CN115565715A - Positive electrode silver paste and preparation method and application thereof - Google Patents
Positive electrode silver paste and preparation method and application thereof Download PDFInfo
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- CN115565715A CN115565715A CN202211315608.4A CN202211315608A CN115565715A CN 115565715 A CN115565715 A CN 115565715A CN 202211315608 A CN202211315608 A CN 202211315608A CN 115565715 A CN115565715 A CN 115565715A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 118
- 239000004332 silver Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 66
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 56
- 239000011521 glass Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 28
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims abstract description 18
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940116411 terpineol Drugs 0.000 claims abstract description 18
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims abstract description 12
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000006259 organic additive Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 32
- 239000000725 suspension Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000007639 printing Methods 0.000 description 13
- 239000012530 fluid Substances 0.000 description 11
- 238000007650 screen-printing Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000008595 infiltration Effects 0.000 description 7
- 238000001764 infiltration Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 6
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 6
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007767 bonding agent Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- -1 silver-aluminum Chemical compound 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a positive electrode silver paste and a preparation method and application thereof. The preparation raw materials of the anode silver paste comprise a powder material and a solvent carrier, wherein the powder material comprises silver powder and sintered glass powder, the solvent carrier comprises a main phase solution and a secondary phase solution, and the main phase solution comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the secondary phase liquid comprises at least one of glycerol and glycol. This positive pole silver thick liquid need not add adhesive and organic additive for the impurity that the silver thick liquid obtained is still less, and the silver thick liquid has high conductivity, can improve the photoelectric conversion efficiency and the stability of battery. The invention also provides the anode silver paste and a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a positive electrode silver paste and a preparation method and application thereof.
Background
Solar energy is an important renewable energy source, and a photovoltaic power generation system is a device for directly converting solar energy into electric energy.
The conductive silver paste is a functional material taking silver powder as a base material. The conductive silver paste has strict requirements on the constituent substances, and the quality, the content, the shape and the size of the conductive silver paste have influence on the performance of the silver paste. The main function of the silver paste is to concentrate current. The basic requirements of the anode silver paste are good printing performance, proper height-width ratio, good ohmic contact with a silicon wafer and low contact resistance, so that the cell has higher photoelectric conversion efficiency.
The current conductive silver paste is mainly a viscous paste of a mechanical mixture composed of high-purity (99.9%) silver powder, glass oxide, an organic carrier, an organic additive and the like. The silver powder is a conductive phase, provides excellent conductivity after being sintered into a film, and the quality of the silver powder directly influences the volume resistance, contact resistance and the like of an electrode material, and further influences the conversion efficiency. The glass oxide, i.e. the glass powder, is molten when sintered at high temperature and burns through the surface of the silicon wafer, and plays a determining role in the sintering of silver powder and the formation of silver-silicon ohmic contact. The organic carrier and the organic additive are used as a temporary bonding phase, so that the paste has certain rheological property to meet the requirements of screen printing. However, the organic additives increase the step of discharging the photoresist, and the organic additives cannot be completely discharged, thereby affecting the performance of the solar cell, and exhaust gas is generated during the photoresist discharging process.
Therefore, a new positive electrode silver paste needs to be developed.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the positive electrode silver paste provided by the invention does not contain a bonding agent and an organic additive, so that the impurities of the silver paste are less, the silver paste has high conductivity, and the photoelectric conversion efficiency and stability of a battery can be improved.
The invention also provides a preparation method of the anode silver paste.
The invention also provides application of the anode silver paste in a solar cell.
The invention provides a positive electrode silver paste, which is prepared from raw materials including a powder material and a solvent carrier, wherein the powder material includes silver powder and sintered glass powder, the solvent carrier includes a primary liquid and a secondary liquid, and the primary liquid includes at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the secondary phase liquid comprises at least one of glycerol and glycol.
