CN106887270B - A kind of solar energy front side silver paste and preparation method thereof that depth-width ratio is high - Google Patents
A kind of solar energy front side silver paste and preparation method thereof that depth-width ratio is high Download PDFInfo
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- CN106887270B CN106887270B CN201710157009.7A CN201710157009A CN106887270B CN 106887270 B CN106887270 B CN 106887270B CN 201710157009 A CN201710157009 A CN 201710157009A CN 106887270 B CN106887270 B CN 106887270B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 55
- 239000004332 silver Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims description 27
- 239000002002 slurry Substances 0.000 claims abstract description 49
- 239000011521 glass Substances 0.000 claims abstract description 40
- 239000012074 organic phase Substances 0.000 claims abstract description 33
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 21
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 21
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 13
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- -1 fatty acid ester Chemical class 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 24
- 238000007650 screen-printing Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- OHBRHBQMHLEELN-UHFFFAOYSA-N acetic acid;1-butoxybutane Chemical compound CC(O)=O.CCCCOCCCC OHBRHBQMHLEELN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000370 laser capture micro-dissection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
A kind of solar energy front side silver paste that depth-width ratio is high, it is characterised in that the raw material including following weight percent: conductive phase silver powder 82~90%, inorganic phase glass powder 1~3%, organic phase carrier 7~15%；Wherein organic phase carrier comprises the following raw materials by weight percent: plasticizer 15~30%, ethyl cellulose 7~15%, thixotropic agent 1~15%, surfactant 0~12%, remaining is solvent.The silver paste slurry screen printability that the present invention is prepared is excellent, the lines depth-width ratio with higher after printing.
Description
Technical field
The present invention relates to a kind of silver paste manufacturing technology field, line after, printing excellent more particularly, to a kind of screen printability
Item has the solar battery positive silver paste of higher depth-width ratio.
Background technique
In solar cells, generally select silk-screen printing technique, front electrode printed to silicon wafer, by dry and
Sintering forms metal electrode.Cost needed for silk-screen printing is few, is conducive to realize solar cell industry and large-scale production.
This requires solar energy positive silver pastes to have good screen printability, and in continuous and printing for a long time, slurry is able to maintain surely
Fixed viscosity, excellent off line property also need to can guarantee that the lines after printing have good plasticity and higher depth-width ratio.
The solar energy front side silver paste of suitable silk-screen printing generally consists of three parts: conductive phase, inorganic phase, organic phase.
Conductive phase is silver powder, the conductive materials as electrode；Inorganic phase is glass powder, and during sintering, glass powder can melt into glass
Glass liquid, sticks in electrode on silicon wafer well；Organic phase is carrier, and powder uniformly disperses in the carrier, and carrier plays connection
The effect of material, and provide slurry suitable rheological characteristic, make slurry be easy to carry out silk-screen printing.
Silk-screen printing technique requires solar energy front side silver paste in printing, and when scraper is run, the viscosity of slurry declines rapidly,
When can guarantee printing in this way, slurry returns ink well, and ink film can be uniformly layered on halftone, while lower viscosity can promote
Make the mesh by halftone that slurry is more easier, makes slurry that there is excellent off line property.After slurry is transferred on silicon wafer, together
The structure of Shi Yaoqiu slurry can be restored rapidly, and line edge is clear after reaching printing, the high effect of depth-width ratio.
But structure here does not imply that the viscosity of slurry, because if the viscosity recovery of slurry is too fast, then after printing
" Self-leveling " of lines is too weak, and lines surface is easy to be uneven.Height different lines in grid line surface are usually with higher
Series resistance and lower short circuit current, influence conversion ratio.And if the viscosity recovery of slurry is too fast, the lines after printing hold
It is also easy to produce " cucurbit section " phenomenon, i.e. grid line lines are a section not very continuous lines, easily cause disconnected grid.
