CN103951262A - Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste - Google Patents
Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste Download PDFInfo
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- CN103951262A CN103951262A CN201410150480.XA CN201410150480A CN103951262A CN 103951262 A CN103951262 A CN 103951262A CN 201410150480 A CN201410150480 A CN 201410150480A CN 103951262 A CN103951262 A CN 103951262A
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- leaded
- tellurium
- bismuth glass
- tellurium bismuth
- solar cell
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of the glass paste. The lead-tellurium-bismuth-containing glass paste is prepared by heating a mixture of 10-40% of PbO, 10-45% of TeO2 and 0.1-5% of Bi2O3 until the mixture is molten, carrying out quenching and ball milling on the obtained product so as to obtain glass particles, adding the glass particles into 10-79% of an organic medium, uniformly stirring the obtained mixture, grinding the obtained mixture until the granularity of the mixture is below 5 mu m, so that lead-tellurium-bismuth-containing glass paste is prepared. The lead-tellurium-bismuth-containing glass paste can replace traditional high-lead-content glass powder, and has the advantages of low lead content, low melting point, good adhesion, low contact resistance, high conversion efficiency and good reliability and the like; after the lead-tellurium-bismuth-containing glass paste is applied to front electrode slurry of crystalline silicon solar cells, solar cells with performances and characteristics comparable to, even more excellent than, the performances and characteristics of conventional solar cells, and the application ratio of the lead-tellurium-bismuth-containing glass paste in positive electrode slurry of solar cells is 0.1-50%.
Description
Technical field
The present invention relates to silicon wafer area of solar cell, particularly relate to leaded tellurium bismuth glass slurry and preparation and application for a kind of solar cell positive electrode.
Background technology
General silicon wafer solar cell is made up of P type silicon wafer semiconducter substrate, n type diffused layer, antireflective coating, backplate and front electrode etc.To be generally the mode that adopts silk screen printing be printed on slurry on antireflective coating through Fast Sintering at 500-900 DEG C and form front electrode.The front electrode slurry that suitability for industrialized production adopts is mainly formed by component rollings such as silver, glass material and organic carriers.In sintering process, in front electrode slurry, the effect of glass material is antireflective coating is melted and remove, and obtains the some contact between front electrode and n type diffused layer, and this process is commonly referred to burns (Fire-through).
In sintering process, glass material is very large on solar cell properties impact.In the time that front electrode does not run through antireflective coating, cohesive strength fluctuation can be caused and the problems such as stable ohmic contact can not be between front electrode and n type diffused layer, obtained, not enough ohmic contact can cause loss between period of output, thereby causes the lower transformation efficiency of solar cell and the decline of current/voltage characteristic.If but front electrode runs through n type diffused layer below and invades semiconducter substrate after running through antireflective coating, and P-N knot may damage, and the packing factor being obtained by current/voltage characteristic measurement can affect adversely.
In order to obtain suitable burning, the glass material that preferably antireflective coating is had to good solubility is as the frit in anode silver paste.The glass material that wherein contains plumbous oxide often forms electrode as the frit in conventional silver slurry, because the softening temperature of flint glass is easy to regulate, have good adhesion with silicon substrate, can burn more up hill and dale antireflective coating, the solar cell properties of preparation is good.But, in recent years along with the raising of people's environmental consciousness, contain the glass material of plumbous oxide due to its toxicity and pollution problem, limit it and further applied.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of low lead tolerance, the good leaded tellurium bismuth glass slurry of low melting point and stability and methods for making and using same thereof, leaded tellurium bismuth glass material and organic medium are mixed with into leaded tellurium bismuth glass slurry by the present invention, its benefit is that slurry is easy to prepare, be conducive to control and the storage of glass powder particles degree, glass powder particles degree is reduced to below 5 microns, there is a certain proportion of nano bismuth oxide powder simultaneously, be conducive to reduce the contact resistance that vitreum is prepared disposed slurry and silicon chip, glass paste sticking power of the present invention is good, contact resistance is low, efficiency of conversion is high, good reliability.
The present invention for the technical scheme that solves its technical problem and adopt is:
The invention provides the leaded tellurium bismuth glass of a kind of solar cell positive electrode and starch, by described leaded tellurium bismuth glass slurry total weight percent, its component and content are as follows:
PbO：10-40%；
TeO
2：10-45%；
Bi
2O
3：0.1-5%；
Organic medium: 10-79%.
Say further, organic medium wherein can be the one in Gum Rosin, acrylic resin and celluosic resin.
Say further, the softening temperature of described leaded tellurium bismuth glass slurry is 200-400 DEG C, and the thermal expansivity that described leaded tellurium bismuth glass is starched within the scope of 25-300 DEG C is 100 × 10
-7/ DEG C-200 × 10
-7/ DEG C.
Say further Bi in described leaded tellurium bismuth glass slurry
2o
3grain diameter be 10nm-5000nm, be preferably 30nm-3000nm, be more preferred from 200nm-500nm.In described leaded tellurium bismuth glass slurry, glass powder particles degree is below 5 μ m.