The invention relates to a technical scheme of the anode silver paste, which at least has the following beneficial effects:
the preparation raw materials of the anode silver paste comprise a powder material and a solvent carrier, wherein the powder material comprises silver powder and sintered glass powder, the solvent carrier comprises a primary solution and a secondary solution, and the primary solution comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the secondary phase liquid comprises at least one of glycerol and glycol. The primary term liquid is used as the integral carrier liquid of the slurry, and the secondary term liquid is used for regulating and controlling the integral rheological property.
According to the positive electrode silver paste, the primary phase liquid comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, and the secondary phase liquid comprises at least one of glycerol and ethylene glycol. The main solution and the secondary solution are not completely miscible, and the main solution and the secondary solution are completely miscible. The main item liquid and the secondary item liquid have different infiltration rates and different contact angles, so that a capillary suspension effect can be generated, and by means of the capillary suspension effect, the positive electrode silver paste disclosed by the invention does not need a bonding agent or an additive, so that the impurities of the silver paste are less, the silver paste has the advantage of high conductivity, and the photoelectric conversion efficiency and the stability of a battery can be improved.
The anode silver paste is suitable for screen printing products, has simple and efficient printing process and low cost, and can be used for industrial large-scale production.
The anode silver paste does not contain a high-molecular binder and an additive, and does not need a step of binder removal in a sintering process after printing, so that the manufacturing flow and the production cost are saved.
The positive electrode silver paste disclosed by the invention is prepared into conductive silver pastes with different rheological properties by using different preparation methods, and can be suitable for more electronic fields.
The components in the main solution of the anode silver paste are completely mutually soluble. The main solution and the secondary solution are not completely miscible. The two fluids have different infiltration rates and different contact angles.
The positive silver grid line of the PERC battery is a pure silver grid line, and other battery technologies are silver-aluminum grid lines or other metal/nonmetal material grid lines. The minimum criteria for PERC cells in the current industry are an average width of 35 μm and an average height of 8 μm. When the positive silver paste is used for printing the positive silver grid line of the PERC battery, the average width is 35 mu m, the average height is 8 mu m, and optimally, the printing effect of about 28 mu m of the average width and about 9 mu m of the average height can be obtained. The grid can not be broken in the printing process, and therefore, the method is suitable for the positive grid line of the solar PERC battery.
According to some embodiments of the invention, the preparation feedstock comprises:
powder material: 85 to 95 portions of the mixture of the components,
solvent carrier: 8 to 12 portions.
According to some embodiments of the invention, the preparation feedstock comprises:
powder material: 89 to 92 portions of the mixture of the components,
solvent carrier: 8.5 to 12 portions.
According to some embodiments of the invention, the preparation feedstock comprises:
powder material: 89.9 to 91.5 portions of,
solvent carrier: 8.5 to 10.5 portions.
According to some embodiments of the invention, the volume percentage of the secondary phase in the solvent carrier is between 0.5% and 7%.
According to some embodiments of the invention, the silver powder has a D50 ranging from 1 μm to 2 μm.
According to some embodiments of the invention, the silver powder has a D50 ranging from 1.2 μm to 2 μm.
According to some embodiments of the invention, the silver powder has a D50 ranging from 1.4 μm to 2 μm.
According to some embodiments of the invention, the silver powder has an effective content of 99.9% or more.
The sintered glass powder is light green powder at 25 ℃, the effective content is more than or equal to 99.0 percent, the softening temperature is about 342 ℃, the water content is less than or equal to 0.5 percent, and the D50 is about 1.92 mu m.
The second aspect of the invention provides a method for preparing the positive electrode silver paste, which comprises the following steps:
s1: sequentially adding the sintered glass powder and the silver powder into the secondary phase solution;
s2: and (3) adding the main solution into the product obtained in the step (S1), and uniformly mixing to obtain the anode silver paste.
