CN102568652A - Crystalline silicon solar cell electrode paste and preparation method thereof - Google Patents
Crystalline silicon solar cell electrode paste and preparation method thereof Download PDFInfo
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- CN102568652A CN102568652A CN2012100467490A CN201210046749A CN102568652A CN 102568652 A CN102568652 A CN 102568652A CN 2012100467490 A CN2012100467490 A CN 2012100467490A CN 201210046749 A CN201210046749 A CN 201210046749A CN 102568652 A CN102568652 A CN 102568652A
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Abstract
The invention relates to crystalline silicon solar cell electrode paste which comprises the following raw materials in percentage by weight: 55 percent to 69.99 percent of metal silver powder; 1 percent to 6 percent of glass binder; 3 percent to 6 percent of organic resin; 20 percent to 30 percent of organic solvent; 0.1 percent to 0.5 percent of rheological agent and 0.1 percent to 5 percent of metal silicide. A preparation method comprises the following steps: 1, preparing the metal silicide; 2, preparing an organic carrier; and 3, preparing the electrode paste. The crystalline silicon solar cell electrode paste and the preparation method have the benefits that in different raw material proportions and at different temperatures, different metal silicides can be formed; by adding the metal silicide powder formed by specific components at a specific temperature, the ohmic contact of a metal electrode and silicon is strengthened and the crystalline silicon solar cell electrode paste has low resistivity; under the condition of not influencing the electrical property of a cell, the silver content can be reduced and the production cost can be saved; the leadless glass binder is selected, the pollution to the environment can be avoided, and the crystalline silicon solar cell electrode paste has strong binding power; and by the silver powder which is meticulously selected and matched, the electrical property is improved.
Description
Technical field
The present invention relates to a kind of crystalline silicon solar battery electrode slurry and preparation method thereof.
Background technology
Solar energy is human inexhaustible clean energy resource, and exhausted day by day along with non-renewable energy resources such as coal, oil on the earth humanly demanded the energy that to turn to solar energy, solar cell be one of to use.When solar radiation arrived solar cell, solar cell utilized the characteristic electron of semi-conducting material to be directly changed into electric energy to luminous energy.In silicon solar cell technology, it is a very important link that electrode is made.From the screen printing technique development seventies in 20th century so far, its technology is very ripe, also is the main flow technology that at present extensive solar cell is produced.
The performance of electrode silver plasm directly affects the performance of battery, is the critical material in the battery manufacture process.The silver slurry is by conducting function phase silver powder, and binding agent glass dust and organic carrier and additive etc. are formulated.Organic carrier mainly carries silver powder, glass dust, and solids is suspended, and disperses, for silk screen printing provides condition; The electric conductivity of silver is very good, and silver powder sintering when high temperature fuses together, and forms the favorable conductive passage; Glass dust bonds together silver and silicon when heat treatment, makes the conductive film layer that on silicon, forms one deck even compact, but forms welding electrode.Additive can improve the rheological characteristic and the thixotropy of slurry, and on the other hand, special trace mineral supplement can strengthen the electrical property of battery.
At present, a lot of about the patent of solar cell silver slurry, but because technical difficulty is rarely found than the silver slurry of low silver content, as carrying on the back the silver content 70 ~ 77% of silver electrode with silver-colored aluminium paste in the Granted publication CN101651155B patent; Back silver paste silver content 85 ~ 95% among the notification number CN101814551A.Silver belongs to noble metal, and silver content is higher, will increase production cost.
Summary of the invention
The purpose of this invention is to provide a kind of crystalline silicon solar battery electrode slurry and preparation method thereof; Through adding the metallic silicon compounds of special temperature preparation; Choose different-shape silver powder and proportioning; Can make electrode slurry keep good printing performance, under the prerequisite of strong adhesive force and good electrical property, reduce silver content.
