CN104575669A - Solar cell back face silver paste and preparing method thereof - Google Patents
Solar cell back face silver paste and preparing method thereof Download PDFInfo
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- CN104575669A CN104575669A CN201510029851.3A CN201510029851A CN104575669A CN 104575669 A CN104575669 A CN 104575669A CN 201510029851 A CN201510029851 A CN 201510029851A CN 104575669 A CN104575669 A CN 104575669A
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Abstract
The invention discloses a solar cell back face silver paste and a preparing method thereof. The silver paste is used for producing back face electrodes of a solar cell. The silver paste comprises, by mass, 45-60% of electric conduction metal powder such as silver powder, copper powder, aluminum powder and nickel powder, 31-46% of organic bond, 1-6% of lead-free bismuthate glass powder and 0-3wt% of additive. The preparing method of the silver paste comprises preparation of the lead-free bismuthate glass powder, preparation of the organic bond, preparation of the additive and the processing technology of the sizing agent. According to the prepared back face electrode silver paste containing the additive, silver layers are compact after the prepared back face electrode silver paste is sintered, makes very good ohmic contact with a silicon wafer and has low series resistance and excellent electrical conductivity, the adhesive force between the back face electrode and the silicon wafer is improved, and the photoelectric converting efficiency is high.
Description
Technical field
The invention belongs to the technical field of slurry used for solar batteries, especially a kind of rear surface of solar cell silver slurry and preparation method thereof.
Background technology
Day by day serious along with environmental pollution, low-carbon environment-friendly idea day by day deep, safety, clean, the energy is more and more by the favor of people efficiently.The wherein main flow that develops as heliotechnics of crystal silicon solar energy battery technology, receive much concern, by the continuous research to solar battery technology, the conversion efficiency of cell piece improves constantly always.
Solar cell is the device by photoelectric effect, light energy conversion being become electric energy.The operation principle of photoelectric effect solar cell: when solar light irradiation is tied at crystal silicon semiconductor p ~ n, form new hole ~ duplet, tie the effect of electric field at p ~ n under, hole flows to p district by n district, electronics flows to n district by p district, just forms electric current after connecting circuit.
In order to the electric current produced by solar cell is drawn, positive and negative electrode need be produced on the surface of solar cell, its negative electrode makes back side main grid by solar cell conductive paste through printing-sintering, plays the effect of to be confluxed by the electric current that aluminium back surface field is collected and deriving.Backplate improves further on the electricity conversion of fine rule close grid high sheet resistance battery sheet at coupling front electrode conductive silver paste and plays an important role.
Rear surface of solar cell electrode slurry is primarily of compositions such as conductive metal powder (as silver powder), organic carrier, glass dust and additives.Wherein silver powder is conducting medium, and glass dust melts when high temperature sintering, between silver powder and semiconductor silicon substrate, form ohmic contact; Organic carrier then plays the effect by silver powder particles dispersion and parcel, makes the silver powder in conductive silver paste not easily precipitate and be oxidized; In order to improve printing effect, usually can add the auxiliary agent of doses in the slurry, improve anti-settling property and the resist sagging of slurry, increase the mobility of silver slurry, keep the stable mobility of appropriateness can ensure the quality of silk screen printing, obtain the main grid of a more satisfactory depth-width ratio; But, except the performance index such as composition, printing, adhesive force, consumption, weldability of backplate slurry, backplate slurry assists the performance of the series resistance (Rs) reducing solar cell also more and more to become a key index of cell piece producer investigation backplate slurry.But this low contact resistance performance of back silver slurry of the prior art still has much room for improvement.In addition, solar cell conductive silver of the prior art starches the normally leaded mixed-powder of glass dust used, although this glass dust softening temperature is low, electric performance stablity is good, lead tolerance is high, and environmental pollution is serious, does not meet environmental requirement.
