CN102831957A - Front-face silver paste used for single crystalline silicon solar cell and preparation method thereof - Google Patents
Front-face silver paste used for single crystalline silicon solar cell and preparation method thereof Download PDFInfo
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- CN102831957A CN102831957A CN2012103046826A CN201210304682A CN102831957A CN 102831957 A CN102831957 A CN 102831957A CN 2012103046826 A CN2012103046826 A CN 2012103046826A CN 201210304682 A CN201210304682 A CN 201210304682A CN 102831957 A CN102831957 A CN 102831957A
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Abstract
The invention discloses a front-face silver paste used for a single crystalline silicon solar cell and a preparation method thereof. The front-face silver paste is formed by mixing a part A paste material and a part B paste material in equal proportion through ball milling. The silver paste prepared in the invention does not contain lead, has small harm to human bodies and the environment and completely conforms to the environmental protection requirement. In the invention, silver powder with the same particle size is selected, other conducting particles are selected to fill gaps among the silver powder, the stacking density of a film is increased, the contact area among the particles is increased, the contraction force of the film is reduced, and the conductivity of the silver paste is increased. In the invention, aluminum powder and copper powder are added into the conducting paste materials, so that the production cost of the silver paste can be reduced, the conductivity of the silver paste is increased, the purpose of lowering the manufacturing cost of the solar cell is achieved, and good economic benefits are achieved.
Description
Technical field
The present invention relates to a kind of monocrystaline silicon solar cell with front side silver paste and preparation method thereof, belong to the solar cell conductive paste preparing technical field.
Background technology
The conductive silver paste of solar cell is prepared from by different proportionings raw material such as silver powder, glass glue, organic solvents, and wherein silver powder is as conducting medium; Glass glue melts when high temperature sintering, between silver powder and silicon base, forms ohmic contact; Organic solvent mainly plays a part to disperse and parcel, and silver powder particles is uniform
Wrap up, make that the silver powder in the conductive silver paste is not easy to produce deposition and oxidation.
The glass binder that present solar cell conductive silver slurry is adopted is a kind of Bi-Si-Pb glass mixed-powder; Though it is low that this glass dust has a softening temperature, advantages such as electric performance stablity, it is higher that this system contains proportion; Pollution to environment is bigger, does not meet environmental requirement.Under the situation that solar cell is popularized day by day, the use of leaded solar cell conductive silver slurry is restricted, will eliminate gradually soon, must develop the unleaded conductive silver paste of high conduction performance, to satisfy large solar battery production demand.The content of the silver powder in the technology silver slurry is higher than more than 70% at present, and production cost is than higher, and reducing silver slurry cost is that the silver slurry is an important step that reduces the solar battery sheet cost, also can let solar cell have more the market advantage; In existing silver slurry, using the particle diameter of silver powder in addition is consistent basically; If the silver powder particle diameter is excessive, crackle appears in the silk screen printing meeting, and can increase contact resistance like this; If the silver powder particle diameter is too small; Agglomeration traits can appear in silver powder, influences the uniformity that silver powder distributes, and therefore is necessary the particle diameter of silver powder is effectively regulated and control.
Summary of the invention
The objective of the invention is to deficiency to prior art; Provide a kind of monocrystaline silicon solar cell with front side silver paste and preparation method thereof; Under the prerequisite that satisfies the solar cell electrical property; Make solar cell meet the leadless environment-friendly requirement of international market, reduce silver slurry production cost simultaneously, make solar cell have more the market advantage solar cell.