The objective of the invention is to realize through following technical scheme:
A kind of crystalline silicon solar battery electrode slurry comprises the raw material of following quality percentage composition: 55% ~ 69.99% silver powder, 1% ~ 6% glass binder; 3% ~ 6% organic resin; 20% ~ 30% organic solvent, 0.1% ~ 0.5% auxiliary rheological agents, 0.1% ~ 5% metal silicide; Said metal silicide is metal and silicon preliminary treatment under 300 ~ 900 ℃ temperature, again through annealing process, pulverizes ball milling at last and processes the metal silication powder; Said metal is selected from one or more among Pt, Pd, Ti, Ni, Al, Mn, Co, the Ag.
Said silver powder is that unsetting silver powder, flake silver powder and spherical silver powder mix, and the mixing quality ratio of wherein unsetting silver powder, flake silver powder and spherical silver powder is: 6 ~ 7.5:1 ~ 3:0 ~ 1, the particle diameter of silver powder are 0.5 ~ 3.5 μ m.
Said glass binder is a kind of crown glass, and its main component is B
2O
3ZnOBi
2O
3, D50 is less than 3.0 microns, and softening point is 430 ~ 480 ℃.
Said organic resin is selected from one or more in ethyl cellulose, cellaburate, polyvinyl butyral and the rosin.
Said organic solvent is selected from one or more in diethylene glycol butyl ether, isopropyl alcohol, diethylene glycol butyl ether acetic acid esters, terpineol, ethylene glycol monobutyl ether, phenmethylol and the ATBC.
Said auxiliary rheological agents is selected from a kind of in dibutyl phthalate, castor oil modified derivative, organic-silicon-modified thing and the lecithin.
The preparation method of described crystalline silicon solar battery electrode slurry may further comprise the steps:
1) preparation of metal silicide: it is 300 ~ 900 ℃ of insulation 1 ~ 2h down that metal-powder and silica flour are placed in the resistance furnace in temperature, and annealing in process is prepared into the metal silication powder that particle diameter is 1 ~ 5 μ m through ball milling;
2) preparation of organic carrier: in the agitated reactor of heat-conducting oil heating; Temperature is controlled at 70 ~ 100 ℃; Described organic solvent, organic resin and auxiliary rheological agents constant temperature in agitated reactor is stirred until dissolving fully; Time obtains prepare electrode slurry needed organic carrier through silk screen filter at 2 ~ 3h after the reactant cooling;
3) metal silicide for preparing in organic carrier, glass binder and the step 1) of preparation the preparation of electrode slurry: with silver powder, step 2) mixes; Stir with the high speed dispersion mixer; Grind 3 ~ 5 times with three-roll grinder again; The particle diameter that obtains electrode slurry at last is 4 ~ 8 μ m, viscosity be 50 ~ 100PaS (25 ℃, 10rpm).
Beneficial effect of the present invention is: metal silicide can form the different metallic silicide under different ratios of raw materials and temperature; Through adding the metal silicide powder that forms under specific components and the temperature; Strengthen the ohmic contact of metal electrode and silicon, have lower resistivity; Can not influence under the battery electrical property situation, reduce the content of silver, save production cost; Select unleaded glass binder for use, can not pollute, and cohesive force is strong environment; Silver powder through meticulous selection collocation improves electrical property.
Embodiment
Embodiment (experiment) 1
1) preparation of metal silicide: it is 750 ℃ of insulation 2h down that metal nickel powder and silica flour are placed in the resistance furnace in temperature, and annealing in process is prepared into the metal silication powder that particle diameter is 3 μ m through ball milling, and it is for use to get metal silicide 1g;
2) preparation of organic carrier: in the agitated reactor of heat-conducting oil heating; Temperature is controlled at 90 ℃; Getting isopropyl alcohol 30g, ethyl cellulose 6g and castor oil modified derivative 0.5g constant temperature in agitated reactor stirs until dissolving fully; Time is 3h, obtains preparing the needed organic carrier 36.5g of electrode slurry through silk screen filter after the reactant cooling;
3) preparation of electrode slurry: get silver powder 56g; The silver powder proportioning is that the mixing quality ratio of unsetting silver powder, flake silver powder and spherical silver powder is 7:2:1, gets step 2) the middle organic carrier 36.5g for preparing, get the metal silicide 1g for preparing in glass binder 4g and the step 1); Above-mentioned substance is mixed; Stir with the high speed dispersion mixer, grind 4 times with three-roll grinder again, obtain electrode slurry at last.
