CN102054882A - Conductive silver paste with grid electrode front of crystalline silicon solar cell and preparation method - Google Patents

Conductive silver paste with grid electrode front of crystalline silicon solar cell and preparation method Download PDF

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CN102054882A
CN102054882A CN2009101979189A CN200910197918A CN102054882A CN 102054882 A CN102054882 A CN 102054882A CN 2009101979189 A CN2009101979189 A CN 2009101979189A CN 200910197918 A CN200910197918 A CN 200910197918A CN 102054882 A CN102054882 A CN 102054882A
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silver paste
conductive silver
silicon solar
crystal silicon
solar energy
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CN102054882B (en
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周文彬
王启明
王德龙
闻卫荣
朱玉明
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SHANGHAI BAOYIN ELECTRONIC MATERIALS Ltd
Shanghai Nuclear Industry N4 Inst
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BAOYIN ELECTRONIC MATERIAL Co Ltd SHANGHAI
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Abstract

The invention relates to a conductive silver paste with grid electrode front of a crystalline silicon solar cell and a preparation method, wherein the conductive silver paste comprises the following components and contents (wt %): 50 to 70 wt % of metal sliver powder, 1 to 3 wt % of glass powder, 0.5 to 5 wt % of polymer resin, 1 to 10 wt % of a metal oxide and 10 to 20 wt % of a solvent; and the preparation method of the conductive silver paste with grid electrode front of a crystalline silicon solar cell comprises preparing materials, preparing a carrier, preparing sliver paste and producing silver paste materials. Compared with the prior art, the conductive silver paste with grid electrode front of a crystalline silicon solar cell and a preparation method provided by the invention have the advantages that the conversion efficiency of crystalline silicon cell is high, the volume resistance of the conductive silver paste material is low, the surface oxidation stability of sliver layer is improved well, the bonding strength between the sliver layer and the silicon is relatively high and the sliver paste has relatively good fine wire printability and relatively wide scope of sintering temperature.