The invention relates to a technical scheme in a preparation method of anode silver paste, which at least has the following beneficial effects:
the invention relates to a preparation method of anode silver paste, which has different liquid adding sequences and different generated soaking effects. The order of addition of the liquids has an effect on the overall wetting, since a completely sufficient homogeneous mixing cannot be achieved. Therefore, the sintered glass powder and the silver powder are required to be sequentially added into the secondary solution in sequence; and then adding the main item solution into the product, and uniformly mixing to obtain the anode silver paste.
Capillary suspensions, which are systems in which particles are dispersed in a continuous liquid phase and stabilized using a small amount of immiscible secondary fluid phase, are the main cause of long-term stability of the suspension due to the formation of capillary bridges between the particles as a result of the addition of the secondary fluid. Whether the secondary fluid has better or less wettability for the particles than the bulk fluid, capillary bridging occurs. The rheology of the capillary suspension can be significantly altered by minimal changes in the overall concentration of the secondary immiscible fluid. Capillary bridging can be used to stabilize particle suspensions and to fine tune their rheological properties. The invention relates to a preparation method of a positive electrode silver paste, wherein a primary secondary liquid comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, and a secondary liquid comprises at least one of glycerol and ethylene glycol. The main solution and the secondary solution are not completely miscible, and the main solution and the secondary solution are completely miscible. The main phase liquid and the secondary phase liquid have different infiltration rates and different contact angles, so that a capillary suspension effect can be generated, and by means of the capillary suspension effect, the positive electrode silver paste disclosed by the invention does not need an adhesive or an additive, so that the impurities of the silver paste are less, the silver paste has the advantage of high conductivity, and the photoelectric conversion efficiency and the stability of a battery can be improved.
According to some embodiments of the invention, in step S2, the mixing is performed in a spin coater.
According to some embodiments of the invention, the spin coater has a speed of 1000rpm to 1500rpm.
According to some embodiments of the invention, the spin coater has a speed of 1200rpm to 1500rpm.
According to some embodiments of the invention, the spin coater has a rotation time of 1000s to 2000s.
According to some embodiments of the invention, the spin coater has a spin time of 1500s to 2000s.
The third aspect of the invention provides an application of the positive electrode silver paste in a solar cell.
The invention relates to a technical scheme of application of anode silver paste in a solar cell, which at least has the following beneficial effects:
the preparation raw materials of the anode silver paste comprise a powder material and a solvent carrier, wherein the powder material comprises silver powder and sintered glass powder, the solvent carrier comprises a main phase solution and a secondary phase solution, and the main phase solution comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the secondary phase liquid comprises at least one of glycerol and glycol. The primary term liquid is used as the integral carrier liquid of the slurry, and the secondary term liquid is used for regulating and controlling the integral rheological property. Wherein, the main phase liquid and the secondary phase liquid are not completely miscible, and the main phase liquid and the secondary phase liquid are completely miscible. The main item liquid and the secondary item liquid have different infiltration rates and different contact angles, so that a capillary suspension effect can be generated, and by means of the capillary suspension effect, the positive electrode silver paste disclosed by the invention does not need a bonding agent or an additive, so that the impurities of the silver paste are less, the silver paste has the advantage of high conductivity, and the photoelectric conversion efficiency and the stability of a battery can be improved. Therefore, when the solar cell is used for a solar cell, the solar cell can have higher photoelectric conversion efficiency and stability.
Drawings
Figure 1 is a schematic view of a printed grid line.
Fig. 2 is a partially enlarged schematic view under a printed grid line 3D microscope.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
In some embodiments of the invention, the invention provides a cathode silver paste, the preparation raw materials comprise a powder material and a solvent carrier, the powder material comprises a silver powder and a sintered glass powder, the solvent carrier comprises a primary phase solution and a secondary phase solution, the primary phase solution comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the secondary collar liquid comprises at least one of glycerol and glycol.
The preparation method of the cathode silver paste comprises the steps of preparing raw materials including a powder material and a solvent carrier, wherein the powder material includes a silver powder and a sintered glass powder, the solvent carrier includes a primary solution and a secondary solution, and the primary solution includes at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the secondary collar liquid comprises at least one of glycerol and glycol. The primary liquid is used as the integral carrier liquid of the slurry, and the secondary liquid is used for regulating and controlling the integral rheological property.