Summary of the invention
Goal of the invention is: in order to overcome the deficiencies in the prior art, the invention provides a kind of rear surface of solar cell silver slurry, and this slurry has without lead content, Environmental Safety health and the good advantage of the little conductivity of contact resistance.Another goal of the invention there is provided a kind of preparation method manufacturing above-mentioned rear surface of solar cell silver slurry.
To achieve these goals, the technical solution used in the present invention is: a kind of rear surface of solar cell silver slurry, it is characterized in that: comprise 45 ~ 60wt% metal powder, the unleaded bismuthate glass powder of 1 ~ 6wt% and 31 ~ 46wt% organic bond, 0% ~ 3wt% auxiliary agent, the Bi that described metal powder comprises silver powder, described unleaded bismuthate glass powder comprises 50 ~ 85wt%
2o
3, the B of the ZnO of 1 ~ 25wt%, 1 ~ 10wt%
2o
3, the Al of 1 ~ 5wt%
2o
3, the SiO of the BaO of 1 ~ 5wt%, 1 ~ 3wt%
2, the Sb of 0 ~ 2wt%
2o
3, described organic bond comprises 1 ~ 15wt% organic carrier and 5 ~ 98wt% organic solvent, and described auxiliary agent is zinc oxide, at least one in titanium oxide, nickel oxide, nickelous selenide and telluride nickel.
Preferred scheme is, described nickelous selenide is h-NiSe, r-NiSe, Ni
2se
3, Ni
0.85se, NiSe
2in at least one.
Preferred scheme is, described cube of NiSe
2domain size distribution is at 3 ~ 5 μm or 0.5 ~ 1 μm or 100nm ~ 200nm.
Preferred scheme is, the particle diameter of described auxiliary agent is less than 5 μm.
Preferred scheme is, described metal powder also comprises at least one in copper powder, aluminium powder and nickel powder.
Preferred scheme is, described organic carrier is at least one in acrylic resin, ethyl cellulose, butyl cellulose.
Preferred scheme is, described organic solvent is at least one of castor oil, terpinol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, sorbitan monostearate.
Preferred scheme is, described organic solvent also comprises the organic additive of 1 ~ 10wt%, and this organic additive is at least one in thixotropic agent, plasticizer, surfactant.
Preferred scheme is, described glass dust average grain diameter≤3 μm.
Another technical scheme of invention is: the preparation method providing a kind of rear surface of solar cell silver slurry, it is characterized in that, comprise the following steps: (1) takes unleaded bismuthate glass powder in proportion, unleaded bismuthate glass powder is warming up to 900 ~ 1300 DEG C, insulation 30 ~ 50min, ball milling 40 ~ 50h after shrend, filters through 200 eye mesh screens and dries at 80 ~ 110 DEG C, obtaining the glass dust of average grain diameter≤3um;
(2) take organic carrier and organic solvent in proportion to carry out water flowing circulation and heat up and be uniformly mixed, keep whipping temp to be 50 ~ 100 DEG C, after dissolving 3 ~ 10h, add surfactant, be incubated 5 ~ 15min, deposit after filtration;
(3) preparation of rear surface of solar cell silver slurry: take conductive metal powder in proportion, by the unleaded bismuthate glass powder in step (1) and the organic bond in step (2) and conductive metal powder mixing, and add auxiliary agent and carry out mix and blend, granularity≤5 μm are ground to three-high mill rolling, viscosity is 290 ~ 380PaS, obtains slurry.
