CN104700923B - A kind of rear surface of solar cell silver paste of high electricity conversion and preparation method thereof - Google Patents

A kind of rear surface of solar cell silver paste of high electricity conversion and preparation method thereof Download PDF

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CN104700923B
CN104700923B CN201310664600.3A CN201310664600A CN104700923B CN 104700923 B CN104700923 B CN 104700923B CN 201310664600 A CN201310664600 A CN 201310664600A CN 104700923 B CN104700923 B CN 104700923B
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silver powder
solar cell
silver
rear surface
silver paste
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CN104700923A (en
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刘飘
祁鑫
刘宵
胡蔚
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HUNAN LEED THICK FILM PASTE CO Ltd
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HUNAN LEED THICK FILM PASTE CO Ltd
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Abstract

The invention discloses a kind of rear surface of solar cell silver paste of high electricity conversion.The weight percentage of each component is:Irregular flake silver powder 20%, dendroid silver powder 10% 25%, lenticular ball shape silver powder 10%, nano-silver powder 5% 15%, glass dust 2.5% 7.5%, polymolecularity organic bond 30% 55%, adhesion promoter 0.1% 5%, auxiliary agent 0.5 3%, the percetage by weight sum of each component is 100%.The invention also discloses the preparation method of the rear surface of solar cell silver paste of above-mentioned high phototranstormation efficiency.Compared with prior art, this slurry employs the combination of irregular flake silver powder and dendroid silver powder to ensure outstanding electrical property, and the silver powder of different shape is then greatly improved the sinterable scope of back silver paste, the use of nano-silver powder can then significantly improve the phototranstormation efficiency of solar cell.

