CN115338421A - Ni-P alloy additive for front silver paste of solar cell, preparation method and application - Google Patents
Ni-P alloy additive for front silver paste of solar cell, preparation method and application Download PDFInfo
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- CN115338421A CN115338421A CN202211140263.3A CN202211140263A CN115338421A CN 115338421 A CN115338421 A CN 115338421A CN 202211140263 A CN202211140263 A CN 202211140263A CN 115338421 A CN115338421 A CN 115338421A
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- solar cell
- silver paste
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910018104 Ni-P Inorganic materials 0.000 title claims abstract description 82
- 229910018536 Ni—P Inorganic materials 0.000 title claims abstract description 82
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 79
- 239000004332 silver Substances 0.000 title claims abstract description 79
- 239000000654 additive Substances 0.000 title claims abstract description 74
- 230000000996 additive effect Effects 0.000 title claims abstract description 74
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 62
- 239000000956 alloy Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011521 glass Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 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 abstract description 26
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 63
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 63
- 239000000843 powder Substances 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 15
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 claims description 11
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000001856 Ethyl cellulose Substances 0.000 claims description 11
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 11
- 229920001249 ethyl cellulose Polymers 0.000 claims description 11
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 11
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 claims description 2
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- 239000010703 silicon Substances 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 45
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 30
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 30
- 239000002002 slurry Substances 0.000 description 30
- 238000005303 weighing Methods 0.000 description 27
- 238000000227 grinding Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005245 sintering Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 230000002028 premature Effects 0.000 description 4
- 230000008018 melting Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910004205 SiNX Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000013082 photovoltaic technology Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- -1 NVP Polymers 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a Ni-P alloy additive for front silver paste of a solar cell, and a preparation method and application thereof. The preparation method comprises the following steps: reacting a mixed reaction system containing nickel salt, a reducing agent, a surfactant and a pH regulator to prepare a Ni-P alloy additive for the front silver paste of the solar cell; wherein the reducing agent comprises sodium hypophosphite; the pH value of the mixed reaction system is 12-13. The Ni-P alloy additive is used for the front silver paste of the solar cell, so that the damage degree of the PN junction of the silicon wafer can be reduced, and the crystalline silicon solar cell is guaranteed to have higher open-circuit voltage; meanwhile, the glass transverse outward expansion degree of the silver electrode grid line caused by glass flowing is reduced, the shading area is reduced, the crystalline silicon solar cell is guaranteed to have high short-circuit current, and the solar cell is guaranteed to have high conversion efficiency.
Description
Technical Field
The invention belongs to the technical field of conductive paste for solar cells, and particularly relates to a Ni-P alloy additive for front silver paste of a solar cell, a preparation method and application.
Background
Compared with the conventional energy, the renewable energy has an unparalleled advantage, and among various renewable energy, solar energy is widely considered as the most valuable clean energy, and the solar energy irradiated to the earth in each hour is equivalent to the sum of various energies required by mankind every year. With the development and utilization of solar energy by people, the photovoltaic industry brought along with the development of solar energy is rapidly developed like a spring bamboo shoot after rain. Solar cells have been widely used in industrial production due to their mature technology and high conversion efficiency, and their application is expected to replace conventional power generation devices. Solar cells are essentially energy converters of solar photovoltaic power generation. Photovoltaic technology can convert sunlight directly into electricity to generate electricity directly. When sunlight incident light irradiates the photovoltaic cell and is absorbed, electron-hole pairs are generated on the surface of the photovoltaic cell and are separated under the action of a built-in electric field formed by the electron-hole pairs, opposite charges appear at two ends of the photovoltaic cell, and a photogenerated voltage is generated. Among all photovoltaic technology products, crystalline silicon solar cells dominate the global photovoltaic market, occupying more than 90% of the market share. The crystalline silicon solar cell is provided with a P-type substrate, a P-doped n-type semiconductor layer is laid to form a P-n junction, an antireflection film is coated on the P-type semiconductor layer, silver paste is printed on the P-type semiconductor layer through screen printing to prepare a front silver paste electrode, and back aluminum paste and a back silver paste electrode are coated on the back of the crystalline silicon solar cell to form a complete cell structure.