It can be further understood that in the positive electrode silver paste of the present invention, the primary secondary solution includes at least two of terpineol, o-benzene, and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, and the secondary solution includes at least one of glycerol and ethylene glycol. The main solution and the secondary solution are not completely miscible, and the main solution and the secondary solution are completely miscible. The main item liquid and the secondary item liquid have different infiltration rates and different contact angles, so that a capillary suspension effect can be generated, and by means of the capillary suspension effect, the positive electrode silver paste disclosed by the invention does not need a bonding agent or an additive, so that the impurities of the silver paste are less, the silver paste has the advantage of high conductivity, and the photoelectric conversion efficiency and the stability of a battery can be improved.
The positive silver paste is suitable for screen printing products, and has the advantages of simple and efficient printing process, low cost and capability of industrial large-scale production.
The positive electrode silver paste does not contain a high-molecular binder and an additive, and a glue discharging step is not needed in a sintering process after printing, so that the manufacturing flow and the production cost are saved.
The conductive silver paste with different rheological properties can be obtained by using different preparation methods, and can be suitable for more electronic fields.
In addition, the components in the main solution of the anode silver paste are completely mutually soluble. The main solution and the secondary solution are not completely miscible. The two fluids have different wetting rates and different contact angles.
Furthermore, the anode silver paste is suitable for the anode grid line of the solar PERC battery, and has the average width of 35 mu m and the average height of 8 mu m.
In some embodiments of the invention, the volume percent of the secondary phase solution in the solvent carrier is between 0.5% and 7%.
In some embodiments of the present invention, the D50 of the silver powder ranges from 1 μm to 2 μm.
In some embodiments of the present invention, the silver powder has a D50 ranging from 1.2 μm to 2 μm.
In some embodiments of the present invention, the silver powder has a D50 ranging from 1.4 μm to 2 μm.
In some embodiments of the invention, the effective content of silver powder is 99.9% or more.
The sintered glass powder is light green powder at 25 ℃, the effective content is more than or equal to 99.0 percent, the softening temperature is about 342 ℃, the water content is less than or equal to 0.5 percent, and the D50 is about 1.92 mu m.
In some embodiments of the present invention, the present invention also provides a method for preparing a positive electrode silver paste, comprising the steps of:
s1: sequentially adding sintered glass powder and silver powder into the secondary solution;
s2: and (3) adding the main item solution into the product obtained in the step (S1), and uniformly mixing to obtain the anode silver paste.
It should be noted that, in the method for preparing the positive electrode silver paste of the present invention, the liquid addition sequence is different, and the produced wetting effect is different. The order of addition of the liquids has an effect on the overall wetting, since a completely sufficient homogeneous mixing cannot be achieved. Therefore, the sintered glass powder and the silver powder are sequentially added into the secondary solution according to the sequence; and then adding the main item solution into the product, and uniformly mixing to obtain the anode silver paste.
In particular, capillary suspensions are systems in which particles are dispersed in a continuous liquid phase and stabilized using a small amount of immiscible secondary fluid phase, the addition of which results in the formation of capillary bridges between the particles, which is a major cause of long-term stability of the suspension. Whether the secondary fluid wets the particles better or second to the bulk fluid, capillary bridging occurs. The rheology of the capillary suspension can be significantly altered by minimal changes in the overall concentration of the secondary immiscible fluid. Capillary bridging can be used to stabilize particle suspensions and to fine tune their rheological properties. The invention relates to a preparation method of a positive electrode silver paste, wherein a primary secondary liquid comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, and a secondary liquid comprises at least one of glycerol and ethylene glycol. The main solution and the secondary solution are not completely miscible, and the main solution and the secondary solution are completely miscible. The main item liquid and the secondary item liquid have different infiltration rates and different contact angles, so that a capillary suspension effect can be generated, and by means of the capillary suspension effect, the positive electrode silver paste disclosed by the invention does not need a bonding agent or an additive, so that the impurities of the silver paste are less, the silver paste has the advantage of high conductivity, and the photoelectric conversion efficiency and the stability of a battery can be improved.