Description

A kind of rear surface of solar cell silver paste of high electricity conversion and preparation method thereof
Technical field
The present invention relates to solar cell photovoltaic field of material technology, specially solar energy crystal silicon cell back side silver paste And preparation method thereof.
Background technology
Solar energy crystalline silicon photovoltaic electricity generation system is the photovoltaic effect using silion cell semiconductor, and solar radiation energy is straight Switch through a kind of new power generating system for being changed to electric energy, due to its green feature, obtain fast development in the whole world at present. At present, the cost of solar cell and transformation efficiency, which turn into, restricts its bottleneck further developed.Solar energy crystal silicon cell is carried on the back The left and right of collected current is played with silver paste in face.
The back side with the important component that silver paste is solar cell, by silver powder, glass dust, organic bond and other help Agent is prepared, and the silion cell back side is printed on by screen printing technique, is first of slurry of silk-screen, after sintering Backplate is formed, collects the electric current of formation.Back silver paste requires excellent printing performance, electric conductivity, weldability Energy and adhesive force.Silver powder plays a part of conductive and welding as function of tonic chord phase in back silver paste;Glass dust is as slave function Phase, the important function of bonding silver powder is played in sintering process.
At present, as problems with occur in the continuous decline for carrying on the back silver-colored silver content, back of the body silver:
1. the reduction of silver content causes adhesive force to occur declining.
2. the reduction of silver content causes welding performance to occur declining.
3. the reduction of silver content causes electrical performance of cell to occur declining.
The content of the invention
The present invention is according to above-mentioned deficiency, there is provided a kind of adhesive force is good, welding performance is strong, the cell piece of high conversion efficiency With back side silver paste.
Technical problem solved by the invention is realized using following technical scheme:
A kind of back silver paste of solar cell of high electricity conversion, the weight percentage of each component are:Irregularly Flake silver powder 10~20%, dendroid silver powder 10~25%, lenticular ball shape silver powder 10-30%, nano-silver powder 5%-15%, glass Glass powder 2.5%-7.5%, polymolecularity organic bond 30%-55%, adhesion promoter 0.1%-5%, auxiliary agent 0.5- 3%, the percetage by weight sum of each component is 100%.
Irregular flake silver powder, dendroid silver powder, lenticular ball shape silver powder, the percetage by weight sum of nano-silver powder For 40-65%.
It with certain thickness flake silver powder, the silver powder thickness is the 2-3 of conventional sheet silver that the irregular flake silver powder, which is, Times, average grain diameter is 1.5-2.5 microns, and purity is more than 99.90%.
The nano-silver powder is the nano-silver powder for having high dispersive characteristic, is disperseed using organic solvent, is disperseed used Organic solvent does not conflict with whole slurry system, and the average grain diameter of nano-silver powder is 5-10 nanometers, and purity is more than 99.90%.
Described glass dust is made up of the raw material of following mass ratio:Bi2O320-60%, PbO 0-20%, ZnO 10- 30%, Al2O35-25%, SiO24-19%, CaO 0.5-11%, BaO 1.2-10%, other micro amount of oxygen compounds 0.5-3%.
Other described micro amount of oxygen compounds are Ga2O3, MnO2, Fe2O3One or more of compositions in several oxides.
Described polymolecularity organic bond is made up of the raw material of following mass ratio:Terpinol 5%-72%, butyl card Must alcohol 12-38%, butyl carbitol acetate 5-15%, ethyl cellulose 3-8%, propandiol butyl ether 0.5-10%, ethylene glycol 0.3-1.5%, butyl acetate cellulose 2-3%.
Described adhesion promoter is to add without polysiloxane non-ionic compound and the conventional use of adhesive force of industry Add agent.
Described auxiliary agent is that esters of acrylic acid levelling agent, organobentonite class thixotropic agent, lipophile dispersant and industry are normal Advise the auxiliary agent used.
The preparation process of the rear surface of solar cell silver paste of the high electricity conversion is:
(1) preparation of glass dust:Weighed by formula rate prepare glass dust raw material it is well mixed after, in vacuum drying oven 100~200 DEG C of drying 2.5-3.5 hours;Then the melting 0.5-1.8 hours at 800-1600 DEG C, dried after deionization water quenching, Ball milling 300-1000 minutes are carried out again, are sieved after drying and are obtained the glass dust that average grain diameter is less than 5 microns.