Here structure refers to the three-dimensional net structure of slurry, when the structure resume speed of slurry is very fast, slurry transfer
To silicon wafer, three-dimensional net structure restores rapidly, then lines have good plasticity, and line edge is clear, is not easy to collapse,
If its viscosity recovery speed is moderate, then lines surface can produce " Self-leveling ".If the three-dimensional net structure of slurry restores too
Slowly, then slurry is transferred on silicon wafer, and lines are easy to produce collapsing, and line edge is easy to trickle, and line thickness broadens.At this point, i.e.
Keep slurry viscosity larger, also be easy to cause broadening for lines in drying section, because the viscosity of slurry declines rapidly, such as when high temperature
Its three-dimensional net structure does not restore, then slurry generates trickling, and plasticity is poor, and lines broaden.
So be suitable for silk-screen printing solar energy front side silver paste should have suitable viscosity, suitable viscosity recovery speed,
And faster three-dimensional net structure resume speed, it could be while guaranteeing good printing, lines are with higher high wide
When marginal definition.Ideal lines answer surface flat and continuous, and edge clear does not collapse, and has good depth-width ratio.
In the prior art, depth-width ratio is highly important index in positive silver paste, and the grid line of cell piece is more and more thinner, industry
Some interior producers, which have begun, to attempt to be blocked, mentioned to reduce grid line to sunlight using the screen painting grid line of 28 μm of openings
High short circuit current, to increase the transformation efficiency of cell piece.And under identical grid line height, grid line is thinner, and resistance is bigger, influences to turn
Change efficiency.Therefore bigger depth-width ratio is conducive to promote transformation efficiency.The depth-width ratio of existing slurry is bad, is primarily due to
Factor of both balance, one is that the slurry is leveled off, and one is plasticity.If plasticity is very good, slurry loses flowability, printing
Lines some places afterwards are very high, and some places are very low, almost without slurry；If levelability is very good, silver paste is stood on silicon wafer
Do not get up, collapse levelling as water.Exactly because the factor that these two aspects mutually restricts, depth-width ratio is not accomplished very high.At present
The depth-width ratio of the silver paste for the best DuPont Corporation done in the world can only accomplish 0.4 or so.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, this application provides a kind of solar energy front side silver paste that depth-width ratio is high and
Preparation method.The silver paste slurry screen printability that the present invention is prepared is excellent, and the lines after printing are with higher high wide
Than.
Technical scheme is as follows:
The applicant provides a kind of solar energy front side silver paste that depth-width ratio is high, the raw material including following weight percent:
Conductive phase silver powder 82~90%, inorganic phase glass powder 1~3%, organic phase carrier 7~15%；Above-mentioned raw materials
The sum of dosage be 100%.
Wherein organic phase carrier comprises the following raw materials by weight percent: plasticizer 15~30%, ethyl cellulose 7~
15%, thixotropic agent 1~15%, surfactant 0~12%, remaining is solvent.Each raw material dosage phase of above-mentioned organic phase carrier
Add as 100%.
Preferably, the silver powder D50 partial size is 0.8~2.5 μm, and tap density is 4.5~6.5g/ml.
Preferably, the inorganic phase glass powder D50 partial size is 0.5~2.0 μm, and Tg point temperature is 250~500 DEG C.
Preferably, the plasticizer is polyalcohol esters, in phosphoric acid ester, phthalate, fatty acid ester
It is one or more.
Preferably, the thixotropic agent is rilanit special, polyamide modified rilanit special, polyamide wax pulp, polyethylene
One of wax liquor, fumed silica, bentonite are a variety of.
Preferably, the surfactant is nonionic surfactant.It is furthermore preferred that the surfactant is tween
20, one of Tween 80, sorbitan ester, alkyl phenol polyoxyethylene ether, aliphatic amine polyoxyethylene ether or a variety of.
Preferably, the ethyl cellulose is N-type or T-type ethyl cellulose or both mixture, ethoxyl content 45
~50%.