For achieving the above object, the technical scheme that the present invention adopts is following:
Monocrystaline silicon solar cell is formed by A, B two parts slurry equal proportion mixing and ball milling with front side silver paste, and the weight portion of its two parts constitutive material is:
The A slurry:
1-5 μ m silver powder 45-50,16-25 μ m silver powder 5-10,61-90nm silver powder 5-10, glass dust A 10-15, organic carrier A 15-20, described glass dust A is processed by the raw material of following weight portion: SiO
220-30, Li
2O 10-20, ZnO 5-10, CuO 5-8, AgO
22-5, CuO 2-5, BaO 1-3, described organic carrier A is processed by the raw material of following weight portion: polyethylene glycol 30-40, triethanolamine 15-20, propylene glycol monobutyl ether 10-20, celluloid 5-10, castor oil 2-5, glyceryl tristearate 0.2-0.5, lactic acid glyceryl ester 2-5;
The B slurry:
1-5 μ m aluminium powder 5-10,16-25 μ m copper powder 5-10, glass dust B 3-6, organic carrier B 5-10, described glass dust B is processed by the raw material of following weight portion: Bi
2O
310-20, B
2O
35-10, SiO
25-8, ZrO
22-5, TiO
22-5, Na
2O 1-5, CaO 1-3, described organic carrier B is processed by the raw material of following weight portion: BC 10-20, propylene glycol monobutyl ether 5-10, benzinum 5-10, celluloid 2-5, organic modified bentonite 2-5, vinyl diphenyl-methane 0.5-1, anilinomethyl triethoxysilane 1-3.
Monocrystaline silicon solar cell may further comprise the steps with the preparation method of front side silver paste:
(1) preparation of glass dust A
Take by weighing each raw material by formulation ratio and put in the silica crucible, put into 1100-1300 ℃ of electric furnace sintering after mixing, insulation 20-30 min pours the glass metal after the fusing in the cold water into; Ball milling is crossed the 200-300 mesh sieve then, and cooling is again 600-700 ℃ of insulation 5-6 hour; Then, quench ball milling again with deionized water; Cross the sieve of different meshes, collect respectively and obtain 1-5 μ m glass dust, 10-15 μ m glass dust and 20-25 μ m glass dust; Use 20-30% salt soak 1-2 hour more respectively, clean to neutral dry for standby then with deionized water;
(2) preparation of glass dust B
Take by weighing each raw material by formulation ratio and put in the silica crucible, put into 1100-1300 ℃ of electric furnace sintering after mixing, insulation 20-30 min pours the glass metal after the fusing in the cold water into; Ball milling is crossed the 200-300 mesh sieve then, cooling; 600-700 ℃ of insulation 5-6 hour, then, quench with deionized water more again; Ball milling, the sieve of different meshes is collected respectively and is obtained 1-5 μ m glass dust and 20-25 μ m glass dust excessively; Use 20-30% salt soak 1-2 hour more respectively, clean to neutral dry for standby then with deionized water;
(3) preparation of organic carrier A
Press formulation ratio with polyethylene glycol, triethanolamine, propylene glycol monobutyl ether mixing, under 80-110 ℃, add celluloid, castor oil, glyceryl tristearate, the dissolving of lactic acid glyceryl ester successively, stirring gets final product;
(4) preparation of organic carrier B
Press formulation ratio with BC, propylene glycol monobutyl ether, benzinum mixing, under 80-110 ℃, add celluloid, organic modified bentonite, vinyl diphenyl-methane, anilinomethyl triethoxysilane dissolving successively, stirring gets final product;
(5) preparation of A slurry
The glass dust A of the prepared different-grain diameter of step (1) is added in step (3) the prepared organic carrier A; Stir mixed; Each again 1-5 μ m silver powder, 16-25 μ m silver powder, 61-90nm silver powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the A slurry;
(6) preparation of B slurry
The glass dust B of the prepared different-grain diameter of step (2) is added in step (4) the prepared organic carrier B, and stirring is mixed, and each again 1-5 μ m aluminium powder, 16-25 μ m copper powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the B slurry;
(7) mixing and ball milling of A slurry and B slurry
A slurry and B slurry equal proportion are mixed, and ball milling is ground to the slurry fineness less than 10 μ m, transfers viscosity, and viscosity is 120-200Pas, promptly gets solar cell front side silver paste of the present invention.