Adopt such scheme, the present invention has following technique effect: because crystal silicon solar batteries back electrode silver paste is the back side being attached to polysilicon by silk screen printing equably, and with being printed on the aluminium paste at the polysilicon back side, by forming backplate and the back of the body electric field of fine and close silver layer after oven dry, infrared Fast Sintering respectively.The preferred auxiliary agent that the present invention utilizes: zinc oxide, titanium oxide, nickel oxide, nickelous selenide and telluride nickel, these oxides effectively can lower the fusing point of glass dust, enable glass dust under high temperature sintering condition rapidly uniform and silicon form good contact, reach the contact improving metal and Si semiconductor, make back of the body silver form good ohmic contact with silicon chip, improve the adhesive force between back of the body silver and silicon chip simultaneously, effectively reduce cell piece ground series resistance, obtain higher electricity conversion.In addition, by regulating proportioning and the Size Matching of oxide in unleaded bismuthate glass powder, realize better grain size distribution, finer and close after sintering, the unleaded softening point of bismuthate glass powder and the controlled of physicochemical characteristics can be realized, optimize the stability of glass dust, the wandering characteristic of sintering and electrical property.After the rear surface of solar cell electrode silver plasm sintering prepared thus, silver layer is fine and close, good ohmic contact is formed with silicon chip, cell piece has very low series resistance and excellent electric conductivity, adhesive force simultaneously between backplate and silicon chip improves, and then can improve the electricity conversion of solar cell.In addition, the glass dust in the present invention is lead-free glass powder, more Environmental Safety.
Below in conjunction with accompanying drawing, the invention will be further described.
Accompanying drawing explanation
Accompanying drawing 1 is specific embodiment of the invention ZnSe
2 1#nanometer regular octahedron diameter of particle is the typical SEM pictures of about 100nm ~ 200nm;
Accompanying drawing 2 is specific embodiment of the invention ZnSe
2 2#nanometer regular octahedron diameter of particle is the typical SEM pictures of about 0.5 ~ 1 μm;
Accompanying drawing 3 is specific embodiment of the invention ZnSe
2 3#micron regular octahedron diameter of particle is the typical SEM pictures of about 3 ~ 5 μm.
Embodiment
Specific embodiments of the invention are rear surface of solar cell silver slurries, its composition and percentage by weight as follows: the unleaded bismuthate glass powder of 45 ~ 60wt% metal powder, 1 ~ 6wt% and 31 ~ 46wt% organic bond, 0% ~ 3wt% auxiliary agent, metal powder mainly contains silver powder, secondly can also have at least one in copper powder, aluminium powder and nickel powder, unleaded bismuthate glass powder comprises the Bi of 50 ~ 85wt%
2o
3, the B of the ZnO of 1 ~ 25wt%, 1 ~ 10wt%
2o
3, the Al of 1 ~ 5wt%
2o
3, the SiO of the BaO of 1 ~ 5wt%, 1 ~ 3wt%
2, the Sb of 0 ~ 2wt%
2o
3, organic bond comprises 1 ~ 15wt% organic carrier and 5 ~ 98wt% organic solvent, and organic carrier is at least one in acrylic resin, ethyl cellulose, butyl cellulose; Organic solvent is at least one of castor oil, terpinol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, sorbitan monostearate; Auxiliary agent is zinc oxide, at least one in titanium oxide, nickel oxide, nickelous selenide and telluride nickel.The particle diameter of auxiliary agent is less than 5 μm, glass dust average grain diameter 2.8 μm.
Above-mentioned nickelous selenide is h-NiSe, r-NiSe, Ni
2se
3, Ni
0.85se, NiSe
2in at least one.NiSe
2for regular octahedron structure, its domain size distribution is at 3 ~ 5 μm or 0.5 ~ 1 μm or 100nm ~ 200nm.This NiSe
2solvent-thermal method can be adopted to prepare, with nickel chloride (NiCl
26H
2o) and selenium powder (Se) react under hydrazine hydrate system, synthesized regular octahedron two nickelous selenide of different-grain diameter by selectivity phase control, particle diameter is the (see figure 1) NiSe of about 100nm ~ 200nm
2regular octahedron powder, particle diameter is the (see figure 2) NiSe of about 0.5 ~ 1 μm
2regular octahedron powder, particle diameter is the (see figure 3) NiSe of about 3 ~ 5 μm
2regular octahedron powder.
