, so that the adhesive force between the slurry and the heterojunction solar cell substrate is improved, the damage of high-temperature sintering to the cell structure is reduced, the energy consumption is less, the process is simple, and the actual production is facilitated.
Detailed Description
The present application will be described in further detail with reference to examples.
The nano silver powder is purchased from Shanghai lane field nano material Co., Ltd, the granularity is 50nm, and the mark is XT-0801-4; the closed isocyanate is purchased from Guangzhou Zengmao chemical technology Co., Ltd, and has the model ZS-1890; the amine complex is purchased from Pingshan chemical company Limited, of Foshan City, with the model of HXR-90B; the anhydride compound is purchased from Guangzhou Yongshi chemical company Limited and has the model number of K-12; the novolac epoxy resin is purchased from Gallery Haoyuan anticorrosive material Limited, and has a model number of 901; the polyurethane resin is purchased from Shenzhen Jitian chemical Co., Ltd, and has the model number of F0401; the organic silicon type leveling agent is purchased from New Corning Material Co., Ltd, of Foshan city, and is a KMT-5510 leveling agent; the saturated polyester resin is purchased from Shanghai international trade company Limited, and has the model of GK-680.
The raw materials used in the following embodiments may be those conventionally commercially available unless otherwise specified.
Preparation example of silver-in-flake aluminum powder
Preparing flaky silver-coated aluminum powder: mixing 8g of anhydrous copper sulfate, 20g of sodium potassium tartrate and 1000ml of water, stirring and dissolving to obtain a copper plating solution, then adding 25g of aluminum powder, stirring and reacting for 5min until the color of the solution is changed from blue to colorless, the color of the aluminum powder is changed from gray to brick-red, filtering, washing and drying in vacuum to obtain copper-coated aluminum powder;
and putting the copper-coated aluminum powder into a 10g/L ammonium sulfate solution, magnetically stirring for 10min, filtering, washing, adding a silver-ammonia solution, stirring for reaction for 10-15min, filtering, washing by deionized water and ethanol, and drying at 60-70 ℃ to obtain the flaky silver-coated aluminum powder.
The average particle diameter of the silver-coated aluminum flake powder is 1.5-3 mu m.
Examples
Example 1
The application discloses heterojunction solar cell is with low-cost conductive paste, including following raw materials: the silver-coated flake aluminum powder is prepared by the preparation example 1, the average particle size of the spherical silver powder is 1 mu m, the phenolic epoxy resin is adopted as the resin, the blocked isocyanate is adopted as the curing agent, the auxiliary agent comprises a reducing agent and a solvent in a mass ratio of 1:10, the reducing agent is sodium hypophosphite, the solvent is benzyl alcohol, and the content of each component is shown in the following table 1.
The preparation method of the low-cost conductive paste for the heterojunction solar cell comprises the following steps:
s1, preparing a mixed resin raw material: weighing resin and a solvent, adding the resin into the solvent, completely dissolving the resin in a constant-temperature water bath at 50 ℃, filtering the solution by using a 200-mesh filter screen, cooling the solution to room temperature, and adjusting the viscosity to be 1Pa for s to obtain an organic carrier;
s2, mixing: stirring and mixing the silver-coated aluminum powder, the spherical silver powder and the nano silver powder in proportion for 5min to obtain conductive powder;
s3, preparing conductive slurry: the organic carrier, the mixed conductive powder, the curing agent and the auxiliary agent are stirred and mixed uniformly according to a certain proportion, then are ground and dispersed until the fineness reaches below 7 mu m, and finally are filtered by a filter screen with 400 meshes to obtain the conductive slurry.
Example 2
The application discloses heterojunction solar cell is with low-cost conductive paste, including following raw materials: the silver-coated flake aluminum powder is prepared from preparation example 1, the average particle size of the spherical silver powder is 2 microns, hydroxylated acrylic resin is adopted as the resin, an amine compound is adopted as the curing agent, the auxiliary agent comprises a reducing agent and a thixotropic agent in a mass ratio of 1:1, ascorbic acid is adopted as the reducing agent, organic bentonite is adopted as the thixotropic agent, and the content of each component is shown in the following table 1.
The preparation method of the low-cost conductive paste for the heterojunction solar cell comprises the following steps:
s1, preparing a mixed resin raw material: weighing resin and a solvent, adding the resin into the solvent, completely dissolving the resin in a constant-temperature water bath at 80 ℃, filtering the solution by using a 400-mesh filter screen, cooling the solution to room temperature, and adjusting the viscosity to 20Pa to obtain an organic carrier;
s2, mixing: stirring and mixing the silver-coated aluminum powder, the spherical silver powder and the nano silver powder in proportion for 10min to obtain conductive powder;
s3, preparing conductive slurry: the organic carrier, the mixed conductive powder, the curing agent and the auxiliary agent are stirred and mixed uniformly according to a certain proportion, then are ground and dispersed until the fineness reaches below 7 mu m, and finally are filtered by a 600-mesh filter screen to obtain the conductive slurry.