Beneficial effect of the present invention is following:
1, not leaded in the silver slurry that the present invention prepares, little to human body and environmental hazard, complete compliance with environmental protection requirements;
2, the present invention has selected for use in the silver slurry with silver powder and other conducting particles of particle diameter and has filled the gap between silver powder, has improved the bulk density of rete, increases interparticle contact area, has reduced the convergent force of rete, thereby has improved the conductive capability of silver-colored slurry;
3, the silver slurry and the silicon chip coefficient of expansion matching that prepare of the present invention is good, shrinks little, the rate of finished products height, resistance is little, can not form pore, can not form crackle;
4, the present invention has added aluminium powder and copper powder and can help to reduce silver slurry production cost in electrocondution slurry, improves the electric conductivity of silver slurry simultaneously, thereby has reached the purpose that reduces the solar cell manufacturing cost, has obtained good economic benefit.
Embodiment
Below in conjunction with embodiment the present invention is explained further details.
Embodiment 1
(1) preparation of glass dust A
Get the raw material of following weight portion: SiO
220 parts, Li
215 parts of O, 5 parts of ZnO, 6 parts of CuO, AgO
23 parts, 3 parts of CuO, 2 parts of BaO are put in the silica crucible, put into 1150 ℃ of electric furnace sintering after mixing, and are incubated 30 min, and the glass metal after the fusing is poured in the cold water; Ball milling is crossed 200 mesh sieves then, and cooling is again 700 ℃ of insulations 5 hours, then; Quench with deionized water again, ball milling, the sieve of different meshes is collected respectively and is obtained 5 μ m glass dust excessively; 10 μ m glass dust and 20 μ m glass dust are used 25% salt soak 2 hours more respectively, clean to neutral dry for standby then with deionized water;
(2) preparation of glass dust B
Get the raw material of following weight portion: Bi
2O
310 parts, B
2O
35 parts, SiO
28 parts, ZrO
25 parts, TiO
22 parts, Na
22 parts of O, 2 parts of CaO put in the silica crucible, put into 1100 ℃ of electric furnace sintering after mixing, and are incubated 30 min, and the glass metal after the fusing is poured in the cold water; Ball milling is crossed 200 mesh sieves then, and cooling is again 600 ℃ of insulations 6 hours; Then, quench ball milling, the sieve of different meshes excessively again with deionized water; Collect respectively and obtain 2 μ m glass dust and 20 μ m glass dust, use 25% salt soak 2 hours more respectively, clean to neutral dry for standby then with deionized water;
(3) preparation of organic carrier A
Get the raw material of following weight portion: 30 parts of polyethylene glycol, 20 parts of triethanolamines, 20 parts of propylene glycol monobutyl ethers, 8 parts in celluloid, 3 parts of castor oil, 0.4 part of glyceryl tristearate, 3 parts of lactic acid glyceryl esters,
Press formulation ratio with polyethylene glycol, triethanolamine, propylene glycol monobutyl ether mixing, under 100 ℃, add celluloid, castor oil, glyceryl tristearate, the dissolving of lactic acid glyceryl ester successively, stirring gets final product;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 10 parts of BCs, 10 parts of propylene glycol monobutyl ethers, 10 parts of benzinums, 3 parts in celluloid, 3 parts of organic modified bentonites, 0.7 part of vinyl diphenyl-methane, 2 parts of anilinomethyl triethoxysilanes,
Press formulation ratio with BC, propylene glycol monobutyl ether, benzinum mixing, under 95 ℃, add celluloid, organic modified bentonite, vinyl diphenyl-methane, anilinomethyl triethoxysilane dissolving successively, stirring gets final product;
(5) preparation of A slurry
Get the raw material of following weight portion: 45 parts in 1 μ m silver powder, 18 5 parts in μ m silver powder, 10 parts in 65nm silver powder, 10 parts of glass dust A, 15 parts of organic carrier A,
Glass dust A is added among the organic carrier A, and stirring is mixed, and each again 1 μ m silver powder, 18 μ m silver powder, 65nm silver powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 10 parts of 2 μ m aluminium powders, 20 5 parts of μ m copper powders, 4 parts of glass dust B, 8 parts of organic carrier B,
Glass dust B is added among the organic carrier B, and stirring is mixed, and each again 2 μ m aluminium powders, 20 μ m copper powders of adding successively in 30-40 minute at interval mixed 2-3 hour, obtain the B slurry;
(7) mixing and ball milling of A slurry and B slurry
A slurry and B slurry equal proportion are mixed, and ball milling is ground to the slurry fineness less than 10 μ m, transfers viscosity, and viscosity is 160Pas, promptly gets solar cell front side silver paste of the present invention.