Above-mentioned organic solvent also comprises the organic additive of 1 ~ 10wt%, and this organic additive is at least one in thixotropic agent, plasticizer, surfactant.
A kind of method preparing above-mentioned rear surface of solar cell silver slurry, it comprises the following steps: (1) takes unleaded bismuthate glass powder in proportion, mixing, loads in corundum crucible, transfers in Elema resistance furnace, be warming up to 900 ~ 1300 DEG C, insulation 30 ~ 50min, proceeds to after shrend in ball grinder, ball milling 40 ~ 50h, filter through 200 eye mesh screens and dry at 80 ~ 110 DEG C, obtaining the glass dust of average grain diameter 2.8um;
(2) organic carrier is taken in proportion and organic solvent puts into agitator, carry out water flowing circulation heat up and be uniformly mixed, keep temperature in agitator to be 50 ~ 100 DEG C, after dissolving 3 ~ 10h, add class of surfactant department 85, insulation 5 ~ 15min, deposits after filtration;
(3) preparation of rear surface of solar cell silver slurry: take conductive metal powder in proportion, by the unleaded bismuthate glass powder in step (1) and the organic bond in step (2) and conductive metal powder mixing, and add auxiliary agent and carry out mix and blend, granularity 4.5 μm is ground to three-high mill rolling, viscosity is 290 ~ 380PaS, obtains slurry.This slurry makes back of the body silver can form good ohmic contact with silicon chip, can improve the adhesive force between back of the body silver and silicon chip simultaneously, effectively reduce the series resistance of cell piece, obtain higher electricity conversion.
Further illustrate referring to specific embodiment; but the present invention is not limited to above-mentioned embodiment; persons skilled in the art are according to content disclosed by the invention; other multiple embodiments can be adopted to implement of the present invention; or every employing project organization of the present invention and thinking; do simple change or change, all fall into protection scope of the present invention.
Embodiment 1. ~ 6.
Solar battery front side metallization silver slurry disclosed by the invention is made up of metal powder, glass dust, organic bond, auxiliary agent, and concrete proportioning is in table 1.
Table 1-solar cell size proportioning
(1) glass dust: take six kinds of oxides by proportioning in table 1, load corundum crucible, put into resistance furnace, be warming up to 1200 DEG C, be incubated 40 minutes, enter ball grinder after shrend, ball milling, after 48 hours, 100 DEG C of oven dry, obtains the glass dust of average grain diameter 2.8um.
(2) metal dust: take metal powder, its concrete composition and percentage by weight are 36% silver powder, 2% copper powder, 5% aluminium powder, 2% nickel powder.
(3) organic bond: take ethyl cellulose 4%, acrylic resin 2%, terpinol 30%, castor oil 4%, butyl 45%, butyl acetate 15% put into agitator, water flowing circulates, heat up, keep temperature in agitator to be 80 DEG C, dissolution time 5 hours; Add class of surfactant department 85, be incubated 10 minutes, deposit after filtration.
(4) auxiliary agent: take zinc oxide, titanium oxide, nickel oxide, nickelous selenide and telluride nickel.
(5) slurry preparation: above-mentioned silver powder, glass dust and organic bond and auxiliary agent are mixed in proportion, be ground to granularity with three-high mill rolling and reach 4.5 μm, viscosity is 60 ~ 120PaS, obtains rear surface of solar cell silver slurry.
(6) performance test: the high efficiency back silver of crystal silicon solar energy battery starched (embodiment 1.) and back electrode silver paste, carry on the back electric field electrode aluminium paste high temperature and once burn altogether fast.After tested, battery performance result is as follows:
Table 2-embodiment is the rear unit for electrical property parameters of slurry sintering 1.
The weight in wet base 0.026g of slurry of the present invention, welding back pull is greater than 6.2N.
