CN101916610A - Back field aluminum paste composition of solar battery and preparation method thereof - Google Patents
Back field aluminum paste composition of solar battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a back field aluminum paste composition of a solar battery, wherein the back field aluminum paste composition of the solar battery comprises the following components in percentage by weight: 70-76 percent of aluminum powder, 1-3 percent of glass binder phase and 20-30 percent of organic carrier, wherein the aluminum powder is formed by mixing fine aluminum powder with grain diameter of 3-5mum and coarse aluminum powder with grain diameter of 6-8mum in a predetermined mass ratio, and the grain diameter ratio of the fine aluminum powder to the coarse aluminum powder is greater than 0.414. In the back field aluminum paste composition of the solar battery and the preparation method thereof provided by the technical scheme of the invention, by reasonably designing the grain diameter ratio of the fine aluminum powder to the coarse aluminum powder, the stress generated in process of sintering is minimum, therefore, the purpose of reducing warping is realized.
Description
Technical field
The present invention relates to the thick-film electronic slurry technical field of compositions, relate in particular to a kind of back field aluminum paste composition of solar battery and preparation method thereof.
Background technology
The high-photoelectric transformation efficiency of single crystal silicon solar cell is 30% in theory, and the peak efficiency of polycrystalline silicon solar cell is 24%.At present, the high conversion efficiency of single crystal silicon solar cell has under lab had large increase, is 24.7%, near the peak efficiency value.And polycrystalline silicon solar cell is owing to exist a lot of crystal boundaries, the formed complex centre of these crystal boundaries, and the photovoltaic conversion efficiency that has caused polysilicon is also well below monocrystalline silicon, and photoelectric conversion efficiency is 19.8%.Efficient is lower than laboratory efficient during suitability for industrialized production, the monocrystalline silicon efficient of solar industry production at present more than 17%, polysilicon efficient is then more than 16%.
From the at present domestic and international silicon solar cell condition of production, most p type silicon materials that adopt are made n-p-p
+The type battery.Diffusion n type silicon forms the solar cell substrate on p type silicon materials, and silicon chip surface is coated with antireflective coating to be reduced sun reflection of light.The thickness of p type silicon is about 200 μ m, by diffuseing to form p-n junction.By silk-screen printing technique silver slurry, silver-colored aluminum electrode slurry, aluminum electrode slurry are printed on silicon chip surface then, form firm contact electrode behind the sintering.
In the manufacturing process of silicon solar cell, because the aluminium low price, purity is easy to control, and easily forms good ohmic contact with alloying with silicon, so usually is used to make the back electrode of silicon solar cell.In addition, the adulterated al element can form p-p at cell backside in the p of routine type silicon
+Knot forms back of the body electric field structure (Back Surface Field), is commonly called as aluminium back of the body field.The aluminum electrode slurry of high-quality has following some material impact for the output characteristic of silicon solar cell: (1) improves open circuit voltage; (2) reduce series resistance; (3) improve the long wave response, effectively reduce back of the body recombination-rate surface.
Solar cell is started late with the domestic research of paste compound, unit such as Yunnan semiconductor factory, the expensive institute of elder brother researches and develops out " efficient, low-cost crystal-silicon solar cell and special-purpose electrocondution slurry thereof " during " eight or five ", and the performance of silver-colored slurry, aluminum electrode slurry and silver-colored aluminium paste has reached U.S. Ferro company corresponding product level.Present domestic solar cell with the main manufacturer of aluminum electrode slurry have join sunlight, Beijing mulberry in Guangzhou Ruxing Technology Development Co., Ltd, Yunnan Kunming Institute of Precious Metals, Beijing can science and technology, the excellent happy photoelectricity in Wuhan etc.The scholar emerging RX8 serial crystal silicon solar cell of having developed in Guangzhou is carried on the back the electric field aluminum electrode slurry, has filled up the blank of China's electrocondution slurry, has created good economic benefit.
Aluminium paste is as a kind of paste compound product, and it mainly is made up of conductive phase (aluminium powder), glassy bond phase, additive, organic carrier.There are some problems usually in aluminum paste composition in the prior art.
At first be because of reducing the warpage issues that silicon wafer thickness brings.The silicon wafer thickness that is typically applied in solar cell is 180 μ m, because silicon materials account for more than 60% of battery cost, reduces cost thereby therefore be devoted to reduce silicon wafer thickness in the industry always.Yet when silicon wafer thickness further reduces, increase, make the product fragment rate increase, cause entreprise cost to rise owing to the aluminium paste sintering stress causes battery sheet warpage.Here, the reason that causes sintering stress to produce is an aluminium (24.9 * 10
-6/ K) and silicon (4.1 * 10
-6/ K) the coefficient of expansion does not match and causes.The method of at present known reduction warpage all is summed up as simple opposition method, promptly adds the high-temperature stable oxide such as the ZrO of the coefficient of expansion in slurry
2, TiO
2, SiO
2Deng, but, can cause the battery contact resistance to rise to a certain extent because this class material is an insulator, thus reduce the transformation efficiency of battery, simultaneously because addition seldom, generally surpasses 1%, on technology, be difficult to they are distributed in the aluminum paste composition uniformly.
In addition, the mutually high pbo glasses that adopt of glassy bond in the aluminium paste of prior art more, lead content causes very big harm up to more than 70% to environment and human body; Its organic carrier then adopts adjacent phenyl ester class as solvent and plasticizer simultaneously, not only can cause environmental pollution to worsen, and can jeopardize the healthy of direct or indirect exposed population group.