Preferably, the solvent is butyl acetate, terpinol, mixed dibasic acid ester and DBE, isophorone
One of or it is a variety of.
The applicant additionally provides a kind of preparation method of solar energy front side silver paste that the depth-width ratio is high, and specific steps are such as
Under:
(1) organic phase carrier is prepared
By ethyl cellulose and plasticizer, thixotropic agent, solvent, surfactant 40~80 DEG C of heating stirrings after mixing
Homogeneous and transparent solution is made in 0.1~1h, the as described organic phase carrier；
(2) preparation of glass paste
Glass powder is taken, is mixed with the organic phase carrier prepared in step (1), after being uniformly dispersed on dispersion machine, in three rollers
Machine upper roller to fineness is 5um or less；
(3) preparation of silver paste
A, it is uniformly dispersed on dispersion machine after mixing the glass paste being prepared in silver powder and step (2), in three rollers
Machine upper roller to fineness is 5um or less；
B, the silver paste slurry placement prepared carries out viscosity test afterwards for 24 hours, if viscosity is excessive, adds suitable solvent
Slurry viscosity is adjusted to 280~320Pa.s.
The present invention is beneficial to be had the technical effect that
In close relations, the content and shape of particle in the slurry of the viscosity and three-dimensional net structure of slurry and organic carrier
When consistent, the viscosity and three-dimensional net structure of slurry depend on the composition of carrier.Second is dissolved in butyl acetate
Base cellulose guarantees that the basic viscosity of slurry, dispersing agent guarantee that the particle in slurry can be very good dispersion in the carrier, and
Plasticizer and thixotropic agent then produce vital influence to the rheological characteristic of slurry.
The rheological characteristic of previous solar energy front side silver paste slurry is adjusted mainly by thixotropic agent, it is a discovery of the invention that by a variety of
The cooperation of plasticizer can both guarantee that slurry had suitable viscosity after printing, and there is suitable viscosity to reduce degree, together
When there is faster three-dimensional network resume speed again.The presence of plasticizer in the slurry, plays certain lubricating action, so that second
The long-chain of base cellulose is easier to tangle and tangle with solution, and sliding is more prone to produce between chain and chain, and makes the silver in slurry
Powder and glass powder can be easier to move, so that slurry has superior thixotropy can after its three-dimensional structure changes
To restore faster.
The presence of thixotropic agent, polyamide portion itself or the formation hydrogen bond tridimensional network between solvent, hydrogen bond are
Stronger interaction key, therefore interfere between plasticizer insertion ethyl cellulose, if hydrogen bond is along ethyl cellulose molecule
Chain distribution is closeer, then the effect that confrontation plasticizer injects accordingly is also stronger, thus it is individually unobvious with a kind of effect of plasticizer,
It needs several plasticizer to be used cooperatively, can be only achieved good effect.After being subjected to shearing force, three-dimensional net structure occurs slurry
After destruction, the presence of plasticizer can accelerate the resume speed of the three-dimensional net structure of slurry.
Compared with prior art, guarantee levelability with the three-dimensional net structure of microcosmic property to technological innovation of the invention
The collapsing diffusion of grid line is reduced simultaneously.Positive silver paste of the present invention is used as plasticising using polyalcohol, the one or more of phosphoric acid ester
Agent, cooperation thixotropic agent use, can effectively improve the rheological characteristic of solar energy front side silver paste, improved slurry on a silicon substrate
Silk-screen printing quality, grid line lines after printing have good plasticity, and improve the depth-width ratio of silver wire after sintering, reduce
The collapsing of silver wire item after sintering, and then reduce shared light-receiving area, improve the transformation efficiency of cell piece.
Specific embodiment
Below with reference to embodiment, the present invention is specifically described.