The high efficiency back silver of crystal silicon solar energy battery starched (embodiment 2.) and back electrode silver paste, carry on the back electric field electrode aluminium paste high temperature and once burn altogether fast.After tested, battery performance result is as follows:
Table 3-embodiment is the rear unit for electrical property parameters of slurry sintering 2.
The weight in wet base 0.026g of slurry of the present invention, welding back pull is greater than 6.5N.
The high efficiency back silver of crystal silicon solar energy battery starched (embodiment 3.) and back electrode silver paste, carry on the back electric field electrode aluminium paste high temperature and once burn altogether fast.After tested, battery performance result is as follows:
Table 4-embodiment is the rear unit for electrical property parameters of slurry sintering 3.
The weight in wet base 0.026g of slurry of the present invention, welding back pull is greater than 6.7N.
The high efficiency back silver of crystal silicon solar energy battery starched (embodiment 4.) and back electrode silver paste, carry on the back electric field electrode aluminium paste high temperature and once burn altogether fast.After tested, battery performance result is as follows:
Table 5-embodiment is the rear unit for electrical property parameters of slurry sintering 4.
The weight in wet base 0.026g of slurry of the present invention, welding back pull is greater than 6.3N.
The high efficiency back silver of crystal silicon solar energy battery starched (embodiment 5.) and back electrode silver paste, carry on the back electric field electrode aluminium paste high temperature and once burn altogether fast.After tested, battery performance result is as follows:
Table 6-embodiment is the rear unit for electrical property parameters of slurry sintering 5.
The weight in wet base 0.026g of slurry of the present invention, welding back pull is greater than 6.3N.
The high efficiency back silver of crystal silicon solar energy battery starched (embodiment 6.) and back electrode silver paste, carry on the back electric field electrode aluminium paste high temperature and once burn altogether fast.After tested, battery performance result is as follows:
Table 7-embodiment is the rear unit for electrical property parameters of slurry sintering 6.
The weight in wet base 0.026g of slurry of the present invention, welding back pull is greater than 6.4N.
From table 2,3,4,5,6,7, each unit for electrical property parameters after the interpolation of auxiliary agent makes slurry sinter has had significant lifting.
Claims (10)
1. a rear surface of solar cell silver slurry, it is characterized in that: comprise 45 ~ 60wt% metal powder, the unleaded bismuthate glass powder of 1 ~ 6wt% and 31 ~ 46wt% organic bond, 0% ~ 3wt% auxiliary agent, the Bi that described metal powder comprises silver powder, described unleaded bismuthate glass powder comprises 50 ~ 85wt%
2o
3, the B of the ZnO of 1 ~ 25wt%, 1 ~ 10wt%
2o
3, the Al of 1 ~ 5wt%
2o
3, the SiO of the BaO of 1 ~ 5wt%, 1 ~ 3wt%
2, the Sb of 0 ~ 2wt%
2o
3, described organic bond comprises 1 ~ 15wt% organic carrier and 5 ~ 98wt% organic solvent, and described auxiliary agent is zinc oxide, at least one in titanium oxide, nickel oxide, nickelous selenide and telluride nickel.
2. rear surface of solar cell silver slurry according to claim 1, is characterized in that: described nickelous selenide is h-NiSe, r-NiSe, Ni
2se
3, Ni
0.85se, NiSe
2in at least one.
3. rear surface of solar cell silver slurry according to claim 2, is characterized in that: described cube of NiSe
2domain size distribution is at 3 ~ 5 μm or 0.5 ~ 1 μm or 100nm ~ 200nm.
4. rear surface of solar cell silver slurry according to claim 1, is characterized in that: the particle diameter of described auxiliary agent is less than 5 μm.
5. rear surface of solar cell silver slurry according to claim 1, is characterized in that: described metal powder also comprises at least one in copper powder, aluminium powder and nickel powder.
6. rear surface of solar cell silver slurry according to claim 1, is characterized in that: described organic carrier is at least one in acrylic resin, ethyl cellulose, butyl cellulose.