In some embodiments of the present invention, in step S2, the mixing is performed in a spin coater.
In some embodiments of the invention, the spin coater has a speed of 1000rpm to 1500rpm.
In some embodiments of the invention, the spin coater has a speed of 1200rpm to 1500rpm.
In some embodiments of the present invention, the spin time of the spin coater is 1000s to 2000s.
In some embodiments of the present invention, the spin time of the spin coater is 1500s to 2000s.
In some embodiments of the invention, the invention also provides application of the positive electrode silver paste in a solar cell.
The preparation raw materials of the positive electrode silver paste comprise a powder material and a solvent carrier, wherein the powder material comprises silver powder and sintered glass powder, the solvent carrier comprises a primary phase solution and a secondary phase solution, and the primary phase solution comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the secondary collar liquid comprises at least one of glycerol and glycol. The primary liquid is used as the integral carrier liquid of the slurry, and the secondary liquid is used for regulating and controlling the integral rheological property. Wherein, the main phase liquid and the secondary phase liquid are not completely miscible, and the main phase liquid and the secondary phase liquid are completely miscible. The main item liquid and the secondary item liquid have different infiltration rates and different contact angles, so that a capillary suspension effect can be generated, and by means of the capillary suspension effect, the positive electrode silver paste disclosed by the invention does not need a bonding agent or an additive, so that the impurities of the silver paste are less, the silver paste has the advantage of high conductivity, and the photoelectric conversion efficiency and the stability of a battery can be improved. Therefore, when the solar cell is used for a solar cell, the solar cell can have higher photoelectric conversion efficiency and stability.
The technical solution of the present invention will be better understood with reference to the following specific examples.
Example 1
This example prepares a positive electrode silver paste.
The silver paste contains 91wt% of powder material and 9wt% of solvent carrier.
The powder material contains:
88wt% of silver powder;
3wt% of sintered glass powder.
The solvent carrier contains:
glycerol accounting for 4% of the total volume of the liquid;
terpineol accounting for 38.4 percent of the total volume of the liquid;
57.6 percent of o-benzene based on the total volume of the liquid.
The preparation method comprises the following steps:
s1: according to the proportion, the glycerol is placed in a container;
s2: adding sintered glass powder and silver powder into a container in which glycerol is placed, and then sequentially dropwise adding terpineol and o-benzene;
and S3, sealing the container, putting the container into a spin coater, and rotating the container for 1500 seconds at the rotating speed of 1200rpm under manual vacuum to fully and uniformly mix the components in the container to obtain the anode silver paste.
Comparative example 1
The comparative example prepares a positive electrode silver paste.
The silver paste contains 91wt% of powder material and 9wt% of solvent carrier.
The powder material contains:
88wt% of silver powder;
3wt% of sintered glass powder.
The solvent carrier contains:
glycerol accounting for 4% of the total volume of the liquid;
terpineol accounting for 38.4 percent of the total volume of the liquid;
o-benzene in an amount of 57.6% by volume of the total liquid.
The preparation method comprises the following steps:
s1: putting silver powder and sintered glass powder into a container according to the mixture ratio;
s2: sequentially dripping glycerol, terpineol and o-benzene into a container in which the silver powder and the sintered glass powder are placed;
and S3, sealing the container, putting the container into a spin coater, and rotating the container for 1500 seconds at the rotating speed of 1200rpm under manual vacuum to fully and uniformly mix the components in the container to obtain the anode silver paste.
Comparative example 2
The comparative example prepares a positive electrode silver paste.
The silver paste contains 91wt% of powder material and 9wt% of solvent carrier.
The powder material contains:
88wt% of silver powder;
3wt% of sintered glass powder.