The present invention also provides the preparation method of above-mentioned solar cell positive electrode with leaded tellurium bismuth glass slurry, and preparation process is carried out in the steps below:
One, get the raw materials ready: by raw material weight per-cent, proportioning raw materials is as follows: PbO:10-40%; TeO
2: 10-45%; Bi
2o
3: 0.1-5%; Organic medium: 10-79%;
Two, by described PbO, TeO
2and Bi
2o
3compound is placed in heating and melting at 700-1000 DEG C, obtains melten glass liquid;
Three, described melten glass liquid is carried out to quench treatment, obtain granular glass;
Four, described granular glass is carried out to ball milling, after sieve, obtain leaded tellurium bismuth glass material;
Five, described leaded tellurium bismuth glass material is added in described organic medium, after stirring, grind, below grinding control granularity to 5 μ m, make the leaded tellurium bismuth glass of solar cell positive electrode and starch.
Say further, in step 4, ball milling and sieve after particle size be controlled at 0.2-20 μ m.
Say further, in step 5, use homogenizer to stir, re-use three-roll grinder and grind.
The present invention also provides the application method of above-mentioned solar cell positive electrode with leaded tellurium bismuth glass slurry, and the usage ratio that described leaded tellurium bismuth glass is starched in solar cell positive electrode slurry is 0.1-50%, is preferably 2-30%, more preferably 6-15%.
The invention has the beneficial effects as follows: leaded tellurium bismuth glass of the present invention is starched with PbO and TeO
2component is main glass-former, has advantages of low melting temperature, highly durable and be easy to silver to be dissolved in sosoloid; And TeO
2have and the utmost point low reactivity of silicon oxide and wider infrared district, high photoelectric coupling coefficient, good corrosion resistance, higher specific refractory power, lower glass melting temperature, the low a series of features such as phonon energy and good chemical stability of seeing through.In addition, in the formula of leaded tellurium glass material, add and have Bi
2o
3, can effectively improve the energy of phonon in glass material and reduce the second-order transition temperature of glass material, can reduce again the contact resistance of silicon chip of solar cell and glass paste.Because above-mentioned leaded tellurium bismuth glass slurry has higher thermostability, chemical stability and stronger corrosion resistance, and higher to silver-colored solid content, lower to the reactivity of silicon oxide, the softening temperature of glass material is 200-400 DEG C, and the thermal expansivity within the scope of 25-300 DEG C is 100 × 10
-7/ DEG C-200 × 10
-7/ DEG C, therefore this leaded tellurium bismuth glass slurry can substitute traditional high lead tolerance glass powder, in silicon wafer front electrode of solar battery slurry, apply, can obtain performance and the quite even more excellent solar cell of characteristic with performance and characteristic and conventional sun power electrode.
Embodiment
Below, by specific specific examples explanation the specific embodiment of the present invention, those skilled in the art can understand advantage of the present invention and effect easily by content disclosed in the present specification.The present invention also can other different mode be implemented, and, under not departing from disclosed category, can give different modifications and change that is.
Embodiment:
1. take each feed composition according to the quality percentage composition data of each embodiment in following table 1;
2. use ball mill to mix load weighted each raw material in step 1, pack in fused quartz or corundum crucible after mixing, in High Temperature Furnaces Heating Apparatus, heat, temperature is controlled at 700-1000 DEG C, forms melten glass liquid;
3. melten glass liquid is poured into water coolingly fast, then dries and obtain granular glass;
4. granular glass is milled to 0.2-20 μ m(with ball mill and is preferably 0.5-3 μ m), the glass powder after ball milling sieves, and obtains the leaded tellurium bismuth glass material of powdery;
5. the leaded tellurium bismuth glass material of getting the powdery that step 4 obtains adds in organic medium, after homogenizer stirs, uses three-roll grinder that its granularity is down to below 5 microns.Wherein, organic medium can be chosen in these several large classes of Gum Rosin, acrylic resin and celluosic resin.Wherein, Bi
2o
3grain diameter be 10nm-5000nm, be preferably 30nm-3000nm, be more preferred from 200nm-500nm.
The leaded tellurium bismuth glass material of getting the powdery that step 4 obtains adopts differential scanning calorimetric analysis method (DSC method) test softening point temperature in right amount, the results are shown in following table 1.
Table 1
Above-mentioned glass paste has replaced traditional flint glass with the plumbous tellurium bismuth glass of low melting temperature, and the glass material eutectic and the stability that obtain are better.The softening temperature of this leaded tellurium bismuth glass slurry is 200-400 DEG C.