(2) preparation of polymolecularity organic bond:Carried out after the raw material for preparing organic bond is weighed by formula rate It is scattered at a high speed, then dissolved by heating under 70-150 degrees Celsius, dissolution time is 80-240 minutes.
(3) by formula, by polymolecularity organic bond prepared by glass dust prepared by silver powder, step (1), step (2) After being configured to slurry, first carry out scattered be ground again at a high speed and roll slurry 5~15 times, finally give back of the body silver of the fineness less than 15 microns Slurry.
Need to be ground after the raw material mixing of glass dust in the step (1) it is scattered, reach color it is homogeneous after dried. In step (2) polymolecularity organic bond prepare non-solid component need to first be stirred after again substep add resin and Auxiliary agent.Need that first the slurry prepared is uniformly dispersed in step (3), be then ground in ball mill, finally roll Meet to require.It is using three-high mill and ball mill that slurry is rolled in grinding of the present invention.
The advantages of the present invention are:
1. the present invention has excellent performance, conversion ratio exceedes existing slurry.
2 present invention have simple preparation method, and preparation cost is low, and production is stable.
3 adhesive force of the present invention are good, environmentally safe.
Auxiliary agent and additive that 4 present invention use have greatly facilitated the overall performance of slurry.
Embodiment:
The present invention is expanded on further below by the detailed description of embodiment, is not limitation of the present invention, Protection scope of the present invention is not limited in following instance.The technical field personnel according to above present disclosure and Method, the reachable purpose of the present invention.
Raw material of the present invention is commercially available convenient source, and equipment is industry conventional equipment.
Embodiment 1
(1) glass dust is prepared:Weigh:Bi2O342.7%, PbO 15.8%, ZnO 27.2%, Al2O3 5.4%, SiO2 7.2%, CaO 0.6%, BaO 2.6%, other micro amount of oxygen compounds 2.6%.Wherein micro amount of oxygen compound is following several oxides In one or more:Ga2O3, MnO, Fe2O3Deng.After well mixed, dried 2.75 hours for 125 DEG C in vacuum drying oven;Then Melting 0.9 hour at 1360 DEG C, is dried after deionization water quenching, then carries out ball milling 750 minutes, is sieved after drying and is obtained average grain Footpath is less than 5 microns of glass dust.
(2) organic system is prepared:Weigh:Terpinol 55.4%, butyl carbitol 25.26%, butyl carbitol acetate 7.6%, ethyl cellulose 4.7%, 3.8% propandiol butyl ether, 0.47% ethylene glycol, 2.77% butyl acetate fiber Element.
(3) silver powder:Lenticular ball shape silver powder purity is more than 99.97%, and average grain diameter is 0.74 micron;Flake silver powder purity More than 99.90%, average grain diameter is 4.1 microns;Nano-silver powder purity is more than 99.98%, and average grain diameter is 6.4 nanometers;Branch Shape silver powder purity is more than 99.92%, and average grain diameter is 1.77 microns.
(4) adhesive force additive:Without polysiloxane non-ionic compound and the conventional use of adhesive force additive of industry.
(5) auxiliary agent:Esters of acrylic acid levelling agent, organobentonite class thixotropic agent, lipophile dispersant and industry routinely make Auxiliary agent.
According to silver powder 51.1%, glass dust 4.9%, organic solvent 40%, adhesive force additive 1.5%, auxiliary agent 2.5%, Carry out disperseing at a high speed 0.5 hour after well mixed, then rolled 13 times using three-high mill, fineness of grind to 9 microns, viscosity is 35000mpa·S.Obtain high transformation efficiency cell piece back side silver paste.By slurry with 325 mesh screen paintings in silicon solar cell 125mm × 125mm back sides, photoelectric transformation efficiency survey is carried out after cell piece is made according to crystal silicon solar cell sheet Making programme Examination, testing mean reach 18.7%.Cell piece after the completion of above-mentioned test is subjected to adhesive force test, existed with Pb-free coating band Welded under 330 degree, then 180 degree carries out pullling test, and test result shows that adhesive force is all higher than 8N.
Embodiment 2