Embodiment (experiment) 2
1) preparation of metal silicide: it is 750 ℃ of insulation 2h down that metal nickel powder and silica flour are placed in the resistance furnace in temperature, and annealing in process is prepared into the metal silication powder that particle diameter is 3 μ m through ball milling, and it is for use to get metal silicide 1g;
2) preparation of organic carrier: in the agitated reactor of heat-conducting oil heating; Temperature is controlled at 90 ℃; Getting isopropyl alcohol 21g, ethyl cellulose 6g and castor oil modified derivative 0.5g constant temperature in agitated reactor stirs until dissolving fully; Time is 3h, obtains preparing the needed organic carrier 27.5g of electrode slurry through silk screen filter after the reactant cooling;
3) preparation of electrode slurry: get silver powder 65g; The silver powder proportioning is that the mixing quality ratio of unsetting silver powder, flake silver powder and spherical silver powder is 7:2:1, gets step 2) the middle organic carrier 27.5g for preparing, get the metal silicide 1g for preparing in glass binder 4g and the step 1); Above-mentioned substance is mixed; Stir with the high speed dispersion mixer, grind 4 times with three-roll grinder again, obtain electrode slurry at last.
Embodiment (experiment) 3
1) preparation of metal silicide: it is 750 ℃ of insulation 2h down that metal nickel powder and silica flour are placed in the resistance furnace in temperature, and annealing in process is prepared into the metal silication powder that particle diameter is 3 μ m through ball milling, and it is for use to get metal silicide 1g;
2) preparation of organic carrier: in the agitated reactor of heat-conducting oil heating; Temperature is controlled at 90 ℃; Getting isopropyl alcohol 21g, ethyl cellulose 6g and castor oil modified derivative 0.5g constant temperature in agitated reactor stirs until dissolving fully; Time is 3h, obtains preparing the needed organic carrier 27.5g of electrode slurry through silk screen filter after the reactant cooling;
3) preparation of electrode slurry: get silver powder 65g; The silver powder proportioning is that the mixing quality ratio of unsetting silver powder, flake silver powder and spherical silver powder is 6:3:1, gets step 2) the middle organic carrier 27.5g for preparing, get the metal silicide 1g for preparing in glass binder 4g and the step 1); Above-mentioned substance is mixed; Stir with the high speed dispersion mixer, grind 4 times with three-roll grinder again, obtain electrode slurry at last.
Embodiment (experiment) 4
1) preparation of metal silicide: it is 750 ℃ of insulation 2h down that metal nickel powder and silica flour are placed in the resistance furnace in temperature, and annealing in process is prepared into the metal silication powder that particle diameter is 3 μ m through ball milling, and it is for use to get metal silicide 1g;
2) preparation of organic carrier: in the agitated reactor of heat-conducting oil heating; Temperature is controlled at 90 ℃; Getting isopropyl alcohol 20g, ethyl cellulose 4g and castor oil modified derivative 0.5g constant temperature in agitated reactor stirs until dissolving fully; Time is 3h, obtains preparing the needed organic carrier 24.5g of electrode slurry through silk screen filter after the reactant cooling;
3) preparation of electrode slurry: get silver powder 68g; The silver powder proportioning is that the mixing quality ratio of unsetting silver powder, flake silver powder and spherical silver powder is 7:2:1, gets step 2) the middle organic carrier 24.5g for preparing, get the metal silicide 1g for preparing in glass binder 4g and the step 1); Above-mentioned substance is mixed; Stir with the high speed dispersion mixer, grind 4 times with three-roll grinder again, obtain electrode slurry at last.