The solvent carrier contains:
glycerol accounting for 4% of the total volume of the liquid;
terpineol accounting for 38.4 percent of the total volume of the liquid;
o-benzene in an amount of 57.6% by volume of the total liquid.
The preparation method comprises the following steps:
s1: according to the proportion, after sequentially dripping glycerol, terpineol and o-benzene into a container, adding silver powder and sintered glass powder;
s2: and sealing the container, putting the container into a spin coater, and rotating for 1500 seconds at the rotating speed of 1200rpm under manual vacuum to fully and uniformly mix the components in the container to obtain the anode silver paste.
In the above examples and comparative examples, silver powder and sintered glass powder were commercially available. The silver powder is purchased from Mitsui chemistry, and the sintered glass powder is front silver grid line glass powder. The sintered glass powder is light green powder at 25 ℃, the effective content is more than or equal to 99.0 percent, the softening temperature is about 342 ℃, the water content is less than or equal to 0.5 percent, and the D50 is about 1.92 mu m.
Test examples
The positive electrode silver pastes prepared in the examples and the comparative examples are subjected to mechanical property, screen printing property, high-temperature sintering property and application property tests. Wherein:
testing the performance of the silver paste: and measuring the rheological properties such as viscosity, yield stress, shear thinning and the like of the silver paste by using a rheometer.
Screen printing: before printing, firstly adjusting adaptive parameters such as the distance between a printing screen and a silicon wafer, the printing speed and the like, then adding silver paste on the screen surface, applying pressure on the silver paste through a scraper, and extruding the silver paste to enable the silver paste to reach the silicon wafer through the screen to form a grid line electrode with a proper shape under the movement of the scraper. During screen printing, the paste is required to exhibit a low high shear viscosity so that the paste flows easily through a screen or into a nozzle during coating, while also having a high shear viscosity and rapid mesh recovery to provide a good mesh structure.
High-temperature sintering property: and placing the silicon wafer with the grid line electrode formed in a high-temperature sintering furnace to finish the sintering process, so that the grid line electrode and the silicon wafer form ohmic contact.
And (3) testing the application performance: testing parameters such as contact resistivity, photoelectric conversion efficiency and the like through electrical detection equipment; the morphology such as line width, aspect ratio, etc. was observed by SEM.
Some of the test results are shown in tables 1 and 2.
TABLE 1 Screen printing Width of silver paste groups
| Group of | Average printing width | Extreme difference in width | Variance of width |
| Silver paste of example 1 | 35.4 | 6.1 | 5.056 |
| Silver paste of comparative example 1 | 27.73 | 5.7 | 4.571 |
| Silver paste of comparative example 2 | 47.95 | 4.5 | 9.259 |
Table 2 screen printing height of silver paste groups
| Group of | Average print height | Extreme difference in height | Height variance |
| Silver paste of example 1 | 7.56 | 4.89 | 3.857 |
| Silver paste of comparative example 1 | 6.51 | 4.18 | 2.467 |
| Silver paste of comparative example 2 | 8.89 | 2.43 | 0.627 |
Table 3 silver paste rheology data for example 1 (25.1 ℃)
As can be seen from table 1, table 2 and table 3, the positive electrode silver paste of the present invention has wide process width, height and rheological parameter coverage range, and is suitable for preparing conductive grid lines for current PERC and TOPCon battery positive electrodes.
In order to ensure good rheological property, the traditional silver paste needs to be regulated and controlled through a complex process, and the rheological parameters of the capillary suspension slurry, such as viscosity, yield stress and the like, can be regulated by changing the total liquid volume ratio of the secondary phase, so that the method is relatively simpler and more convenient. The long-term stability is improved by adjusting the yield stress and the shear viscosity to suppress sedimentation, and more importantly, a higher aspect ratio can be achieved.