Example 3
The application discloses heterojunction solar cell is with low-cost conductive paste, including following raw materials: the silver-coated aluminum alloy comprises flake silver-coated aluminum powder, spherical silver powder, nano silver powder, resin, a curing agent and an auxiliary agent, wherein the flake silver-coated aluminum powder is prepared by the preparation example 1, the average particle size of the spherical silver powder is 1 mu m, the resin adopts bisphenol A epoxy resin and bisphenol F epoxy resin with the mass ratio of 1:1, the curing agent adopts an anhydride compound, the auxiliary agent is a thixotropic agent, the thixotropic agent adopts fumed silica, and the content of each component is shown in the following table 1.
The preparation method of the low-cost conductive paste for the heterojunction solar cell comprises the following steps:
s1, preparing a mixed resin raw material: weighing resin and a solvent, adding the resin into the solvent, completely dissolving the resin in a constant-temperature water bath at 65 ℃, filtering the solution by using a 300-mesh filter screen, cooling the solution to room temperature, and adjusting the viscosity to be 12Pa for s to obtain an organic carrier;
s2, mixing: stirring and mixing the silver-coated aluminum powder, the spherical silver powder and the nano silver powder in proportion for 8min to obtain conductive powder;
s3, preparing conductive slurry: the organic carrier, the mixed conductive powder, the curing agent and the auxiliary agent are stirred and mixed uniformly according to a certain proportion, then are ground and dispersed until the fineness reaches below 7 mu m, and finally are filtered by a 500-mesh filter screen to obtain the conductive slurry.
Example 4
The application discloses heterojunction solar cell is with low-cost conductive paste, including following raw materials: the silver-coated aluminum paste comprises flake silver-coated aluminum powder, spherical silver powder, nano silver powder, resin, a curing agent and an auxiliary agent, wherein the flake silver-coated aluminum powder is prepared by the preparation example 1, the average particle size of the spherical silver powder is 1 mu m, the resin adopts saturated polyester resin, the curing agent adopts closed isocyanate, the auxiliary agent is a leveling agent, the leveling agent adopts an organic silicon type, and the content of each component is shown in the following table 1.
The preparation method of the low-cost conductive paste for the heterojunction solar cell comprises the following steps:
s1, preparing a mixed resin raw material: weighing resin and a solvent, adding the resin into the solvent, completely dissolving the resin in a constant-temperature water bath at 65 ℃, filtering the solution by using a 300-mesh filter screen, cooling the solution to room temperature, and adjusting the viscosity to be 12Pa for s to obtain an organic carrier;
s2, mixing: stirring and mixing the silver-coated aluminum powder, the spherical silver powder and the nano silver powder in proportion for 8min to obtain conductive powder;
s3, preparing conductive slurry: the organic carrier, the mixed conductive powder, the curing agent and the auxiliary agent are stirred and mixed uniformly according to a certain proportion, then are ground and dispersed until the fineness reaches below 7 mu m, and finally are filtered by a 500-mesh filter screen to obtain the conductive slurry.
Example 5
The difference from example 1 is that DETA is used as the curing agent and the contents of the components are shown in Table 1 below.
Comparative example
Comparative example 1
The difference from example 1 is that the raw materials of the conductive paste are the flake silver powder, the resin, the curing agent and the auxiliary agent.
Comparative example 2
The difference from example 1 is that the silver-coated aluminum flakes were replaced with silver flakes, and the contents of the respective components are shown in table 1 below.
Comparative example 3
The difference from example 1 is that the spherical silver powder was replaced with the plate-like silver powder, and the contents of the respective components are shown in table 1 below.
Comparative example 4
The difference from example 1 is that the nano silver powder was replaced with the spherical silver powder, and the contents of the respective components are shown in table 1 below.