The conductive paste for the crystalline silicon solar cell belongs to one of thick film conductive pastes and mainly comprises an organic carrier, silver powder or aluminum powder and an inorganic phase adhesive. The inorganic phase adhesive is generally low-melting glass powder, the melting point is below 600 ℃, and the inorganic phase adhesive can be easily welded with other substances, and the glass powder is an important factor for determining contact resistance, surface etching reaction and the performance of the whole battery piece. The type and quantity of the glass powder have great influence on the open circuit voltage of the solar cell and the filling factor of the paste under the high-temperature sintering condition, and in the sintering step of the solar cell manufacturing process, the glass powder in the silver electrode paste is bonded with the lower silicon layer through corroding the SiNx antireflection film layer, so that the good ohmic contact can be guaranteed to be formed through full and complete reaction. The softening temperature of the glass powder is an important index for measuring the performance of the glass powder, if the softening temperature is low, the glass powder can be softened too early in the high-temperature sintering process, the p-n junction is easy to be punctured, and a slurry sintering film can not be in good contact with a silicon wafer, so that the performance of the whole electrode is poor; when the glass softening temperature is higher, the glass powder is not easy to melt in the high-temperature sintering process, and cannot react with the anti-reflection film and penetrate through the anti-reflection film to contact with silicon, so that the adhesive force of the slurry sintering film is reduced.
The conventional technical means for adjusting the softening point of the glass powder is to reduce the softening temperature of the glass by adjusting the proportion of low-melting point oxides and high-melting point oxides in the glass powder and adding network external oxides, and the softening temperature is usually reduced by adjusting TeO 2 、PbO、Bi 2 O 3 、WO 3 、SiO、ZnO、Li 2 O、Na 2 O、TiO 2 And the composition ratio of the oxides is equal. The low softening point enables the glass to flow prematurely and fully contact with the Si substrate, so that the solar cell has good contact performance, namely a high filling factor, but the open-circuit voltage is low; a higher softening point causes the glass to flow later, giving the solar cell a higher open circuit voltage, but poor contact performance, i.e. a poor fill factor. The adjustment of the oxide composition in the glass can only be balanced between the open-circuit voltage and the fill factor, and it is difficult to obtain a higher open-circuit voltage and fill factor at the same time. Therefore, it is an urgent need to solve the problems of making the solar cell have a higher open-circuit voltage and a higher fill factor, and increasing the short-circuit current and the conversion efficiency of the solar cell.
Disclosure of Invention
The invention mainly aims to provide a Ni-P alloy additive for front silver paste of a solar cell, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a Ni-P alloy additive for silver paste on the front surface of a solar cell, which comprises the following steps:
reacting a mixed reaction system containing nickel salt, a reducing agent, a surfactant and a pH regulator to prepare a Ni-P alloy additive for the front silver paste of the solar cell;
wherein the reducing agent comprises sodium hypophosphite; the pH value of the mixed reaction system is 12-13.
The embodiment of the invention also provides the Ni-P alloy additive for the solar cell front silver paste prepared by the preparation method, wherein the content of P in the Ni-P alloy additive is 5-20 wt%.
The embodiment of the invention also provides application of the Ni-P alloy additive for the front silver paste of the solar cell in preparation of the front silver paste of the solar cell.
The embodiment of the invention also provides the solar cell front silver paste which comprises the Ni-P alloy additive for the solar cell front silver paste.
Compared with the prior art, the invention has the beneficial effects that:
(1) The Ni-P alloy additive provided by the invention can reduce the damage degree to the PN junction of the silicon wafer and ensure that the crystalline silicon solar cell has higher open-circuit voltage;
(2) The Ni-P alloy additive provided by the invention can reduce the transverse outward expansion degree of glass caused by glass flowing of silver electrode grid lines, reduce the shading area and ensure that a crystalline silicon solar cell has higher short-circuit current;
(3) In the process of slurry sintering, P atoms in Ni-P re-diffuse into the silicon wafer, so that the doping concentration of the silicon wafer is improved, and the solar cell has better conversion efficiency.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made long-term research and extensive practice to provide the technical scheme of the present invention, the glass frit in the conductive paste (front silver paste) for the solar cell determines the conversion efficiency of the solar cell, and the flowing glass frit corrodes SiNx for a long time in the early stage of sintering process to form good ohmic contact but has the risk of breaking down PN junction; the later the glass frit flows, the damage degree to the PN junction is reduced, and the solar cell has a higher open circuit voltage. The prior art means generally combines contact performance and open circuit voltage by adjusting the softening point of the glass, but cannot simultaneously have high open circuit voltage under the condition of high contact. The invention breaks through the technical means of the traditional glass frit by using the Ni-P alloy additive, has higher contact performance and open-circuit voltage and greatly improves the conversion efficiency of the solar cell.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Specifically, as one aspect of the technical scheme of the invention, the preparation method of the Ni-P alloy additive for the front silver paste of the solar cell, which relates to the technical scheme, comprises the following steps:
reacting a mixed reaction system containing nickel salt, a reducing agent, a surfactant and a pH regulator to prepare a Ni-P alloy additive for the front silver paste of the solar cell;
wherein the reducing agent comprises sodium hypophosphite; the pH value of the mixed reaction system is 12-13.