(1) glass dust is prepared:Weigh:Bi2O322.5%, PbO 19.1%, ZnO 30%, Al2O3 15.4%, SiO2 4.1%, CaO 0.7%, BaO 1.3%, other micro amount of oxygen compounds 2.8%.Wherein micro amount of oxygen compound is following several oxides In one or more:Ga2O3, MnO, Fe2O3Deng.After well mixed, dried 2.75 hours for 125 DEG C in vacuum drying oven;Then Melting 0.9 hour at 1360 DEG C, is dried after deionization water quenching, then carries out ball milling 750 minutes, is sieved after drying and is obtained average grain Footpath is less than 5 microns of glass dust.
(2) organic system is prepared:Weigh:Terpinol 41.29%, butyl carbitol 36.37%, butyl carbitol acetate 10.5%, ethyl cellulose 5.7%, 2.9% propandiol butyl ether, 0.47% ethylene glycol, 2.77% butyl acetate fiber Element.
(3) silver powder:Lenticular ball shape silver powder purity is more than 99.97%, and average grain diameter is 0.74 micron;Flake silver powder purity More than 99.90%, average grain diameter is 4.1 microns;Nano-silver powder purity is more than 99.98%, and average grain diameter is 6.4 nanometers;Branch Shape silver powder purity is more than 99.92%, and average grain diameter is 1.77 microns.
(4) adhesive force additive:Without polysiloxane non-ionic compound and the conventional use of adhesive force additive of industry.
(5) auxiliary agent:Esters of acrylic acid levelling agent, organobentonite class thixotropic agent, lipophile dispersant and industry routinely make Auxiliary agent.
According to silver powder 55.5%, glass dust 4.5%, organic solvent 36%, adhesive force additive 1.5%, auxiliary agent 2.5%, Carry out disperseing at a high speed 0.5 hour after well mixed, then rolled 13 times using three-high mill, fineness of grind to 9 microns, viscosity is 39000mpa·S.Obtain high transformation efficiency cell piece back side silver paste.By slurry with 325 mesh screen paintings in silicon solar cell 125mm × 125mm back sides, photoelectric transformation efficiency survey is carried out after cell piece is made according to crystal silicon solar cell sheet Making programme Examination, testing mean reach 18.7%.Cell piece after the completion of above-mentioned test is subjected to adhesive force test, existed with Pb-free coating band Welded under 330 degree, then 180 degree carries out pullling test, and test result shows that adhesive force is all higher than 8N.
Slurry Pmpp Uoc Isc Rs Rsh FF NCell
Contrast 4.28477 0.62979 8.583254 0.003117 190.8252 78.78507 0.181958
Embodiment 2 4.293052 0.630909 8.63821 0.002839 192.249 79.06055 0.189298
Embodiment 3
(1) glass dust is prepared:Weigh:Bi2O335.5%, PbO 15.5%, ZnO 25%, Al2O3 15%, SiO2 4%, CaO 0.7%, BaO 1.3%, other micro amount of oxygen compounds 3%.Wherein micro amount of oxygen compound is in following several oxides It is one or more of:Ga2O3, MnO, Fe2O3Deng.After well mixed, dried 2.75 hours for 125 DEG C in vacuum drying oven;Then exist Melting 0.9 hour at 1360 DEG C, is dried after deionization water quenching, then carries out ball milling 750 minutes, and being sieved after drying obtains average grain diameter Glass dust less than 5 microns.
(2) organic system is prepared:Weigh:Terpinol 40%, butyl carbitol 35%, butyl carbitol acetate 15%, Ethyl cellulose 5%, 2% propandiol butyl ether, 0.5% ethylene glycol, 2.5% butyl acetate cellulose.
(3) silver powder:Lenticular ball shape silver powder purity is more than 99.97%, and average grain diameter is 0.74 micron;Flake silver powder purity More than 99.90%, average grain diameter is 4.1 microns;Nano-silver powder purity is more than 99.98%, and average grain diameter is 6.4 nanometers;Branch Shape silver powder purity is more than 99.92%, and average grain diameter is 1.77 microns.
(4) adhesive force additive:Without polysiloxane non-ionic compound and the conventional use of adhesive force additive of industry.
(5) auxiliary agent:Esters of acrylic acid levelling agent, organobentonite class thixotropic agent, lipophile dispersant and industry routinely make Auxiliary agent.
According to silver powder 48.9%, glass dust 4.1%, organic solvent 41%, adhesive force additive 4.5%, auxiliary agent 1.5%, Carry out disperseing at a high speed 0.5 hour after well mixed, then rolled 13 times using three-high mill, fineness of grind to 9 microns, viscosity is 25000mpa·S.Obtain high transformation efficiency cell piece back side silver paste.By slurry with 325 mesh screen paintings in silicon solar cell 125mm × 125mm back sides, photoelectric transformation efficiency survey is carried out after cell piece is made according to crystal silicon solar cell sheet Making programme Examination, testing mean reach 18.7%.Cell piece after the completion of above-mentioned test is subjected to adhesive force test, existed with Pb-free coating band Welded under 330 degree, then 180 degree carries out pullling test, and test result shows that adhesive force is all higher than 8N.
Slurry Pmpp Uoc Isc Rs Rsh FF NCell
Contrast 4.28477 0.62979 8.583254 0.003117 190.8252 78.78507 0.181958
Embodiment 3 4.29935 0.631067 8.626596 0.002822 192.7703 79.13188 0.190268