Comparative example's (experiment) 1
1) preparation of organic carrier: in the agitated reactor of heat-conducting oil heating; Temperature is controlled at 90 ℃; Getting isopropyl alcohol 20g, ethyl cellulose 3g and castor oil modified derivative 0.5g constant temperature in agitated reactor stirs until dissolving fully; Time is 3h, obtains preparing the needed organic carrier 23.5g of electrode slurry through silk screen filter after the reactant cooling;
2) preparation of electrode slurry: get silver powder 72g; The silver powder proportioning is that the mixing quality ratio of unsetting silver powder, flake silver powder and spherical silver powder is 1:0:0, gets the organic carrier 23.5g for preparing in the step 1), gets glass binder 4g; Above-mentioned substance is mixed; Stir with the high speed dispersion mixer, grind 4 times with three-roll grinder again, obtain electrode slurry at last.
Comparative example's (experiment) 2
1) preparation of organic carrier: in the agitated reactor of heat-conducting oil heating; Temperature is controlled at 90 ℃; Getting isopropyl alcohol 20g, ethyl cellulose 3g and castor oil modified derivative 0.5g constant temperature in agitated reactor stirs until dissolving fully; Time is 3h, obtains preparing the needed organic carrier 23.5g of electrode slurry through silk screen filter after the reactant cooling;
2) preparation of electrode slurry: get silver powder 72g; The silver powder proportioning is that the mixing quality ratio of unsetting silver powder, flake silver powder and spherical silver powder is 0:0:1, gets the organic carrier 23.5g for preparing in the step 1), gets glass binder 4g; Above-mentioned substance is mixed; Stir with the high speed dispersion mixer, grind 4 times with three-roll grinder again, obtain electrode slurry at last.
Table one is the raw material composition
of the foregoing description (experiment) gained electrode slurry
1, the preparation of solar cell
The silicon chip that uses solar cell factory to handle, promptly through cleaning, making herbs into wool is spread, and the silicon chip of etching and PECVD is printed on the cell back face, the required figure of formation electrode through screen process press with the electrode slurry of above-mentioned experiment gained.All printings, oven dry, sintering obtains preparing the battery sheet of electrode with reference to Battery Plant's production technology.
2, the evaluation of battery
1) printing:
Whether the slurry that check is disposed in the printing process easy blocking half tone, and whether the electrode pattern of printing is complete, level and smooth and do not have a disappearance.
2) adhesive force:
According to assembly production standard technology, use welding welding printing backplane, and carry out 180 degree disbonded tests, tensiometer test pulling force.
3) electrical property
Use experimental slurries, prepare the battery sheet according to the solar cell standard technology, and utilize the electric property of cell tester test battery sheet, like the I-V measurement of halm.Measure transformation efficiency Eff, series resistance Rs.Battery conversion efficiency is high, and series resistance is low, and the battery sheet power generation performance of expression preparation is better.
Table two is the test result of above-mentioned experiment
The test shows of above-mentioned experiment, the present invention has reduced silver content under the condition of feedstock optimization proportioning, and the gained electrode slurry is functional, satisfies the production demand of solar cell, and can reduce cost.
Claims (7)
1. crystalline silicon solar battery electrode slurry; It is characterized in that, comprise the raw material of following quality percentage composition: 55% ~ 69.99% silver powder, 1% ~ 6% glass binder; 3% ~ 6% organic resin; 20% ~ 30% organic solvent, 0.1% ~ 0.5% auxiliary rheological agents, 0.1% ~ 5% metal silicide; Said metal silicide be metal and silicon 300 ~ 900 ℃ of following preliminary treatment, again through annealing process, pulverize ball milling at last and process the metal silication powder, wherein said metal is selected from one or more among Pt, Pd, Ti, Ni, Al, Mn, Co, the Ag.
2. crystalline silicon solar battery electrode slurry according to claim 1; It is characterized in that: said silver powder is that unsetting silver powder, flake silver powder and spherical silver powder mix, and the mixing quality ratio of wherein unsetting silver powder, flake silver powder and spherical silver powder is: 6 ~ 7.5:1 ~ 3:0 ~ 1.
3. crystalline silicon solar battery electrode slurry according to claim 2 is characterized in that: said glass binder is a crown glass, and its main component is B
2O
3ZnOBi
2O
3, D50 is less than 3 μ m, and softening point is 430 ~ 480 ℃.