Further, the Ni-P alloy additive is Ni-P alloy powder.
In some preferred embodiments, the nickel salt includes nickel sulfate, and is not limited thereto.
In some preferred embodiments, the surfactant comprises any one of PVP, NVP, PVPP, or a combination of two or more thereof, without limitation thereto.
In some preferred embodiments, the pH adjusting agent includes any one or a combination of two or more of NaOH, KOH, and ammonia water, and is not limited thereto.
In some preferred embodiments, the concentration of the nickel salt in the mixed reaction system is 0.05 to 0.5mol/L.
In some preferred embodiments, the molar ratio of the reducing agent to nickel salt is from 2 to 8: 1.
In some preferred embodiments, the surfactant is used in an amount of 10 to 30wt% of the nickel salt.
In some preferred embodiments, the method of preparation comprises: mixing a surfactant with a nickel salt solution, then adding a pH regulator to regulate the pH value of the obtained mixed solution to be 12-13, adding a reducing agent to form the mixed reaction system, and stirring and reacting for 1.5 hours at 90 ℃.
In some more specific embodiments, the method for preparing the Ni-P alloy additive for the front silver paste of the solar cell comprises the following steps: the Ni-P alloy additive is prepared through the chemical reduction reaction of sodium hypophosphite and nickel sulfate, wherein the nickel sulfate is a main salt and provides Ni required in the chemical reaction process 2+ Is a source of nickel in the Ni-P alloy; sodium hypophosphite is a reducing agent which can provide electrons required for reducing nickel ions to remove Ni 2+ Reducing the nickel into elemental metallic nickel. In addition, surfactants PVP and NaOH are needed in the chemical reaction process, the surfactants can ensure the smooth progress of the oxidation-reduction reaction, and the NaOH is used for adjusting the pH value. The concentration of the nickel sulfate plating solution is 0.05-0.5 mol/L, too high concentration can lead to larger Ni-P alloy particles generated in the chemical plating process, and too low concentration can lead to slow reaction process or even no reaction; the dosage of the sodium hypophosphite is 2 to 8 times of the mole number of the nickel sulfate, and the P content in the Ni-P coating can be adjusted by controlling the proportion of the sodium hypophosphite to the nickel sulfate. The consumption of the surface active agent PVP is 20 percent of the mass of the nickel sulfate, after the plating solution is prepared, the pH is adjusted to 12, and the solution is heated to 90 ℃ under the condition of stirringAnd carrying out a warm reaction for 1.5h to obtain uniform Ni-P alloy particles, wherein the diameters of the particles are adjusted by controlling the concentration of the nickel sulfate solution. The Ni-P alloy powder is added into the conductive slurry after being centrifuged and washed, and is used as an inorganic phase additive.
In some more specific embodiments, the method for preparing the Ni-P alloy additive for the solar cell front silver paste comprises the following steps:
(1) Weighing nickel sulfate and preparing a nickel sulfate solution with the concentration of 0.05 mol/L-0.5 mol/L;
(2) Weighing a surfactant PVP (polyvinyl pyrrolidone) with the surface accounting for 20% of the mass of the nickel sulfate, and dissolving the surfactant PVP in a nickel sulfate solution;
(3) Adding dissolved NaOH solution, and adjusting pH to 12
(4) Weighing sodium hypophosphite according to 2-8 times of the mole number of the nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
(5) Heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
(6) And centrifuging and washing to remove redundant ions to obtain the required Ni-P alloy additive.