Adopt screen process press that the silver slurry is printed on 125mm * 125mm Si substrate,, carry out quick fired electrodes lead-in wire at 900 ℃ more then 200 ℃ of dryings; The contact conductor surface silvery white of processing behind the high temperature sintering, smooth zero defect, peel strength 9 N/cm; Soldering is functional, side's resistance＜10 Siements/sq, and the solar cell photoelectric transformation efficiency of preparation is 19.1%;, the tensile test result is Fu Zheli>10N/mm
2
Embodiment 2
(1) preparation of glass dust A
Get the raw material of following weight portion: SiO
230 parts, Li
210 parts of O, 10 parts of ZnO, 5 parts of CuO, AgO
235 parts, 5 parts of CuO, 3 parts of BaO are put in the silica crucible, put into 1200 ℃ of electric furnace sintering after mixing, and are incubated 30 min; Glass metal after the fusing is poured in the cold water, and ball milling is crossed 200 mesh sieves then, cooling; 700 ℃ of insulations 6 hours, then, quench ball milling again with deionized water again; Cross the sieve of different meshes, collect respectively and obtain 2 μ m glass dust, 14 μ m glass dust and 24 μ m glass dust; Use 30% salt soak 2 hours more respectively, clean to neutral dry for standby then with deionized water;
(2) preparation of glass dust B
Get the raw material of following weight portion: Bi
2O
320 parts, B
2O
38 parts, SiO
26 parts, ZrO
23 parts, TiO
24 parts, Na
25 parts of O, 2 parts of CaO put in the silica crucible, put into 1150 ℃ of electric furnace sintering after mixing, and are incubated 30 min, and the glass metal after the fusing is poured in the cold water; Ball milling is crossed 200 mesh sieves then, and cooling is again 700 ℃ of insulations 5 hours; Then, quench ball milling, the sieve of different meshes excessively again with deionized water; Collect respectively and obtain 3 μ m glass dust and 24 μ m glass dust, use 25% salt soak 2 hours more respectively, clean to neutral dry for standby then with deionized water;
(3) preparation of organic carrier A
Get the raw material of following weight portion: 40 parts of polyethylene glycol, 15 parts of triethanolamines, 15 parts of propylene glycol monobutyl ethers, 10 parts in celluloid, 4 parts of castor oil, 0.5 part of glyceryl tristearate, 5 parts of lactic acid glyceryl esters,
Press formulation ratio with polyethylene glycol, triethanolamine, propylene glycol monobutyl ether mixing, under 100 ℃, add celluloid, castor oil, glyceryl tristearate, the dissolving of lactic acid glyceryl ester successively, stirring gets final product;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 20 parts of BCs, 5 parts of propylene glycol monobutyl ethers, 10 parts of benzinums, 5 parts in celluloid, 3 parts of organic modified bentonites, 0.8 part of vinyl diphenyl-methane, 2 parts of anilinomethyl triethoxysilanes,
Press formulation ratio with BC, propylene glycol monobutyl ether, benzinum mixing, under 95 ℃, add celluloid, organic modified bentonite, vinyl diphenyl-methane, anilinomethyl triethoxysilane dissolving successively, stirring gets final product;
(5) preparation of A slurry
Get the raw material of following weight portion: 50 parts in 3 μ m silver powder, 20 10 parts in μ m silver powder, 10 parts in 70nm silver powder, 15 parts of glass dust A, 20 parts of organic carrier A,
Glass dust A is added among the organic carrier A, and stirring is mixed, and each again 3 μ m silver powder, 20 μ m silver powder, 70nm silver powder of adding successively in 40 minutes at interval mixed 3 hours, obtains the A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 5 parts of 2 μ m aluminium powders, 16 10 parts of μ m copper powders, 5 parts of glass dust B, 8 parts of organic carrier B,
Glass dust B is added among the organic carrier B, and stirring is mixed, and each again 2 μ m aluminium powders, 16 μ m copper powders of adding successively in 40 minutes at interval mixed 3 hours, obtain the B slurry;
(7) mixing and ball milling of A slurry and B slurry
A slurry and B slurry equal proportion are mixed, and ball milling is ground to the slurry fineness less than 10 μ m, transfers viscosity, and viscosity is 180Pas, promptly gets solar cell front side silver paste of the present invention.