4. crystalline silicon solar battery electrode slurry according to claim 3 is characterized in that: said organic resin is selected from one or more in ethyl cellulose, cellaburate, polyvinyl butyral and the rosin.
5. crystalline silicon solar battery electrode slurry according to claim 4 is characterized in that: said organic solvent is selected from one or more in diethylene glycol butyl ether, isopropyl alcohol, diethylene glycol butyl ether acetic acid esters, terpineol, ethylene glycol monobutyl ether, phenmethylol and the ATBC.
6. crystalline silicon solar battery electrode slurry according to claim 5 is characterized in that: said auxiliary rheological agents is selected from a kind of in dibutyl phthalate, castor oil modified derivative, organic-silicon-modified thing and the lecithin.
7. the preparation method of each said described crystalline silicon solar battery electrode slurry of claim 1-6 is characterized in that, may further comprise the steps:
1) preparation of metal silicide: it is 300 ~ 900 ℃ of insulation 1 ~ 2h down that metal-powder and silica flour are placed in the resistance furnace in temperature, and annealing in process is prepared into the metal silication powder that particle diameter is 1 ~ 5 μ m through ball milling;
2) preparation of organic carrier: in the agitated reactor of heat-conducting oil heating; Temperature is controlled at 70 ~ 100 ℃; Described organic solvent, organic resin and auxiliary rheological agents constant temperature in agitated reactor is stirred until dissolving fully; Time obtains prepare electrode slurry needed organic carrier through silk screen filter at 2 ~ 3h after the reactant cooling;
3) metal silicide for preparing in organic carrier, glass binder and the step 1) of preparation the preparation of electrode slurry: with silver powder, step 2) mixes; Stir with the high speed dispersion mixer; Grind 3 ~ 5 times with three-roll grinder again; The particle diameter that obtains electrode slurry at last is 4 ~ 8 μ m, viscosity be 50 ~ 100PaS (25 ℃, 10rpm).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956749A (en) * | 2012-11-20 | 2013-03-06 | 泰通(泰州)工业有限公司 | Manufacturing Preparation process of solar cell electrode |
| 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 |
| CN105913897A (en) * | 2016-06-01 | 2016-08-31 | 江苏泓源光电科技股份有限公司 | Crystalline silicon solar cell silver paste with low silver content and preparation method thereof |
| US10784383B2 (en) | 2015-08-07 | 2020-09-22 | E I Du Pont De Nemours And Company | Conductive paste composition and semiconductor devices made therewith |
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| CN101377966A (en) * | 2008-09-27 | 2009-03-04 | 彩虹集团公司 | Method for preparing leadless silver electrode slurry for glass substrates |
| CN101651155A (en) * | 2009-09-09 | 2010-02-17 | 谭富彬 | Composition and preparation method of silicon solar battery electrode slurry |
| CN102314955A (en) * | 2010-06-30 | 2012-01-11 | 比亚迪股份有限公司 | Solar conductive slurry, and preparation method thereof and electrode preparation method |
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2012
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Patent Citations (5)
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| JPS5556669A (en) * | 1978-10-20 | 1980-04-25 | Matsushita Electric Ind Co Ltd | Semiconductor device and its manufacture |
| JPH06204511A (en) * | 1993-01-07 | 1994-07-22 | Dai Ichi Kogyo Seiyaku Co Ltd | Electrode paste for semiconductor substrate |
| CN101377966A (en) * | 2008-09-27 | 2009-03-04 | 彩虹集团公司 | Method for preparing leadless silver electrode slurry for glass substrates |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956749A (en) * | 2012-11-20 | 2013-03-06 | 泰通(泰州)工业有限公司 | Manufacturing Preparation process of solar cell electrode |
| 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 |
| US10784383B2 (en) | 2015-08-07 | 2020-09-22 | E I Du Pont De Nemours And Company | Conductive paste composition and semiconductor devices made therewith |
| CN105913897A (en) * | 2016-06-01 | 2016-08-31 | 江苏泓源光电科技股份有限公司 | Crystalline silicon solar cell silver paste with low silver content and preparation method thereof |
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