Embodiment 1
A kind of preparation method for the solar energy front side silver paste that depth-width ratio is high, includes the following steps:
(1) organic phase carrier is prepared
Ethoxyl content is 4.7 parts of N-type ethyl cellulose of 45%, the T-type ethyl cellulose that ethoxyl content is 50%
8.7 parts, 13.3 parts of tributyl phosphate, 13.3 parts of pentaerythritol fatty acid ester, 13.3 parts of rilanit special, polysorbas20: 10 parts, diethyl two
After mixing, homogeneous and transparent solution is made, i.e., in heating stirring 30min under the conditions of 45 DEG C to 36.7 parts of alcohol monobutyl ether acetate
It is configured to organic phase carrier；
(2) glass paste is prepared
Taking D50 is 0.6 μm, and Tg point is 3 parts of glass powder of 262 DEG C, is being divided with 15 parts of organic phase carrier of step (1) preparation
It dissipates after being uniformly dispersed on machine, in three-roller upper roller to fineness 5um hereinafter, glass paste is made；
(3) silver paste is prepared
Taking D50 is 0.9 μm, and tap density is 82 parts of silver powder of 5.2g/ml, 18 parts of glass paste with step (2) preparation,
After being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um or less.
The silver paste placement prepared carries out viscosity test afterwards for 24 hours, if viscosity is excessive, adds suitable diethylene glycol fourth
Slurry viscosity is adjusted to 280~320Pa.s by ether acetate, and the performance data of final silver paste is as shown in table 1.
Embodiment 2
A kind of preparation method for the solar energy front side silver paste that depth-width ratio is high, includes the following steps:
(1) organic phase carrier is prepared
Ethoxyl content is 4.2 parts of N-type ethyl cellulose of 45%, the T-type ethyl cellulose that ethoxyl content is 50%
4.2 parts, 4.2 parts of dibutyl phthalate, 12.5 parts of pentaerythritol fatty acid ester, 1.7 parts of polyamide modified rilanit special, tween
80:8.3 parts, after mixing, homogeneous and transparent solution is made in heating stirring 40min under the conditions of 50 DEG C to 64.9 parts of terpinol,
It is configured to organic phase carrier；
(2) glass paste is prepared
Taking D50 is 0.9 μm, and Tg point is 3 parts of glass powder of 439 DEG C, and organic phase carrier 12 part with step (1) preparation is being divided
It dissipates after being uniformly dispersed on machine, in three-roller upper roller to fineness 5um hereinafter, glass paste is made；
(3) silver paste is prepared
Taking D50 is 1.2 μm, and tap density is 85 parts of silver powder of 6.2g/ml, 15 parts of glass paste with step (2) preparation,
After being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um or less.
The silver paste placement prepared carries out viscosity test afterwards for 24 hours, if viscosity is excessive, adding suitable terpinol will be starched
Viscosity-adjusting agent is expected to 280~320Pa.s, and the performance data of final silver paste is as shown in table 1.
Embodiment 3
A kind of preparation method for the solar energy front side silver paste that depth-width ratio is high, includes the following steps:
(1) organic phase carrier is prepared
Ethoxyl content is 8 parts of N-type ethyl cellulose of 45%, 11.4 parts of dioctyl adipate, 17 parts of tributyl phosphate,
5.7 parts of fumed silica, Tween 80: 5.7 parts, 52.2 parts of mixed dibasic acid ester (DBE) after mixing, in 65 DEG C of conditions
Lower heating stirring 20min, is made homogeneous and transparent solution, that is, is configured to organic phase carrier；
(2) glass paste is prepared
Taking D50 is 2.0 μm, and Tg point is 1.2 parts of glass powder of 340 DEG C, 8.8 parts of organic phase carrier with step (1) preparation
After being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um hereinafter, glass paste is made；
(3) silver paste is prepared
Taking D50 is 1.2 μm, and tap density is 90 parts of silver powder of 5.5g/ml, 10 parts of glass paste with step (2) preparation,
After being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um or less.