TABLE 4 Electrical Properties of the silver paste groups
| Group of | ETA(％) | Voc(V) | Isc(A) | FF(％) | Jo1(A/cm 2 ) |
| Silver paste of example 1 | 23.445 | 0.6965 | 13.5867 | 81.87 | 6.77E-14 |
| Silver paste of comparative example 1 | 23.415 | 0.6960 | 13.5768 | 81.80 | 9.13E-10 |
| Silver paste of comparative example 2 | 23.429 | 0.6962 | 13.5677 | 81.89 | 1.51E-10 |
According to the test results in table 4, the performance of the cathode silver paste of the present invention is optimal for the cathode silver paste of the solar cell, and the aspect ratio and the electrical property of the cathode silver paste are superior to those of the silver pastes of comparative examples 1 and 2.
The printed grid line is shown in figure 1. In addition, the printed grid lines were tested using a 3D microscope to observe the print topography, as shown in fig. 2. The observation shows that the problems of grid line false printing, burr, screen plate blocking, screen sticking and the like do not occur in the screen printing stage of the anode silver paste. The silver pastes of comparative examples 1 and 2 are easy to have the problems of grid line virtual printing, burr, screen blocking, screen sticking and the like.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. The positive electrode silver paste is characterized in that raw materials for preparation comprise a powder material and a solvent carrier, the powder material comprises a silver powder and sintered glass powder, the solvent carrier comprises a primary solution and a secondary solution, and the primary solution comprises at least two of terpineol, o-benzene and 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; the secondary top liquid comprises at least one of glycerol and glycol.
2. The cathode silver paste according to claim 1, wherein the preparation raw materials comprise, in parts by mass:
powder material: 85 to 95 portions of the mixture of the components,
solvent carrier: 8 to 12 portions.
3. The cathode silver paste of claim 1, wherein the volume percentage of the secondary solution in the solvent carrier is 0.5-7%.
4. The cathode silver paste according to any one of claims 1 to 3, wherein the D50 of the silver powder is in a range of 1 μm to 2 μm.
5. The cathode silver paste according to any one of claims 1 to 3, wherein the effective content of the silver powder is not less than 99.9%.
6. The method for preparing the positive electrode silver paste of any one of claims 1 to 5, wherein the steps comprise:
s1: sequentially adding the sintered glass powder and the silver powder into the secondary solution;
s2: and (3) adding the main item solution into the product obtained in the step (S1), and uniformly mixing to obtain the anode silver paste.
7. The method according to claim 6, wherein in step S2, the mixing is performed in a spin coater.
8. The method according to claim 7, wherein the spin coater has a rotation speed of 1000rpm to 1500rpm.
9. The method according to claim 7, wherein the spin coater has a rotation time of 1000s to 2000s.
10. Use of the positive electrode silver paste of any one of claims 1 to 5 in a solar cell.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816200A (en) * | 2016-12-29 | 2017-06-09 | 无锡优顺能源开发科技有限公司 | A kind of silicon solar cell front electrode silver slurry and preparation method thereof |
| CN107808705A (en) * | 2017-10-20 | 2018-03-16 | 张东 | A kind of solar cell front side silver paste and preparation method thereof |
| CN109478572A (en) * | 2016-07-06 | 2019-03-15 | 卡尔斯鲁厄技术研究所 | Technique for can print slurry from capillary suspension production high conductivity |
| CN112951479A (en) * | 2021-02-07 | 2021-06-11 | 北京中科纳通电子技术有限公司 | Conductive silver paste for filter and preparation method thereof |
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| CN109478572A (en) * | 2016-07-06 | 2019-03-15 | 卡尔斯鲁厄技术研究所 | Technique for can print slurry from capillary suspension production high conductivity |
| CN106816200A (en) * | 2016-12-29 | 2017-06-09 | 无锡优顺能源开发科技有限公司 | A kind of silicon solar cell front electrode silver slurry and preparation method thereof |
| CN107808705A (en) * | 2017-10-20 | 2018-03-16 | 张东 | A kind of solar cell front side silver paste and preparation method thereof |
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