Description

Crystal silicon solar energy battery front grid conductive silver paste and preparation method thereof
Technical field
The present invention relates to a kind of used for solar batteries conductive silver paste, especially relate to a kind of crystal silicon solar energy battery front grid conductive silver paste and preparation method thereof.
Background technology
Solar energy is human inexhaustible regenerative resource. also is clean energy resource, do not produce any environmental pollution.In the middle of effective utilization of solar energy; Big sun can solar photovoltaic utilization be a research field with fastest developing speed in the last few years, most active, is one of project that wherein attracts most attention.Large-scale development and utilize photovoltaic solar generating, improving the photoelectric conversion efficiency of battery and reducing production costs is its core place, since nearly ten years people to the solar cell theoretic knowledge further deeply, the improvement of production technology, the infiltration of IC technology and the appearance of new battery structure, the conversion efficiency of battery is greatly improved.
Along with solar power generation is more and more paid attention to by people, countries in the world are one after another at the exploitation solar module, and the production of 10 years photovoltaic modulies from now on will be with 20-30% even higher increasing velocity development.Fast-developing roof plan, various tax reduction and exemption policy and subsidy policy and ripe gradually green electric power supply price provide solid foundation for the development in photovoltaic market.Market will be progressively by the alternative energy source transition of the additional energy in outlying district and rural area to the whole society.In prediction next century, photovoltaic generation becomes one of human basic energy resource.
The future prospect of photovoltaic is familiar with by more and more many national government and financial quarters (as the World Bank).Particularly the numerous and confused photovoltaic development plan of formulating in many developed countries and area since 97 years is installed 4.6GW (USDOE's planning contains 1,000,000 roof plans) as the U.S. to planning accumulative total in 2010; European Union's accumulative total is installed 6.7GW (regenerative resource white paper), and wherein 3.7GW is installed in inside, Europe, the 3GW outlet; Japan's accumulative total is installed 5GW (the new sunlight program of NEDO Japan), estimates the 1.8GW of other developing countries (estimating about 10%), and world's accumulative total is installed 18GW.Be more than 200 times in 1998, world's photovoltaic module price when the time comes: 1-1.5 dollar/Wp, installation cost be below 2 dollars, cost of electricity-generating 6-8 cent part/KWh.
This patent relates to used for solar batteries proprietary material-electrode slurry.Solar cell is to utilize to be subjected to that solar light irradiation evokes electronics and the potential difference that produces and obtain electric energy.Because of the surface (phototropic face) of Si sheet makes P diffuse to form the n N-type semiconductor N as coexisting substances, the aluminium that utilizes at the back side diffuses to form P shape semiconductor, has so just formed the form that P-n engages.On the N type semiconductor front as output current can electrode uses is exactly conductive paste for solar cell.
The silver paste that generally uses at present is The foreign chicken products such as Dupont and FERRO, mainly have following problem: the crystal silicon cell transformation efficiency is not high enough, the volume resistance of conductive silver paste is bigger, the silver layer surface non-oxidizability is relatively poor, silver layer and silicon bond strength are general, and silver slurry sintering range is narrower.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists that a kind of crystal silicon cell conversion ratio height, volume resistance are low, the fine rule printing preferably crystal silicon solar energy battery with front grid conductive silver paste and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of crystal silicon solar energy battery front grid conductive silver paste is characterized in that this conductive silver paste comprises following component and content (wt%):
Silver powder 75-80;
Glass dust 1-3;
Macromolecule resin 0.5-5;
Organo-metallic compound 0.5-3;
Metal oxide 1-10;
Solvent 10-20.
Described silver powder is spherical silver powder, and the grain diameter of this silver powder is 0.4-1 μ m, and tap density is 3.5-5.0g/ml.
Described glass dust is lead-free glass powder, and sintering temperature is 680-780 ℃.
Described macromolecule resin comprises ethyl cellulose resin.
Described organo-metallic compound comprises Indium Tris acetylacetonate, acetylacetone,2,4-pentanedione gallium or copper naphthenate.
Described metal oxide is selected from one or more in zinc oxide, tin oxide or the titanium oxide.
Described solvent comprises 12 ester alcohol.
A kind of crystal silicon solar energy battery preparation method of front grid conductive silver paste is characterized in that this method may further comprise the steps:
(1) get the raw materials ready, get the raw materials ready according to following component and content (wt%):
(2) preparation of carrier: take by weighing macromolecule resin and solvent, be heated to 80 ℃ and constant temperature then, be dissolved to viscosity at the 15000-35000 centipoise, with resin filtering and impurity removing on 300-400 purpose screen cloth, obtain carrier again until resin constant temperature;
(3) preparation of silver slurry: take by weighing silver powder, glass dust, organo-metallic compound and metal oxide, it is fully mixed in batch mixer with carrier, re-use high speed dispersor and carry out high speed dispersion, obtain uniform slurry;
(4) production of silver paste: above-mentioned slurry is ground in three-high mill, and the fine setting by solvent reaches below the 15 μ m silver slurry fineness, and viscosity is 800-1200PaS, makes crystal silicon solar energy battery with front grid conductive silver paste.
Compared with prior art, the present invention solves electric conductivity, non-oxidizability by spherical silver powder; Solve sintering range and bond strength by glass dust; Solve cell conversion efficiency by organo-metallic compound and metal oxide; Solve fine rule silk screen printing performance by resin and solvent, thereby improve the crystal silicon cell transformation efficiency, reduce the volume resistance of conductive silver paste, improve the silver layer surface non-oxidizability, silver layer and silicon bond strength are than higher, and silver slurry has the sintering range of fine rule printing and broad preferably, as monocrystalline silicon, polysilicon solar cell front grid conductive silver paste, import substitution product.