Adopt screen process press that the silver slurry is printed on 125mm * 125mm Si substrate,, carry out quick fired electrodes lead-in wire at 900 ℃ more then 200 ℃ of dryings; The contact conductor surface silvery white of processing behind the high temperature sintering, smooth zero defect, peel strength 10 N/cm; Soldering is functional, side's resistance＜8 Siements/sq, and the solar cell photoelectric transformation efficiency of preparation is 19.8%;, the tensile test result is Fu Zheli>12N/mm
2
Claims (2)
1. a monocrystaline silicon solar cell is used front side silver paste, it is characterized in that, it is formed by A, B two parts slurry equal proportion mixing and ball milling, and the weight portion of its two parts constitutive material is:
The A slurry:
1-5 μ m silver powder 45-50,16-25 μ m silver powder 5-10,61-90nm silver powder 5-10, glass dust A 10-15, organic carrier A 15-20, described glass dust A is processed by the raw material of following weight portion: SiO
220-30, Li
2O 10-20, ZnO 5-10, CuO 5-8, AgO
22-5, CuO 2-5, BaO 1-3, described organic carrier A is processed by the raw material of following weight portion: polyethylene glycol 30-40, triethanolamine 15-20, propylene glycol monobutyl ether 10-20, celluloid 5-10, castor oil 2-5, glyceryl tristearate 0.2-0.5, lactic acid glyceryl ester 2-5;
The B slurry:
1-5 μ m aluminium powder 5-10,16-25 μ m copper powder 5-10, glass dust B 3-6, organic carrier B 5-10, described glass dust B is processed by the raw material of following weight portion: Bi
2O
310-20, B
2O
35-10, SiO
25-8, ZrO
22-5, TiO
22-5, Na
2O 1-5, CaO 1-3, described organic carrier B is processed by the raw material of following weight portion: BC 10-20, propylene glycol monobutyl ether 5-10, benzinum 5-10, celluloid 2-5, organic modified bentonite 2-5, vinyl diphenyl-methane 0.5-1, anilinomethyl triethoxysilane 1-3.