TABLE 1 ingredient content table
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Flaky silver-coated aluminum powder | 60 | 90 | 75 | 75 | 75 | 75 | 75 | 75 |
| Spherical silver powder | 10 | 1 | 5 | 5 | 5 | 5 | 5 | 5 |
| Nano silver powder | 10 | 1 | 5 | 5 | 5 | 5 | 5 | 5 |
| Resin composition | 3 | 6 | 5 | 5 | 5 | 5 | 5 | 5 |
| Curing agent | 1 | 3 | 2 | 2 | 2 | 2 | 2 | 2 |
| Auxiliary agent | 5 | 20 | 13 | 13 | 13 | 13 | 13 | 13 |
Performance test
(1) And (3) carrying out a screening test: the conductive pastes prepared in examples 1 to 5 and comparative examples 1 to 4 were respectively printed on HIT cells of 120mm × 110mm × 95mm, a screen printing plate of 360 mesh-16 μm line diameter-30 μm line width specification was selected, continuous printing was performed for 3 hours, and the blocking and breaking conditions were observed, and the test results are shown in Table 2 below.
(2) Line aspect ratio after curing: after the conductive pastes prepared in examples 1-5 and comparative examples 1-4 were cured on HIT cells of 120mm × 110mm × 95mm, the aspect ratio of the grid lines was measured according to standard SJ/T11759-.
(3) Adhesion test (adhesion characterized by welding pull): the conductive pastes prepared in the examples 1 to 5 and the comparative examples 1 to 4 are respectively printed on HIT batteries with the thickness of 120mm multiplied by 110mm multiplied by 95mm by using a screen printing plate with the specification of 360 meshes to 16 mu m line diameter to 30 mu m line width, a square pattern with the length of 10cm and the width of 1mm is printed, welding is carried out after solidification, and the welding tension is tested, wherein the larger the welding tension is, the larger the adhesive force is, and the test results are shown in the following table 2.
(4) Conductivity test (conductivity characterized by resistivity): the conductive pastes prepared in the examples 1 to 5 and the comparative examples 1 to 4 are respectively printed with a square pattern with the length of 10cm and the width of 1mm on a HIT battery with the thickness of 120mm multiplied by 110mm multiplied by 95mm by selecting a screen printing plate with the specification of 360 meshes to 16 mu m line diameter to 30 mu m line width, the resistance value is measured after curing, and the resistivity (rho) is converted according to the formula rho = R multiplied by delta multiplied by d/L (omega is cm);
r-resistance value (omega) of the tested sample;
delta-thickness (cm) of the test specimen;
d-width (cm) of the sample to be measured;
l-the length (cm) of the sample to be measured;
the lower the resistivity, the better the conductivity, and the test results are shown in table 2 below.
TABLE 2 test results of examples and comparative examples
| Net passing property | Line aspect ratio | Welding tension/(N/mm) | Resistance rate/omega is into cm | |
| Example 1 | Continuously printing for 3h without blocking the net | 0.37 | 2.0 | 7.7×10-6 |
| Example 2 | Continuously printing for 3h without blocking the net | 0.38 | 2.0 | 7.8×10-6 |
| Example 3 | Continuously printing for 3h without blocking the net | 0.38 | 1.9 | 7.6×10-6 |
| Example 4 | Continuously printing for 3h without blocking the net | 0.37 | 1.9 | 7.8×10-6 |
| Example 5 | Continuously printing for 3h without blocking the net | 0.34 | 1.7 | 8.0×10-6 |
| Comparative example 1 | Continuously printing for 1.5h, blocking the net | 0.29 | 1.8 | 7.2×10-6 |
| Comparative example 2 | Continuously printing for 2.5h, blocking the net | 0.33 | 1.8 | 7.4×10-6 |
| Comparative example3 | Continuously printing for 2.5h, blocking the net | 0.32 | 1.7 | 7.5×10-6 |
| Comparative example 4 | Continuously printing for 3h without blocking the net | 0.34 | 1.5 | 8.0×10-6 |
In summary, the following conclusions can be drawn:
1. as can be seen by combining example 1 and comparative examples 1-2, and table 2, the addition of the silver-coated flake aluminum powder can improve the reticulation of the conductive paste, probably because: the relative molecular mass of the silver is much larger than that of the aluminum, and after the aluminum powder is coated by the silver powder, the specific surface area of the flaky silver coated aluminum powder is larger than that of the flaky silver powder under the same mass, so that the dispersibility is better, the dispersion in the conductive paste is more uniform, the agglomeration phenomenon among silver particles is reduced, and the improvement of the screening performance of the conductive paste is facilitated.
2. Combining examples 1-3 and comparative examples 1-3 and combining table 2, it can be seen that the co-addition of the flake-like silver-coated aluminum powder and the spherical silver powder can further improve the reticulation of the conductive paste, probably because: the screening performance of the spherical silver powder is excellent, the screening performance of the prepared conductive paste can be further improved by matching with the flaky silver-coated aluminum powder, and the prepared conductive paste has good conductivity and the characteristics of excellent screening performance and good printing performance by adjusting the proportion of the spherical silver powder and the flaky silver-coated aluminum powder.