Description of drawings
Fig. 1 is the structural representation of solar components.
1 is that front grid conductive silver paste, 2 is that antireflection layer, 3 is that N type semiconductor, 4 is that P type semiconductor, 5 is backplate among the figure.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
A kind of crystal silicon solar energy battery preparation method of front grid conductive silver paste, this method may further comprise the steps:
(1) gets the raw materials ready, get the raw materials ready: silver powder 72kg, glass dust 2kg, macromolecule resin 3kg, organo-metallic compound 1kg, metal oxide 7kg, solvent 11kg according to following component.Used silver powder is spherical silver powder, and grain diameter is 0.4 μ m, tap density 4.0g/ml; Used glass dust is lead-free glass powder, and sintering temperature is 750 ℃; Used macromolecule resin is an ethyl cellulose, and viscosity grade is 4; Used organo-metallic compound is an Indium Tris acetylacetonate; Used metal oxide is a zinc oxide, average grain diameter 0.2 μ m; Used solvent is 12 ester alcohol;
(2) preparation of carrier: take by weighing ethyl cellulose and 12 ester alcohol, be heated to 80 ℃ and constant temperature, be dissolved to viscosity at the 15000-25000 centipoise, with resin filtering and impurity removing on 300-400 purpose screen cloth, obtain carrier again until resin constant temperature;
(3) preparation of silver slurry: take by weighing silver powder, lead-free glass powder, Indium Tris acetylacetonate and zinc oxide, it is fully mixed in batch mixer with carrier, re-use high speed dispersor and carry out high speed dispersion, obtain uniform slurry;
(4) production of silver paste: above-mentioned slurry is ground in three-high mill, and the fine setting by solvent makes silver slurry fineness reach 10 μ m, and viscosity is 800-1200PaS, makes crystal silicon solar energy battery with front grid conductive silver paste.
Above-mentioned silver slurry is sprayed on the solar components, and as shown in Figure 1, solar components comprises front grid conductive silver paste 1, antireflection layer 2, N type semiconductor 3, P type semiconductor 4 and backplate 5.Front grid conductive silver paste 1 is located at the top of antireflection layer 2, and the bottom of antireflection layer 2 is followed successively by N type semiconductor 3, P type semiconductor 4 and backplate 5, arranges in order.
Embodiment 2
(1) gets the raw materials ready, get the raw materials ready: silver powder 76kg, glass dust 2kg, macromolecule resin 3kg, organo-metallic compound 1kg, metal oxide 7kg, solvent 11kg according to following component.Used silver powder is spherical silver powder, and grain diameter is 0.6 μ m, tap density 4.4g/ml; Used glass dust is lead-free glass powder, and sintering temperature is 720 ℃; Used macromolecule resin is an ethyl cellulose, and viscosity grade is 7; Used organo-metallic compound is a copper naphthenate; Used metal oxide is a tin oxide, average grain diameter 0.2 μ m; Used solvent is 12 ester alcohol;
(2) preparation of carrier: take by weighing ethyl cellulose and 12 ester alcohol, be heated to 80 ℃ and constant temperature, be dissolved to viscosity at the 25000-35000 centipoise, with resin filtering and impurity removing on 300-400 purpose screen cloth, obtain carrier again until resin constant temperature;
(3) preparation of silver slurry: take by weighing silver powder, lead-free glass powder, copper naphthenate and tin oxide, it is fully mixed in batch mixer with carrier, re-use high speed dispersor and carry out high speed dispersion, obtain uniform slurry;
(4) production of silver paste: above-mentioned slurry is ground in three-high mill, and the fine setting by solvent reaches below the 15 μ m silver slurry fineness, and viscosity is 800-1200PaS, makes crystal silicon solar energy battery with front grid conductive silver paste.
Embodiment 3
(1) gets the raw materials ready, get the raw materials ready: silver powder 75kg, glass dust 3kg, macromolecule resin 0.5kg, organo-metallic compound 0.5kg, metal oxide 1kg, solvent 10kg according to following component.Used silver powder is spherical silver powder, and grain diameter is 0.4 μ m, tap density 3.5g/ml; Used glass dust is lead-free glass powder, and sintering temperature is 680 ℃; Used macromolecule resin is an ethyl cellulose, and viscosity grade is 5; Used organo-metallic compound is the acetylacetone,2,4-pentanedione gallium; Used metal oxide is a titanium oxide, average grain diameter 0.5 μ m; Used solvent is 12 ester alcohol;
(2) preparation of carrier: take by weighing ethyl cellulose and 12 ester alcohol, be heated to 80 ℃ and constant temperature, be dissolved to viscosity at 15000 centipoises, with resin filtering and impurity removing on 300 purpose screen cloths, obtain carrier again until resin constant temperature;
(3) preparation of silver slurry: take by weighing silver powder, lead-free glass powder, acetylacetone,2,4-pentanedione gallium and titanium oxide, it is fully mixed in batch mixer with carrier, re-use high speed dispersor and carry out high speed dispersion, obtain uniform slurry;
(4) production of silver paste: above-mentioned slurry is ground in three-high mill, and the fine setting by solvent makes silver slurry fineness reach 8 μ m, and viscosity is 800PaS, makes crystal silicon solar energy battery with front grid conductive silver paste.
Embodiment 4
(1) gets the raw materials ready, get the raw materials ready: silver powder 80kg, glass dust 1kg, macromolecule resin 5kg, organo-metallic compound 3kg, metal oxide 10kg, solvent 20kg according to following component.Used silver powder is spherical silver powder, and grain diameter is 1 μ m, tap density 5.0g/ml; Used glass dust is lead-free glass powder, and sintering temperature is 780 ℃; Used macromolecule resin is an ethyl cellulose, and viscosity grade is 6; Used organo-metallic compound is a copper naphthenate; Used metal oxide is a zinc oxide, average grain diameter 0.3 μ m; Used solvent is 12 ester alcohol;
(2) preparation of carrier: take by weighing ethyl cellulose and 12 ester alcohol, be heated to 80 ℃ and constant temperature, be dissolved to viscosity at 35000 centipoises, with resin filtering and impurity removing on 400 purpose screen cloths, obtain carrier again until resin constant temperature;
(3) preparation of silver slurry: take by weighing silver powder, lead-free glass powder, copper naphthenate and zinc oxide, it is fully mixed in batch mixer with carrier, re-use high speed dispersor and carry out high speed dispersion, obtain uniform slurry;
(4) production of silver paste: above-mentioned slurry is ground in three-high mill, and the fine setting by solvent makes silver slurry fineness reach 10 μ m, and viscosity is 1200PaS, makes crystal silicon solar energy battery with front grid conductive silver paste.