According to the invention, the Ni-P alloy additive is added into the front silver paste of the solar cell as an inorganic phase additive, the particle size of the Ni-P alloy additive is 0.5-2 μm, and the Ni-P alloy additive as an inorganic phase additive diffuses P atoms into a silicon wafer due to the existence of P in the slurry sintering process, so that the re-doping effect is achieved, and the conversion efficiency of the solar cell is improved; in addition, due to the higher melting point of Ni-P, the premature flow of glass can be inhibited, the thickening degree of a silver electrode grid line caused by the flow of the glass is reduced, the shading area of the silver electrode is reduced, the short-circuit current of the solar cell is improved, and meanwhile, due to the inhibition of the premature flow of the glass, the damage degree of the glass to a PN junction is reduced, and the open-circuit voltage of the solar cell is improved.
The embodiment of the invention also provides the Ni-P alloy additive for the front silver paste of the solar cell, which is prepared by the preparation method, wherein the content of P in the Ni-P alloy additive is 5-20 wt%.
In some preferred embodiments, the Ni-P alloying addition has a particle size of 0.5 to 2 μm.
In another aspect of the embodiment of the invention, the application of the Ni-P alloy additive for the front silver paste of the solar cell in preparing the front silver paste of the solar cell is also provided.
In another aspect of the embodiment of the invention, a solar cell front silver paste is also provided, which includes the aforementioned Ni-P alloy additive for solar cell front silver paste.
In some preferred embodiments, the Ni-P alloy additive content in the solar cell front silver paste is 0.1 to 1.0wt%.
In some preferred embodiments, the solar cell front side silver paste further comprises: glass powder, conductive silver powder, polyvinyl butyral, ethyl cellulose, propylene glycol butyl ether acetate and ethylene glycol monobutyl ether acetate.
The Ni-P alloy additive is used as an inorganic phase additive of the solar cell, has a higher melting point, prevents transitional corrosion of a PN junction caused by premature flow of glass powder, and enables the solar cell to have higher open-circuit voltage; the glass is softened and then infiltrated with Ni-P alloy, so that the transverse diffusion of the glass after sintering is small, the width of a silver electrode grid line is reduced, namely, the shading area is reduced, and the solar cell has high short-circuit current; in addition, due to the existence of P in the Ni-P alloy, P atoms are diffused to the silicon wafer again in the sintering process, the doping concentration in the silicon wafer is increased, and the conversion efficiency of the solar cell is improved.
The Ni-P alloy additive provided by the invention can be used as an inorganic phase additive of a solar cell to inhibit the premature flow of glass, reduce the damage degree of the glass to PN junctions and increase the open-circuit voltage; the transverse line diffusion of the glass is inhibited, the width of the silver electrode grid line is reduced, the shading area is reduced, and the short-circuit current is improved; phosphorus atoms in the additive diffuse to the silicon wafer during slurry sintering, so that the doping concentration of the silicon wafer is improved, and the conversion efficiency is improved.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments, which are implemented on the premise of the technical solutions of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples below were obtained from conventional biochemicals unless otherwise specified.
Example 1
The Ni-P alloy additive for the crystalline silicon solar cell front silver paste has the particle size of 1.2 mu m, wherein the mass percentage of P in the Ni-P alloy additive is 5.5%.
The procedure for the preparation of the inorganic phase additive of this example was as follows:
(1) Weighing nickel sulfate and preparing into nickel sulfate solution with concentration of 0.2mol/L
(2) Weighing a surface active agent PVP (polyvinyl pyrrolidone) with the mass of 20% of that of the nickel sulfate, and dissolving the PVP in a nickel sulfate solution;
(3) Adding dissolved NaOH solution, and adjusting the pH value to 12;
(4) Weighing sodium hypophosphite according to 3 times of the mole number of the nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
(5) Heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
(6) And centrifuging and washing to remove redundant ions to obtain the required Ni-P powder.
Preparing the front silver paste of the solar cell: respectively mixing 2.5wt% of glass powder, 0.1wt% of Ni-P powder, 87.4wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate and 3wt% of ethylene glycol monobutyl ether acetate for 1h, grinding the slurry by using a three-roll grinder, testing the grinding fineness by using a scraper plate fineness agent, and obtaining the solar cell front silver paste slurry with the grinding fineness of the slurry being less than 10 mu m.
Example 2
The Ni-P alloy additive for the crystalline silicon solar cell front silver paste has the particle size of 0.8 mu m, wherein the mass percentage of P in the Ni-P alloy additive is 8.4%.