3. As can be seen by combining example 1 and comparative example 4 with table 2, the addition of the nano silver powder can improve the adhesion between the conductive paste and the battery substrate, which may be due to: the nano silver powder has the characteristic of low-temperature sintering, can be used as an auxiliary bonding phase after sintering and curing, and has a synergistic effect with resin, so that the adhesive force between the conductive paste and the heterojunction solar cell substrate is improved, and the conductive paste is more firmly connected with the heterojunction solar cell substrate after curing.
4. As can be seen from the combination of examples 1 and 5 and table 2, the curing agent employs the blocked isocyanate, the amine compound, and the anhydride compound, which are beneficial to improving the printing effect of the conductive paste on the heterojunction solar cell substrate, and obtaining the grid line with a more appropriate aspect ratio, and the reasons may be that: the curing agent such as blocked isocyanate, amine compound, anhydride compound and the like is used as a latent curing agent, does not react with a resin part at room temperature, can quickly react with a functional group part of the resin when heated, and is beneficial to improving the printing effect of the conductive paste on the substrate.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The low-cost conductive paste for the heterojunction solar cell is characterized by comprising the following raw materials in parts by weight: 60-90 parts of flake silver-coated aluminum powder, 1-10 parts of spherical silver powder, 1-10 parts of nano silver powder, 3-6 parts of resin, 1-3 parts of curing agent and 5-20 parts of auxiliary agent.
2. The low-cost electroconductive paste for a heterojunction solar cell of claim 1, wherein: the average particle diameter of the silver-coated flaky aluminum powder is 1.5 to 3 mu m, and the adhesion amount of silver particles coated on the surfaces of aluminum particles is 20 to 80 parts by weight relative to 100 parts by weight of the aluminum powder.
3. The low-cost conductive paste for a heterojunction solar cell of claim 2, wherein: the preparation method of the flaky silver-coated aluminum powder comprises the following steps: mixing 8-10g of anhydrous copper sulfate, 20-25g of potassium sodium tartrate and 1000ml of water, stirring and dissolving to obtain a copper plating solution, then adding 25-30g of aluminum powder, stirring and reacting for 5-8min until the color of the solution changes from blue to colorless and the color of the aluminum powder changes from gray to brick red, filtering, washing and drying in vacuum to obtain copper-coated aluminum powder; and putting the copper-coated aluminum powder into a 10g/L ammonium sulfate solution, magnetically stirring for 10min, filtering, washing, adding a silver-ammonia solution, stirring for reaction for 10-15min, filtering, washing by deionized water and ethanol, and drying at 60-70 ℃ to obtain the flaky silver-coated aluminum powder.
4. The low-cost electroconductive paste for a heterojunction solar cell of claim 1, wherein: the average grain diameter of the spherical silver powder is 1-2 μm.
5. The low-cost electroconductive paste for a heterojunction solar cell of claim 1, wherein: the resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, saturated polyester resin, hydroxylated acrylic resin, novolac epoxy resin and saturated polyester resin.
6. The low-cost electroconductive paste for a heterojunction solar cell of claim 1, wherein: the curing agent is one of blocked isocyanate, amine complex and anhydride compound.
7. The low-cost electroconductive paste for a heterojunction solar cell of claim 1, wherein: the auxiliary agent is at least one of a reducing agent, a thixotropic agent, a flatting agent and a solvent;
the reducing agent is one of sodium hypophosphite, hydrazine hydrate, ascorbic acid and formaldehyde;
the thixotropic agent is one of fumed silica, organic bentonite, hydrogenated castor oil and polyamide wax;
the leveling agent is one of an organic silicon type and an acrylate type;
the solvent is one or more of benzyl alcohol, diethylene glycol ethyl ether acetate and DBE.
8. The method of claim 1, comprising the steps of:
s1, preparing a mixed resin raw material: weighing resin and a solvent, adding the resin into the solvent, completely dissolving in a constant-temperature water bath at 50-80 ℃, filtering by using a filter screen with 200-400 meshes, cooling to room temperature, and adjusting the viscosity to be 1-20Pa to obtain an organic carrier;
s2, mixing: stirring and mixing the silver-coated aluminum powder, the spherical silver powder and the nano silver powder in proportion for 5-10min to obtain conductive powder;
s3, preparing conductive slurry: the organic carrier, the mixed conductive powder, the curing agent and the auxiliary agent are stirred and mixed uniformly according to a certain proportion, then are ground and dispersed until the fineness reaches below 7 mu m, and finally are filtered by a filter screen with 600 meshes of 400 meshes to obtain the conductive slurry.
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