Claims (8)

1. a crystal silicon solar energy battery is characterized in that this conductive silver paste comprises following component and content (wt%) with front grid conductive silver paste:
Silver powder 75-80;
Glass dust 1-3;
Macromolecule resin 0.5-5;
Organo-metallic compound 0.5-3;
Metal oxide 1-10;
Solvent 10-20.
2. a kind of crystal silicon solar energy battery according to claim 1 is characterized in that with front grid conductive silver paste described silver powder is spherical silver powder, and the grain diameter of this silver powder is 0.4-1 μ m, and tap density is 3.5-5.0g/ml.
3. a kind of crystal silicon solar energy battery according to claim 1 is characterized in that with front grid conductive silver paste described glass dust is lead-free glass powder, and sintering temperature is 680-780 ℃.
4. a kind of crystal silicon solar energy battery according to claim 1 is characterized in that with front grid conductive silver paste described macromolecule resin comprises ethyl cellulose resin.
5. a kind of crystal silicon solar energy battery according to claim 1 is characterized in that with front grid conductive silver paste described organo-metallic compound comprises Indium Tris acetylacetonate, acetylacetone,2,4-pentanedione gallium or copper naphthenate.
6. a kind of crystal silicon solar energy battery according to claim 1 is characterized in that with front grid conductive silver paste described metal oxide is selected from one or more in zinc oxide, tin oxide or the titanium oxide.
7. a kind of crystal silicon solar energy battery according to claim 1 is characterized in that with front grid conductive silver paste described solvent comprises 12 ester alcohol.
8. a crystal silicon solar energy battery is characterized in that this method may further comprise the steps with the preparation method of front grid conductive silver paste:
(1) get the raw materials ready, get the raw materials ready according to following component and content (wt%):
Figure F2009101979189C0000012
Figure F2009101979189C0000021
(2) preparation of carrier: take by weighing macromolecule resin and solvent, be heated to 80 ℃ and constant temperature then, be dissolved to viscosity at the 15000-35000 centipoise, with resin filtering and impurity removing on 300-400 purpose screen cloth, obtain carrier again until resin constant temperature;
(3) preparation of silver slurry: take by weighing silver powder, glass dust, organo-metallic compound and metal oxide, it is fully mixed in batch mixer with carrier, re-use high speed dispersor and carry out high speed dispersion, obtain uniform slurry;
(4) production of silver paste: above-mentioned slurry is ground in three-high mill, and the fine setting by solvent reaches below the 15 μ m silver slurry fineness, and viscosity is 800-1200PaS, makes crystal silicon solar energy battery with front grid conductive silver paste.
CN2009101979189A 2009-10-29 2009-10-29 Conductive silver paste with grid electrode front of crystalline silicon solar cell and preparation method Expired - Fee Related CN102054882B (en)