The silver paste placement prepared carries out viscosity test afterwards for 24 hours, if viscosity is excessive, adds suitable mixing dioctyl phthalate
Slurry viscosity is adjusted to 280~320Pa.s by dimethyl ester, and the performance data of final silver paste is as shown in table 1.
Embodiment 4
A kind of preparation method for the solar energy front side silver paste that depth-width ratio is high, includes the following steps:
(1) organic phase carrier is prepared
Ethoxyl content is 5 parts of N-type ethyl cellulose of 45%, the T-type ethyl cellulose 5 that ethoxyl content is 50%
Part, 15 parts of triphenyl phosphate, 15 parts of glycol ester, 10 parts of polyamide wax pulp, Tween 80: 10 parts, 40 parts of isophorone mixing are equal
After even, heating stirring 30min under the conditions of 60 DEG C is made homogeneous and transparent solution, that is, is configured to organic phase carrier；
(2) glass paste is prepared
Taking D50 is 1.2 μm, and Tg point is 2 parts of glass powder of 380 DEG C, 10 parts of organic phase carrier with step (1) preparation,
After being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um hereinafter, glass paste is made；
(3) silver paste is prepared
Taking D50 is 1.2 μm, and tap density is 88 parts of silver powder of 4.6g/ml, 12 parts of glass paste with step (2) preparation,
After being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um or less.
The silver paste placement prepared carries out viscosity test afterwards for 24 hours, if viscosity is excessive, adding suitable isophorone will
Slurry viscosity is adjusted to 280~320Pa.s, and the performance data of final silver paste is as shown in table 1.
Embodiment 5
A kind of preparation method for the solar energy front side silver paste that depth-width ratio is high, includes the following steps:
(1) organic phase carrier is prepared
Ethoxyl content is 9.5 parts of T-type ethyl cellulose of 50%, 4.8 parts of tributyl phosphate, pentaerythritol fatty acid ester 23.8
Part, 9.5 parts of polyethylene wax liquor, Tween 80: 9.5 parts, 42.9 parts of butyl acetate after mixing, in 50 DEG C of conditions
Lower heating stirring 55min, is made homogeneous and transparent solution, that is, is configured to organic phase carrier；
(2) glass paste is prepared
Taking D50 is 1.5 μm, and Tg point is 1.5 parts of glass powder of 485 DEG C, the organic phase carrier 10.5 with step (1) preparation
Part, after being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um hereinafter, glass paste is made；
(3) silver paste is prepared
Taking D50 is 1.2 μm, and tap density is 88 parts of silver powder of 5.5g/ml, 12 parts of glass paste with step (2) preparation,
After being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um or less.
The silver paste placement prepared carries out viscosity test afterwards for 24 hours, if viscosity is excessive, adds suitable diethylene glycol fourth
Slurry viscosity is adjusted to 280~320Pa.s by ether acetate, and the performance data of final silver paste is as shown in table 1.
Comparative example
The preparation method of the solar energy front side silver paste of no plasticizer addition, includes the following steps:
(1) organic phase carrier is prepared
Ethoxyl content is 11.1 parts of N-type ethyl cellulose of 45%, the T-type ethyl cellulose that ethoxyl content is 50%
2.2 parts, 11.1 parts of polyamide modified rilanit special, Tween 80: 11.1 parts, 64.5 parts of butyl acetate mixing are equal
After even, heating stirring 40min under the conditions of 75 DEG C is made homogeneous and transparent solution, that is, is configured to organic phase carrier.
(2) glass paste is prepared
Taking D50 is 1.5 μm, and Tg point is 3 parts of glass powder of 415 DEG C, and 9 parts of organic phase carrier with step (1) preparation are dividing
It dissipates after being uniformly dispersed on machine, in three-roller upper roller to fineness 5um hereinafter, glass paste is made；
(3) silver paste is prepared
Taking D50 is 1.2 μm, and tap density is 88 parts of silver powder of 5.5g/ml, 12 parts of glass paste with step (2) preparation,
After being uniformly dispersed on dispersion machine, in three-roller upper roller to fineness 5um or less.