The procedure for the preparation of the inorganic phase additive in this example was as follows:
(1) Weighing nickel sulfate and preparing into nickel sulfate solution with concentration of 0.15mol/L
(2) Weighing a surfactant PVP (polyvinyl pyrrolidone) with the surface accounting for 20% of the mass of the nickel sulfate, and dissolving the surfactant PVP in a nickel sulfate solution;
(3) Adding dissolved NaOH solution, and adjusting the pH value to 12;
(4) Weighing sodium hypophosphite according to 5 times of the mole number of the nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
(5) Heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
(6) And centrifuging and washing to remove redundant ions to obtain the required Ni-P powder.
Preparing the front silver paste of the solar cell: respectively mixing 2.5wt% of glass powder, 0.4wt% of Ni-P powder, 87.1wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate and 3wt% of ethylene glycol butyl ether acetate for 1h, grinding the slurry by using a three-roll grinder, testing the grinding fineness by using a scraper plate fineness agent, and obtaining the front silver paste slurry of the solar cell, wherein the grinding fineness of the slurry is less than 10 mu m.
Example 3
The Ni-P alloy additive for the crystalline silicon solar cell front silver paste has the particle size of 1.9 mu m, wherein the mass percentage of P in the additive is 12%.
The procedure for the preparation of the inorganic phase additive in this example was as follows:
(1) Weighing nickel sulfate and preparing nickel sulfate solution with concentration of 0.35mol/L
(2) Weighing a surface active agent PVP (polyvinyl pyrrolidone) with the mass of 20% of that of the nickel sulfate, and dissolving the PVP in a nickel sulfate solution;
(3) Adding dissolved NaOH solution, and adjusting the pH value to 12;
(4) Weighing sodium hypophosphite according to 7 times of the mole number of the nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
(5) Heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
(6) And centrifuging and washing to remove redundant ions to obtain the required Ni-P powder.
Preparing the front silver paste of the solar cell: 2.5wt% of glass powder, 0.8wt% of Ni-P powder, 86.7wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate and 3wt% of ethylene glycol monobutyl ether acetate were mixed for 1 hour, the slurry was ground using a three-roll grinder, the grinding fineness was measured using a scraper fineness agent, and the grinding fineness of the slurry was 10 μm or less, thereby obtaining a solar cell front side silver paste.
Example 4
The Ni-P alloy additive for the crystalline silicon solar cell front silver paste has the particle size of 1.4 mu m, wherein the mass ratio of P in the additive is 18%.
The procedure for the preparation of the inorganic phase additive of this example was as follows:
(1) Weighing nickel sulfate and preparing into nickel sulfate solution with concentration of 0.3mol/L
(2) Weighing a surface active agent PVP (polyvinyl pyrrolidone) with the mass of 20% of that of the nickel sulfate, and dissolving the PVP in a nickel sulfate solution;
(3) Adding dissolved NaOH solution, and adjusting the pH value to 12;
(4) Weighing sodium hypophosphite according to 8 times of the mole number of the nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
(5) Heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
(6) And centrifuging and washing to remove redundant ions to obtain the required Ni-P powder.
Preparing the front silver paste of the solar cell: 2.5wt% of glass powder, 1.0wt% of Ni-P powder, 86.5wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate, and 3wt% of ethylene glycol butyl ether acetate were mixed for 1 hour, the slurry was ground using a three-roll grinder, the grinding fineness was measured using a scraper fineness agent, and the grinding fineness of the slurry was 10 μm or less, respectively, to obtain a solar cell front side silver paste.
Comparative example 1
The Ni-P alloy additive for the crystalline silicon solar cell front silver paste has the particle size of 1.2 mu m, wherein the mass percentage of P in the Ni-P alloy additive is 5.5%.
The procedure for the preparation of the inorganic phase additive in this example was as follows:
weighing nickel sulfate and preparing into nickel sulfate solution with concentration of 0.2mol/L
Weighing a surface active agent PVP (polyvinyl pyrrolidone) with the mass of 20% of that of the nickel sulfate, and dissolving the PVP in a nickel sulfate solution;
adding dissolved NaOH solution, and adjusting the pH value to 14;
weighing sodium hypophosphite according to 3 times of the mole number of the nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
and centrifuging and washing to remove redundant ions to obtain the required Ni-P powder.