2. a monocrystaline silicon solar cell as claimed in claim 1 is characterized in that may further comprise the steps with the preparation method of front side silver paste:
(1) preparation of glass dust A
Take by weighing each raw material by formulation ratio and put in the silica crucible, put into 1100-1300 ℃ of electric furnace sintering after mixing, insulation 20-30 min pours the glass metal after the fusing in the cold water into; Ball milling is crossed the 200-300 mesh sieve then, and cooling is again 600-700 ℃ of insulation 5-6 hour; Then, quench ball milling again with deionized water; Cross the sieve of different meshes, collect respectively and obtain 1-5 μ m glass dust, 10-15 μ m glass dust and 20-25 μ m glass dust; Use 20-30% salt soak 1-2 hour more respectively, clean to neutral dry for standby then with deionized water;
(2) preparation of glass dust B
Take by weighing each raw material by formulation ratio and put in the silica crucible, put into 1100-1300 ℃ of electric furnace sintering after mixing, insulation 20-30 min pours the glass metal after the fusing in the cold water into; Ball milling is crossed the 200-300 mesh sieve then, cooling; 600-700 ℃ of insulation 5-6 hour, then, quench with deionized water more again; Ball milling, the sieve of different meshes is collected respectively and is obtained 1-5 μ m glass dust and 20-25 μ m glass dust excessively; Use 20-30% salt soak 1-2 hour more respectively, clean to neutral dry for standby then with deionized water;
(3) preparation of organic carrier A
Press formulation ratio with polyethylene glycol, triethanolamine, propylene glycol monobutyl ether mixing, under 80-110 ℃, add celluloid, castor oil, glyceryl tristearate, the dissolving of lactic acid glyceryl ester successively, stirring gets final product;
(4) preparation of organic carrier B
Press formulation ratio with BC, propylene glycol monobutyl ether, benzinum mixing, under 80-110 ℃, add celluloid, organic modified bentonite, vinyl diphenyl-methane, anilinomethyl triethoxysilane dissolving successively, stirring gets final product;
(5) preparation of A slurry
The glass dust A of the prepared different-grain diameter of step (1) is added in step (3) the prepared organic carrier A; Stir mixed; Each again 1-5 μ m silver powder, 16-25 μ m silver powder, 61-90nm silver powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the A slurry;
(6) preparation of B slurry
The glass dust B of the prepared different-grain diameter of step (2) is added in step (4) the prepared organic carrier B, and stirring is mixed, and each again 1-5 μ m aluminium powder, 16-25 μ m copper powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the B slurry;
(7) mixing and ball milling of A slurry and B slurry
A slurry and B slurry equal proportion are mixed, and ball milling is ground to the slurry fineness less than 10 μ m, transfers viscosity, and viscosity is 120-200Pas, promptly gets solar cell front side silver paste of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210304682.6A CN102831957B (en) | 2012-08-24 | 2012-08-24 | Front-face silver paste used for single crystalline silicon solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210304682.6A CN102831957B (en) | 2012-08-24 | 2012-08-24 | Front-face silver paste used for single crystalline silicon solar cell and preparation method thereof |
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|---|---|
| CN102831957A true CN102831957A (en) | 2012-12-19 |
| CN102831957B CN102831957B (en) | 2014-07-30 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5422597A (en) * | 1977-07-21 | 1979-02-20 | Murata Manufacturing Co | Conductive paste |
| JP2005123141A (en) * | 2003-10-20 | 2005-05-12 | Murata Mfg Co Ltd | Conductive paste and piezoelectric ceramic electronic component |
| CN101697337A (en) * | 2009-09-25 | 2010-04-21 | 南京金视显科技有限公司 | Low-silver photosensitive silver paste for PDP site selection electrodes, and preparation method thereof |
| CN101728001A (en) * | 2009-11-12 | 2010-06-09 | 东南大学 | Lead-free and low-silver photosensitive silver paste and preparation method thereof |
| CN102013282A (en) * | 2010-12-21 | 2011-04-13 | 昆明理工大学 | Silver paste special for glass defogging heater wires and preparation method thereof |
-
2012
- 2012-08-24 CN CN201210304682.6A patent/CN102831957B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5422597A (en) * | 1977-07-21 | 1979-02-20 | Murata Manufacturing Co | Conductive paste |
| JP2005123141A (en) * | 2003-10-20 | 2005-05-12 | Murata Mfg Co Ltd | Conductive paste and piezoelectric ceramic electronic component |
| CN101697337A (en) * | 2009-09-25 | 2010-04-21 | 南京金视显科技有限公司 | Low-silver photosensitive silver paste for PDP site selection electrodes, and preparation method thereof |
| CN101728001A (en) * | 2009-11-12 | 2010-06-09 | 东南大学 | Lead-free and low-silver photosensitive silver paste and preparation method thereof |
| CN102013282A (en) * | 2010-12-21 | 2011-04-13 | 昆明理工大学 | Silver paste special for glass defogging heater wires and preparation method thereof |
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| CN102831957B (en) | 2014-07-30 |
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