The silver paste placement prepared carries out viscosity test afterwards for 24 hours, if viscosity is excessive, adds suitable diethylene glycol fourth
Slurry viscosity is adjusted to 280~320Pa.s by ether acetate, and the performance data of final silver paste is as shown in table 1.
Test case:
Examples 1 to 5 and the prepared silver paste of comparative example is enterprising in rheometer (anton-paar/MCR102,25 DEG C)
Row rheometer test, and carry out silk-screen printing on screen process press and be fabricated to solar battery sheet, manufactured cell piece is surveyed in I/V
Electric performance test is carried out on examination instrument, and in the grid line lines situation of laser capture microdissection microscopic observation cell piece.Test data such as 1 institute of table
Show.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example | |
| Slurry viscosity/10rpm (Pa.s) | 295 | 311 | 301 | 303 | 307 | 318 |
| Shear shinning index (1 1/s/10 1/s) | 10.6 | 12.3 | 12.7 | 13.5 | 12.9 | 8.3 |
| Structure resume speed/10s G ' (%) | 49.5 | 51.32 | 78.59 | 93.38 | 74.51 | 24.68 |
| Depth-width ratio | 0.33 | 0.35 | 0.43 | 0.56 | 0.40 | 0.25 |
| Open-circuit voltage Mv | 630.15 | 630.27 | 630.23 | 630.29 | 630.13 | 630.19 |
| Short circuit current A | 8.879 | 8.911 | 8.952 | 8.985 | 8.949 | 8.855 |
| Series resistance m Ω | 1.78 | 1.73 | 1.59 | 1.55 | 1.61 | 1.85 |
| Parallel resistance Ω | 439 | 450 | 448 | 453 | 450 | 421 |
| Conversion ratio % | 18.42 | 18.47 | 18.59 | 18.65 | 18.51 | 18.37 |
By upper table data it is found that being added to the plasticizer of variety classes and ratio in Examples 1 to 5, according to its mutually it
Between mating reaction it is different, lead to the data variation for examining wide ratio of silver paste.Wherein, the depth-width ratio of embodiment 5 is best, accordingly
Thin grid it is thinner, shading-area is smaller, therefore highest when its short circuit current in transformation efficiency.5 lines of embodiment it is not only thin and
And lines are more complete uniform, for corresponding series resistance also with regard to very little, the two factors ensure that the higher conversion effect of cell piece
Rate.Instead without the comparative example of addition plasticizer, lines depth-width ratio is small, and shading-area is big, causes short circuit current small；Print lines
Width is flat, and lines are inhomogenous, causes series resistance big, therefore it is minimum to integrate transformation efficiency.
Claims (4)
1. a kind of solar energy front side silver paste that depth-width ratio is high, it is characterised in that the raw material including following weight percent:
Conductive phase silver powder 82~90%, inorganic phase glass powder 1~3%, organic phase carrier 7~15%；
Wherein organic phase carrier comprises the following raw materials by weight percent: plasticizer 15~30%, ethyl cellulose 7~
15%, thixotropic agent 1~15%, surfactant 0~12%, remaining is solvent；
The silver powder D50 partial size is 0.8~2.5 μm, and tap density is 4.5~6.5g/ml；
The inorganic phase glass powder D50 partial size is 0.5~2.0 μm, and Tg point temperature is 250~500 DEG C；
The plasticizer is polyalcohol esters, phosphoric acid ester, phthalate, a variety of in fatty acid ester；
The thixotropic agent is rilanit special, polyamide modified rilanit special, polyamide wax pulp, polyethylene wax liquor, vapor phase method
One of silica, bentonite are a variety of；
The surfactant is polysorbas20, Tween 80, sorbitan ester, alkyl phenol polyoxyethylene ether, fatty amine polyoxy second
One of alkene ether is a variety of.