Preparing the front silver paste of the solar cell: respectively mixing 2.5wt% of glass powder, 0.1wt% of Ni-P powder, 87.4wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate and 3wt% of ethylene glycol monobutyl ether acetate for 1h, grinding the slurry by using a three-roll grinder, testing the grinding fineness by using a scraper plate fineness agent, and obtaining the solar cell front silver paste slurry with the grinding fineness of the slurry being less than 10 mu m.
Comparative example 2
The Ni-P alloy additive for the crystalline silicon solar cell front silver paste has the particle size of 3 mu m, wherein the mass percentage of P in the Ni-P alloy additive is 5.8%.
The procedure for the preparation of the inorganic phase additive in this example was as follows:
weighing nickel sulfate and preparing into nickel sulfate solution with concentration of 0.6mol/L
Weighing a surfactant PVP (polyvinyl pyrrolidone) with the surface accounting for 20% of the mass of the nickel sulfate, and dissolving the surfactant PVP in a nickel sulfate solution;
adding dissolved NaOH solution, and adjusting the pH value to 12;
weighing sodium hypophosphite according to 3 times of the mole number of the nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
and centrifuging and washing to remove redundant ions to obtain the required Ni-P powder.
Preparing the front silver paste of the solar cell: respectively mixing 2.5wt% of glass powder, 0.1wt% of Ni-P powder, 87.4wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate and 3wt% of ethylene glycol monobutyl ether acetate for 1h, grinding the slurry by using a three-roll grinder, testing the grinding fineness by using a scraper plate fineness agent, and obtaining the solar cell front silver paste slurry with the grinding fineness of the slurry being less than 10 mu m.
Comparative example 3
The Ni-P alloy additive for the crystalline silicon solar cell front silver paste has the particle size of 0.7 mu m, wherein the mass percentage of P in the additive is 1.4%.
The procedure for the preparation of the inorganic phase additive in this example was as follows:
weighing nickel sulfate and preparing into nickel sulfate solution with concentration of 0.2mol/L
Weighing a surfactant PVP (polyvinyl pyrrolidone) with the surface accounting for 20% of the mass of the nickel sulfate, and dissolving the surfactant PVP in a nickel sulfate solution;
adding dissolved NaOH solution, and adjusting the pH value to 12;
weighing sodium hypophosphite according to 0.5 time of the mole number of nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
and centrifuging and washing to remove redundant ions to obtain the required Ni-P powder.
Preparing the front silver paste of the solar cell: respectively mixing 2.5wt% of glass powder, 0.1wt% of Ni-P powder, 87.4wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate and 3wt% of ethylene glycol monobutyl ether acetate for 1h, grinding the slurry by using a three-roll grinder, testing the grinding fineness by using a scraper plate fineness agent, and obtaining the solar cell front silver paste slurry with the grinding fineness of the slurry being less than 10 mu m.
Comparative example 4
The Ni-P alloy additive for the crystalline silicon solar cell front silver paste has the particle size of 1.2 mu m, wherein the mass percentage of P in the additive is 5.5%.
The procedure for the preparation of the inorganic phase additive in this example was as follows:
weighing nickel sulfate and preparing into nickel sulfate solution with concentration of 0.2mol/L
Weighing a surface active agent PVP (polyvinyl pyrrolidone) with the mass of 20% of that of the nickel sulfate, and dissolving the PVP in a nickel sulfate solution;
adding dissolved NaOH solution, and adjusting the pH value to 12;
weighing sodium hypophosphite according to 3 times of the mole number of the nickel sulfate, and dissolving the sodium hypophosphite in a nickel sulfate solution;
heating to 90 ℃ while stirring, and reacting for 1.5h at constant temperature;
and centrifuging and washing to remove redundant ions to obtain the required Ni-P powder.
Preparing the front silver paste of the solar cell: respectively mixing 2.5wt% of glass powder, 2.5wt% of Ni-P powder, 85wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate and 3wt% of ethylene glycol monobutyl ether acetate for 1h, grinding the slurry by using a three-roll grinder, and testing the grinding fineness by using a scraper plate fineness agent, wherein the grinding fineness of the slurry is less than 10 mu m, thus obtaining the front silver paste of the solar cell.
Comparative example 5
Commercial Ni powder is purchased as an additive for the front silver paste of the crystalline silicon solar cell, and the particle size of the Ni powder is 0.7 mu m.