Claims (5)

  1. A kind of 1. rear surface of solar cell silver paste of high electricity conversion, it is characterised in that:The weight percentage of each component For:Irregular flake silver powder 20%, dendroid silver powder 10%-25%, lenticular ball shape silver powder 10%, nano-silver powder 5%- 15%, glass dust 2.5%-7.5%, polymolecularity organic bond 30%-55%, adhesion promoter 0.1%-5%, auxiliary agent 0.5-3%, the percetage by weight sum of each component is 100%, and wherein glass dust is by following material composition:Bi2O320-60%, PbO 0-20%, ZnO 10-30%, Al2O35-25%, SiO24-19%, CaO 0.5-11%, BaO 1.2-10%, other Micro amount of oxygen compound 0.5-3%, other micro amount of oxygen compounds are Ga2O3、MnO2、Fe2O3In one or more of compositions.
  2. A kind of 2. rear surface of solar cell silver paste of high electricity conversion according to claim 1, it is characterised in that:Institute Irregular flake silver powder is stated to be 2-3 times of conventional sheet silver with certain thickness flake silver powder, the silver powder thickness, average grain diameter For 1.5-2.5 microns, purity is more than 99.90%.
  3. A kind of 3. rear surface of solar cell silver paste of high electricity conversion according to claim 1, it is characterised in that:Institute It is the nano-silver powder for having high dispersive characteristic to state nano-silver powder, is disperseed using organic solvent, disperse organic solvent used with Whole slurry system does not conflict, and the average grain diameter of nano-silver powder is 5-10 nanometers, and purity is more than 99.90%.
  4. A kind of 4. rear surface of solar cell silver paste of high electricity conversion according to claim 1, it is characterised in that:Institute The polymolecularity organic bond stated is made up of the raw material of following mass ratio:Terpinol 5%-72%, butyl carbitol 12- 38%, butyl carbitol acetate 5-15%, ethyl cellulose 3-8%, propandiol butyl ether 0.5-10%, ethylene glycol 0.3- 1.5%, butyl acetate cellulose 2-3%.
  5. 5. the preparation method of the rear surface of solar cell silver paste of high electricity conversion as claimed in claim 1, it is characterised in that Preparation process is:
    (1) preparation of glass dust:Weigh Bi2O3、PbO、ZnO、Al2O3、SiO2, CaO, BaO, other micro amount of oxygen compounds are well mixed Afterwards, 100~200 DEG C of drying 2.5-3.5 hours in vacuum drying oven;Then the melting 0.5-1.8 hours at 800-1600 DEG C, go Dried after ion water quenching, then carry out ball milling 300-1000 minutes, sieved after drying and obtain the glass that average grain diameter is less than 5 microns Powder;
    (2) preparation of polymolecularity organic bond:Carried out at a high speed after the raw material for preparing organic bond is weighed by formula rate It is scattered, then dissolved by heating under 70-150 degrees Celsius, dissolution time is 80-240 minutes;
    (3) by formula, polymolecularity organic bond prepared by glass dust prepared by silver powder, step (1), step (2) is prepared Into after slurry, first carry out scattered be ground again at a high speed and roll slurry 5-15 times, finally give the back silver paste that fineness is less than 15 microns.
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CN106611625A (en) * 2015-10-21 2017-05-03 湖南利德电子浆料股份有限公司 Low silver content efficient back passivation solar cell back silver paste
CN105845756B (en) * 2016-05-20 2017-07-14 浙江光隆能源科技股份有限公司 Close main grid polycrystalline back of solar cell silver paste of grid four and preparation method thereof
CN107731345B (en) * 2016-07-05 2019-02-15 浙江光隆能源科技股份有限公司 The preparation method of the back of solar cell silver paste of the anti-crack of the high-tensile strength of improvement
CN107591218B (en) * 2017-09-08 2019-05-24 江苏正能电子科技有限公司 Full Al-BSF crystal silicon solar battery back face silver paste, preparation method and the usage
CN109215838A (en) * 2018-11-22 2019-01-15 河北晶乐光电科技有限公司 Crystal silicon solar energy battery back electrode slurry, preparation method and battery
CN114907794A (en) * 2021-02-08 2022-08-16 翌骅实业股份有限公司 Low-silver solid content conductive adhesive and preparation method thereof

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CN102364583A (en) * 2011-09-30 2012-02-29 宁波广博纳米新材料股份有限公司 Silver paste for back face of lead-free crystal silicon solar cell and preparation method thereof
CN102664057A (en) * 2012-05-17 2012-09-12 合肥工业大学 Conductive copper paste for surface electrodes of chip ceramic capacitor and preparation method thereof
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CN1687992A (en) * 2005-05-13 2005-10-26 范琳 Electrode thick liquid without lead and silver and mfg. method thereof
CN101650982A (en) * 2009-08-18 2010-02-17 深圳市中金岭南科技有限公司 Conductive silver paste with low halogen content
CN102364583A (en) * 2011-09-30 2012-02-29 宁波广博纳米新材料股份有限公司 Silver paste for back face of lead-free crystal silicon solar cell and preparation method thereof
CN102664057A (en) * 2012-05-17 2012-09-12 合肥工业大学 Conductive copper paste for surface electrodes of chip ceramic capacitor and preparation method thereof
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Denomination of invention: A silver paste on the back of a solar cell with high photoelectric conversion efficiency and its preparation method

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