2. silver paste according to claim 1, it is characterised in that the ethyl cellulose be N-type or T-type ethyl cellulose or
The two mixture, ethoxyl content are 45~50%.
3. silver paste according to claim 1, it is characterised in that the solvent be butyl acetate, terpinol,
One of mixed dibasic acid ester and DBE, isophorone are a variety of.
4. a kind of preparation method of the high solar energy front side silver paste of any one of claims 1 to 3 depth-width ratio, it is characterised in that
Specific step is as follows:
(1) organic phase carrier is prepared
By ethyl cellulose and plasticizer, thixotropic agent, solvent, surfactant 40~80 DEG C of heating stirrings 0.1 after mixing
Homogeneous and transparent solution is made in~1h, the as described organic phase carrier；
(2) preparation of glass paste
Glass powder is taken, is mixed with the organic phase carrier prepared in step (1), after being uniformly dispersed on dispersion machine, on three-roller
Roller to fineness is 5um or less；
(3) preparation of silver paste
A, it is uniformly dispersed on dispersion machine after mixing the glass paste being prepared in silver powder and step (2), on three-roller
Roller to fineness is 5um or less；
B, the silver paste slurry placement prepared carries out viscosity test afterwards for 24 hours, if viscosity is excessive, adding suitable solvent will be starched
Expect viscosity-adjusting agent to 280~320Pa.s.
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| CN108586832B (en) * | 2018-03-28 | 2020-11-13 | 山东建邦胶体材料有限公司 | Special carrier containing thermal gel for solar cell front silver paste and preparation method thereof |
| CN109243669B (en) * | 2018-09-28 | 2020-05-08 | 常州聚和新材料股份有限公司 | Conductive front silver paste and preparation method thereof |
| CN110061074B (en) * | 2019-03-05 | 2021-07-27 | 苏州市贝特利高分子材料股份有限公司 | PERC solar cell |
| CN110010302A (en) * | 2019-03-05 | 2019-07-12 | 苏州市贝特利高分子材料股份有限公司 | A method of preparing PERC battery silver paste |
| CN110060794A (en) * | 2019-03-05 | 2019-07-26 | 苏州市贝特利高分子材料股份有限公司 | PERC silver paste based on granularity compounding |
| CN110265173B (en) * | 2019-04-22 | 2021-04-27 | 苏州市贝特利高分子材料股份有限公司 | Method for preparing organic carrier for fine-line high-aspect-ratio silk-screen printing paste |
| CN110164584B (en) * | 2019-04-22 | 2020-11-10 | 苏州市贝特利高分子材料股份有限公司 | Fine line high aspect ratio silk-screen printing slurry based on vinyl chloride-vinyl acetate copolymer organic carrier |
| CN110111923B (en) * | 2019-04-22 | 2020-11-06 | 苏州市贝特利高分子材料股份有限公司 | Solar cell with thin line high aspect ratio electrode |
| CN110164586B (en) * | 2019-04-22 | 2020-11-27 | 苏州市贝特利高分子材料股份有限公司 | Organic system for fine line high aspect ratio screen printing pastes |
| CN110379537A (en) * | 2019-07-15 | 2019-10-25 | 浙江中希电子科技有限公司 | A kind of solar energy front side conductive silver paste and its preparation method and application |
| CN110534228B (en) * | 2019-08-30 | 2021-07-20 | 湖南诺尔得材料科技有限公司 | Nano conductive silver paste and preparation method and application thereof |
| CN114203337A (en) * | 2021-12-13 | 2022-03-18 | 江苏聚盈新材料科技有限公司 | High-recovery solar cell front silver paste and preparation method thereof |
| CN114530277B (en) * | 2022-03-23 | 2024-06-21 | 河北晶乐光电科技有限公司 | Back electrode silver paste composition, preparation method thereof and solar cell |
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