Preparing the front silver paste of the solar cell: respectively mixing 2.5wt% of glass powder, 0.1wt% of commercial Ni powder, 87.4wt% of conductive silver powder, 3wt% of polyvinyl butyral, 3wt% of ethyl cellulose, 1wt% of propylene glycol butyl ether acetate and 3wt% of ethylene glycol monobutyl ether acetate for 1 hour, grinding the slurry by using a three-roll grinder, testing the grinding fineness by using a scraper plate fineness agent, and obtaining the front silver paste of the solar cell, wherein the grinding fineness of the slurry is less than 10 micrometers.
And (3) performance characterization: the solar cell front side silver paste of examples 1-4 and comparative examples 1-5 were characterized in solar cells and compared with commercial pastes, and the characterization data is shown in table 1.
Table 1 properties of the solar cell front side silver paste in the solar cell using the solar cell front side silver paste slurries described in examples 1 to 4 and comparative examples 1 to 5
Can show
| Name (R) | Open circuit voltage/V | Short-circuit current/A | Contact resistance/omega | Fill factor/%) | Conversion efficiency/%) |
| Commercial pulp | 0.6822 | 11.175 | 0.00124 | 82.11 | 22.823 |
| Example 1 | 0.6833 | 11.180 | 0.00122 | 82.17 | 22.874 |
| Example 2 | 0.6837 | 11.191 | 0.00120 | 82.20 | 22.912 |
| Example 3 | 0.6841 | 11.196 | 0.00118 | 82.23 | 22.933 |
| Example 4 | 0.6844 | 11.198 | 0.00125 | 82.09 | 22.881 |
| Comparative example 1 | 0.6838 | 11.182 | 0.00137 | 81.87 | 22.794 |
| Comparative example 2 | 0.6836 | 11.190 | 0.00140 | 81.80 | 22.772 |
| Comparative example 3 | 0.6835 | 11.182 | 0.00133 | 81.93 | 22.812 |
| Comparative example 4 | 0.6837 | 11.210 | 0.00153 | 81.23 | 22.537 |
| Comparative example 5 | 0.6847 | 11.219 | 0.00161 | 80.88 | 22.507 |
In addition, the inventors of the present invention have also made experiments with other raw materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. The preparation method of the Ni-P alloy additive for the front silver paste of the solar cell is characterized by comprising the following steps of: reacting a mixed reaction system containing nickel salt, a reducing agent, a surfactant and a pH regulator to prepare a Ni-P alloy additive for the front silver paste of the solar cell;
wherein the reducing agent comprises sodium hypophosphite; the pH value of the mixed reaction system is 12-13.
2. The method of claim 1, wherein: the nickel salt comprises nickel sulfate;
and/or the surfactant comprises any one or a combination of more than two of PVP, NVP and PVPP;
and/or the pH regulator comprises any one or the combination of more than two of NaOH, KOH and ammonia water.
3. The method of claim 1, wherein: the concentration of nickel salt in the mixed reaction system is 0.05-0.5 mol/L;
and/or the molar ratio of the reducing agent to the nickel salt is 2-8: 1;
and/or the dosage of the surfactant is 10-30 wt% of the nickel salt.
4. The production method according to claim 1, characterized by comprising: mixing a surfactant with a nickel salt solution, adding a pH regulator to regulate the pH value of the obtained mixed solution to 12-13, adding a reducing agent to form the mixed reaction system, and stirring and reacting at 90 ℃ for 1.5 hours.
5. The Ni-P alloy additive for the silver paste on the front surface of the solar cell, prepared by the preparation method of any one of claims 1 to 4, wherein the content of P in the Ni-P alloy additive is 5 to 20wt%.
6. The Ni-P alloy additive for the front silver paste of the solar cell according to claim 5, wherein the Ni-P alloy additive comprises the following components in percentage by weight: the particle size of the Ni-P alloy additive is 0.5-2 mu m.
7. Use of the Ni-P alloy additive for solar cell front side silver paste according to claim 5 or 6 in the preparation of solar cell front side silver paste.
8. A solar cell front side silver paste, comprising the Ni-P alloy additive for solar cell front side silver paste according to claim 5 or 6.
9. The solar cell front side silver paste of claim 8, wherein: the content of the Ni-P alloy additive in the front silver paste of the solar cell is 0.1-1.0 wt%.
10. The solar cell front side silver paste of claim 8, wherein: the front silver paste of the solar cell further comprises glass powder, conductive silver powder, polyvinyl butyral, ethyl cellulose, propylene glycol butyl ether acetate and ethylene glycol monobutyl ether acetate.
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