Above-mentioned leaded tellurium bismuth glass is starched with PbO and TeO
2component is main glass-former, has advantages of low melting temperature, highly durable and be easy to silver to be dissolved in sosoloid; And TeO
2have and the utmost point low reactivity of silicon oxide and wider infrared district, high photoelectric coupling coefficient, good corrosion resistance, higher specific refractory power, lower glass melting temperature, the low a series of features such as phonon energy and good chemical stability of seeing through.In addition, in the formula of leaded tellurium glass material, add and have Bi
2o
3, can effectively improve the energy of phonon in glass material and reduce the second-order transition temperature of glass material, can reduce again the contact resistance of silicon chip of solar cell and glass paste.Because above-mentioned leaded tellurium bismuth glass slurry has higher thermostability, chemical stability and stronger corrosion resistance, and higher to silver-colored solid content, lower to the reactivity of silicon oxide, the softening temperature of glass material is 200-400 DEG C, and the thermal expansivity within the scope of 25-300 DEG C is 100 × 10
-7/ DEG C-200 × 10
-7/ DEG C, therefore this leaded tellurium bismuth glass slurry can substitute traditional high lead tolerance glass powder, in silicon wafer front electrode of solar battery slurry, apply, can obtain performance and the quite even more excellent solar cell of characteristic with performance and characteristic and conventional sun power electrode.
The usage ratio that described leaded tellurium bismuth glass is starched in solar cell positive electrode slurry is 0.1-50%, is preferably 2-30%, more preferably 6-15%.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as limiting the scope of the invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with claim.
Claims (10)
1. a solar cell positive electrode is starched with leaded tellurium bismuth glass, it is characterized in that, by described leaded tellurium bismuth glass slurry total weight percent, its component and content are as follows:
PbO：10-40%；
TeO
2：10-45%；
Bi
2O
3：0.1-5%；
Organic medium: 10-79%.
2. solar cell positive electrode as claimed in claim 1 is starched with leaded tellurium bismuth glass, it is characterized in that, described organic medium is the one in Gum Rosin, acrylic resin and celluosic resin.
3. solar cell positive electrode as claimed in claim 1 is starched with leaded tellurium bismuth glass, it is characterized in that, the softening temperature of described leaded tellurium bismuth glass slurry is 200-400 DEG C, and the thermal expansivity that described leaded tellurium bismuth glass is starched within the scope of 25-300 DEG C is 100 × 10
-7/ DEG C-200 × 10
-7/ DEG C.
4. solar cell positive electrode as claimed in claim 1 is starched with leaded tellurium bismuth glass, it is characterized in that, Bi in described leaded tellurium bismuth glass slurry
2o
3grain diameter be 10nm-5000nm, in described leaded tellurium bismuth glass slurry, glass powder particles degree is below 5 μ m.
5. a preparation method for leaded tellurium bismuth glass slurry for solar cell positive electrode, is characterized in that, preparation process is carried out in the steps below:
One, get the raw materials ready: by raw material weight per-cent, proportioning raw materials is as follows: PbO:10-40%; TeO
2: 10-45%; Bi
2o
3: 0.1-5%; Organic medium: 10-79%;
Two, by described PbO, TeO
2and Bi
2o
3compound is placed in heating and melting at 700-1000 DEG C, obtains melten glass liquid;
Three, described melten glass liquid is carried out to quench treatment, obtain granular glass;
Four, described granular glass is carried out to ball milling, after sieve, obtain leaded tellurium bismuth glass material;
Five, described leaded tellurium bismuth glass material is added in described organic medium, after stirring, grind, below grinding control granularity to 5 μ m, make the leaded tellurium bismuth glass of solar cell positive electrode and starch.
6. the preparation method of leaded tellurium bismuth glass slurry for solar cell positive electrode as claimed in claim 5, is characterized in that, in step 4, ball milling and sieve after particle size be controlled at 0.2-20 μ m.
7. the preparation method of leaded tellurium bismuth glass slurry for solar cell positive electrode as claimed in claim 5, is characterized in that, in step 5, uses homogenizer to stir, and re-uses three-roll grinder and grinds.
8. an application method for leaded tellurium bismuth glass slurry for the solar cell positive electrode as described in claim 1 to 7, is characterized in that, the usage ratio that described leaded tellurium bismuth glass is starched in solar cell positive electrode slurry is 0.1-50%.
9. the application method of leaded tellurium bismuth glass slurry for solar cell positive electrode as claimed in claim 8, is characterized in that, the usage ratio that described leaded tellurium bismuth glass is starched in solar cell positive electrode slurry is 2-30%.
10. the application method of leaded tellurium bismuth glass slurry for solar cell positive electrode as claimed in claim 9, is characterized in that, the usage ratio that described leaded tellurium bismuth glass is starched in solar cell positive electrode slurry is 6-15%.
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|---|---|---|---|
| CN201410150480.XA CN103951262B (en) | 2014-04-15 | 2014-04-15 | Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste |
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|---|---|---|---|
| CN201410150480.XA CN103951262B (en) | 2014-04-15 | 2014-04-15 | Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste |
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| CN103951262B CN103951262B (en) | 2017-01-25 |
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| CN107089798A (en) * | 2015-11-20 | 2017-08-25 | 硕禾电子材料股份有限公司 | Oxide crystallization, its preparation method and the electrically-conducting paint comprising oxide crystallization |
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| CN107089798A (en) * | 2015-11-20 | 2017-08-25 | 硕禾电子材料股份有限公司 | Oxide crystallization, its preparation method and the electrically-conducting paint comprising oxide crystallization |
| CN107089798B (en) * | 2015-11-20 | 2021-01-26 | 硕禾电子材料股份有限公司 | Oxide crystal, method for preparing the same, and conductive coating material containing the same |
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