7. rear surface of solar cell silver slurry according to claim 1, is characterized in that: described organic solvent is at least one of castor oil, terpinol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, sorbitan monostearate.
8. rear surface of solar cell silver slurry according to claim 7, it is characterized in that: described organic solvent also comprises the organic additive of 1 ~ 10wt%, this organic additive is at least one in thixotropic agent, plasticizer, surfactant.
9. rear surface of solar cell silver slurry according to claim 1, is characterized in that: described glass dust average grain diameter≤3 μm.
10. the preparation method of the rear surface of solar cell silver slurry according to claim 1-9 any one, it is characterized in that, comprise the following steps: (1) takes unleaded bismuthate glass powder in proportion, unleaded bismuthate glass powder is warming up to 900 ~ 1300 DEG C, insulation 30 ~ 50min, ball milling 40 ~ 50h after shrend, filters through 200 eye mesh screens and dries at 80 ~ 110 DEG C, obtaining the glass dust of average grain diameter≤3um;
(2) take organic carrier and organic solvent in proportion to carry out water flowing circulation and heat up and be uniformly mixed, keep whipping temp to be 50 ~ 100 DEG C, after dissolving 3 ~ 10h, add surfactant, be incubated 5 ~ 15min, deposit after filtration;
(3) preparation of rear surface of solar cell silver slurry: take conductive metal powder in proportion, by the unleaded bismuthate glass powder in step (1) and the organic bond in step (2) and conductive metal powder mixing, and add auxiliary agent and carry out mix and blend, granularity≤5 μm are ground to three-high mill rolling, viscosity is 290 ~ 380PaS, obtains slurry.
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| CN106128554A (en) * | 2016-09-23 | 2016-11-16 | 苏州柏特瑞新材料有限公司 | A kind of aging resistance crystal silicon solar batteries back electrode silver slurry |
| CN106128633A (en) * | 2016-06-16 | 2016-11-16 | 赵兰 | A kind of preparation method of solar battery front side lead-free silver slurry |
| CN107301886A (en) * | 2017-05-15 | 2017-10-27 | 江苏东昇光伏科技有限公司 | Back electrode electrocondution slurry and preparation method thereof in a kind of solar cell |
| TWI638793B (en) | 2017-04-28 | 2018-10-21 | 碩禾電子材料股份有限公司 | Conductive paste for solar cell, solar cell and manufacturing method thereof, and solar cell module |
| CN108806828A (en) * | 2017-04-28 | 2018-11-13 | 硕禾电子材料股份有限公司 | For the conductive paste of solar cell, solar cell and its manufacturing method and solar cell module |
| CN109754899A (en) * | 2017-11-03 | 2019-05-14 | 丹阳八紫光能有限公司 | A kind of photovoltaic cell silver paste |
| CN112908511A (en) * | 2021-04-14 | 2021-06-04 | 上海日御新材料科技有限公司 | Silver conductor paste for battery back electrode |
| CN113096846A (en) * | 2021-03-23 | 2021-07-09 | 华中科技大学 | P-type emitter ohmic contact silver electrode slurry |
| CN114843004A (en) * | 2022-04-15 | 2022-08-02 | 北京大学深圳研究生院 | Conductive silver paste and preparation method and application thereof |
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| CN109754899A (en) * | 2017-11-03 | 2019-05-14 | 丹阳八紫光能有限公司 | A kind of photovoltaic cell silver paste |
| CN113096846A (en) * | 2021-03-23 | 2021-07-09 | 华中科技大学 | P-type emitter ohmic contact silver electrode slurry |
| CN112908511A (en) * | 2021-04-14 | 2021-06-04 | 上海日御新材料科技有限公司 | Silver conductor paste for battery back electrode |
| CN114843004A (en) * | 2022-04-15 | 2022-08-02 | 北京大学深圳研究生院 | Conductive silver paste and preparation method and application thereof |
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