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CN102262916A (en) * 2011-07-19 2011-11-30 彩虹集团公司 Front silver paste for crystalline silicon solar cell and preparation method
CN102568648A (en) * 2011-12-29 2012-07-11 广东爱康太阳能科技有限公司 Conductive silver paste and preparation method thereof
CN102629496A (en) * 2012-04-27 2012-08-08 西安银泰新能源材料科技有限公司 Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry
CN103093861A (en) * 2013-02-17 2013-05-08 上海大洲电子材料有限公司 Low-cost unleaded environmental protection silver paste for back electrode of silicon solar cell and application thereof
CN103440898A (en) * 2013-08-06 2013-12-11 浙江光达电子科技有限公司 Solar cell front face electrode silver paste with low silver content and method for preparing same
CN103578604A (en) * 2013-09-22 2014-02-12 杭州正银电子材料有限公司 Front-face electrode slurry with low silver content for silica-based solar cell main grid and preparation method of front-face electrode slurry
CN103915248A (en) * 2014-03-27 2014-07-09 深圳振华富电子有限公司 Manufacturing method of base metal terminal electrode inductor
CN104185875A (en) * 2012-03-28 2014-12-03 东丽株式会社 Photosensitive conductive paste and method for manufacturing conductive substrate with wiring
CN105590663A (en) * 2016-01-07 2016-05-18 清华大学 Lead-free and bismuth-free conductive silver paste, preparation method of silver grid line, and silicon solar cell
CN105761775A (en) * 2014-12-18 2016-07-13 上海宝银电子材料有限公司 Conductive silver paste for on-chip inductor external electrode and preparation method of conductive silver paste
CN106573301A (en) * 2014-07-31 2017-04-19 同和电子科技有限公司 Silver powder, method for producing same, and conductive paste
CN107274962A (en) * 2017-05-18 2017-10-20 江苏东昇光伏科技有限公司 A kind of slurry used for solar batteries and preparation method thereof
US9993871B2 (en) 2014-07-31 2018-06-12 Dowa Electronics Materials Co., Ltd. Silver powder, method for producing same, and conductive paste
CN109192396A (en) * 2018-09-28 2019-01-11 王敏 A kind of preparation method of anti-oxidative conductive silver paste thick-film material
CN113471314A (en) * 2021-05-07 2021-10-01 盐城工学院 Method for preparing selective emitter by using gallium-doped silicon nano slurry

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CN102262916A (en) * 2011-07-19 2011-11-30 彩虹集团公司 Front silver paste for crystalline silicon solar cell and preparation method
CN102568648A (en) * 2011-12-29 2012-07-11 广东爱康太阳能科技有限公司 Conductive silver paste and preparation method thereof
CN104185875A (en) * 2012-03-28 2014-12-03 东丽株式会社 Photosensitive conductive paste and method for manufacturing conductive substrate with wiring
CN102629496A (en) * 2012-04-27 2012-08-08 西安银泰新能源材料科技有限公司 Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry
CN102629496B (en) * 2012-04-27 2015-02-18 西安银泰新能源材料科技有限公司 Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry
CN103093861A (en) * 2013-02-17 2013-05-08 上海大洲电子材料有限公司 Low-cost unleaded environmental protection silver paste for back electrode of silicon solar cell and application thereof
CN103440898A (en) * 2013-08-06 2013-12-11 浙江光达电子科技有限公司 Solar cell front face electrode silver paste with low silver content and method for preparing same
CN103440898B (en) * 2013-08-06 2017-06-06 浙江光达电子科技有限公司 A kind of front electrode of solar battery silver paste of low silver content and preparation method thereof
CN103578604A (en) * 2013-09-22 2014-02-12 杭州正银电子材料有限公司 Front-face electrode slurry with low silver content for silica-based solar cell main grid and preparation method of front-face electrode slurry
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CN106573301B (en) * 2014-07-31 2019-08-09 同和电子科技有限公司 Silver powder and its conductive paste
CN106573301A (en) * 2014-07-31 2017-04-19 同和电子科技有限公司 Silver powder, method for producing same, and conductive paste
US9993871B2 (en) 2014-07-31 2018-06-12 Dowa Electronics Materials Co., Ltd. Silver powder, method for producing same, and conductive paste
US10252331B2 (en) 2014-07-31 2019-04-09 Dowa Electronics Materials Co., Ltd. Silver powder, method for producing same, and conductive paste
CN105761775A (en) * 2014-12-18 2016-07-13 上海宝银电子材料有限公司 Conductive silver paste for on-chip inductor external electrode and preparation method of conductive silver paste
CN105761775B (en) * 2014-12-18 2017-07-21 上海宝银电子材料有限公司 A kind of chip inductor external electrode conductive silver paste and preparation method thereof
CN105590663A (en) * 2016-01-07 2016-05-18 清华大学 Lead-free and bismuth-free conductive silver paste, preparation method of silver grid line, and silicon solar cell
CN107274962A (en) * 2017-05-18 2017-10-20 江苏东昇光伏科技有限公司 A kind of slurry used for solar batteries and preparation method thereof
CN109192396A (en) * 2018-09-28 2019-01-11 王敏 A kind of preparation method of anti-oxidative conductive silver paste thick-film material
CN113471314A (en) * 2021-05-07 2021-10-01 盐城工学院 Method for preparing selective emitter by using gallium-doped silicon nano slurry

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