Summary of the invention
The purpose of this invention is to provide a kind of back field aluminum paste composition of solar battery and preparation method thereof, to solve the problems referred to above that aluminum paste composition exists in the prior art.
In order to achieve the above object, technical scheme of the present invention proposes a kind of back field aluminum paste composition of solar battery, and its composition comprises that aluminium powder, glassy bond reach organic carrier mutually, and the quality proportioning of described each composition is:
Aluminium powder, 70-76%; The glassy bond phase, 1-3%; Organic carrier, 20-30%;
Wherein, described aluminium powder is mixed by default quality proportioning by the atomized aluminium of particle diameter 3-5 μ m and the Grenaille of particle diameter 6-8 μ m, and the size ratio of described atomized aluminium and described Grenaille is greater than 0.414.
In the above-mentioned back field aluminum paste composition of solar battery, the quality proportioning of described atomized aluminium and described Grenaille is 4: 6.
In the above-mentioned back field aluminum paste composition of solar battery, described atomized aluminium and described Grenaille be purity greater than 99%, oxygen content is less than the ball aluminum powder of 600ppm.
In the above-mentioned back field aluminum paste composition of solar battery, the quality proportioning of the composition that described glassy bond comprises mutually and each composition is:
Bi
2O
3，65-75％；SiO
2，5-10％；B
2O
3，6-8％；Al
2O
3，0-2％；ZnO，8-10％；CaO?0-2％。
In the above-mentioned back field aluminum paste composition of solar battery, the quality proportioning of the composition that described organic carrier comprises and each composition is:
Ethyl cellulose, 3-5%; Terpinol, 30-45%; The diethylene glycol butyl ether, 20-40%; Diethylene glycol-butyl ether acetic acid esters, 10-20%; Lecithin, 0.2-1%.
Technical scheme of the present invention also proposes a kind of preparation method of back field aluminum paste composition of solar battery, may further comprise the steps:
Prepare each composition by following quality proportioning: aluminium powder, 70-76%; The glassy bond phase, 1-3%; Organic carrier, 20-30%; Wherein, described lead powder is mixed by default quality proportioning by the atomized aluminium of particle diameter 3-5 μ m and the Grenaille of particle diameter 6-8 μ m, and the size ratio of described atomized aluminium and described Grenaille is greater than 0.414;
Ready described each composition is fully mixed, obtain aluminum paste composition through grinding then.
Among the preparation method of above-mentioned back field aluminum paste composition of solar battery, the quality proportioning of described atomized aluminium and described Grenaille is 4: 6.
Among the preparation method of above-mentioned back field aluminum paste composition of solar battery, the quality proportioning of the composition that described glassy bond comprises mutually and each composition is:
Bi
2O
3，65-75％；SiO
2，5-10％；B
2O
3，6-8％；Al
2O
3，0-2％；ZnO，8-10％；CaO?0-2％。
Among the preparation method of above-mentioned back field aluminum paste composition of solar battery, the quality proportioning of the composition that described organic carrier comprises and each composition is:
Ethyl cellulose, 3-5%; Terpinol, 30-45%; The diethylene glycol butyl ether, 20-40%; Diethylene glycol-butyl ether acetic acid esters, 10-20%; Lecithin, 0.2-1%.
Among the preparation method of above-mentioned back field aluminum paste composition of solar battery, describedly obtain aluminum paste composition and specifically comprise: on three-roll grinder, to grind and be separated into fineness less than 15 μ m, viscosity aluminum paste composition at 28000-36000PaS through grinding.
Back field aluminum paste composition of solar battery that technical solution of the present invention provides and preparation method thereof, by the particle diameter proportioning of appropriate design thickness aluminium powder, the stress minimum that makes the sintering process generation, thus realization reduces the purpose of warpage.
Further, back field aluminum paste composition of solar battery that technical solution of the present invention provides and preparation method thereof is by adopting the Bi-Si-B system glassy bond phase of nonlead system, adopt diethylene glycol-butyl ether acetic acid esters to replace traditional adjacent benzene class simultaneously, thereby eliminated the lead contamination of glassy bond phase and the environmental hazard of organic carrier in the aluminum paste composition as solvent in the organic carrier and plasticizer.
Description of drawings
Fig. 1 prepares the method embodiment flow chart of back field aluminum paste composition of solar battery for invention;
Fig. 2 utilizes the solar cell that back field aluminum paste composition of the present invention makes and the performance data contrast schematic diagram of conventional solar cells.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
The back field aluminum paste composition of solar battery composition of the embodiment of the invention comprises that aluminium powder, glassy bond reach organic carrier mutually, and the quality proportioning of each composition is: aluminium powder, 70-76%; The glassy bond phase, 1-3%; Organic carrier, 20-30%.Wherein, above-mentioned aluminium powder is mixed by default quality proportioning by the atomized aluminium of particle diameter 3-5 μ m and the Grenaille of particle diameter 6-8 μ m, and the size ratio of atomized aluminium and Grenaille is greater than 0.414.And the preferred mass proportioning of above-mentioned atomized aluminium and Grenaille is 4: 6.In addition, atomized aluminium and Grenaille also preferably be purity greater than 99%, oxygen content is less than the ball aluminum powder of 600ppm.
Adopt the prepared aluminum paste composition of above-mentioned aluminium powder to have very little warpage, thereby do not make battery keep high-performance owing to do not add any low bulk oxide simultaneously, its principle is as described below.Though the generation of warpage is because the coefficient of expansion of aluminium and silicon does not match, thereby produces sintering stress and caused warpage, if proportioning that can appropriate design aluminium powder particle diameter, made the stress minimum that sintering process produces, just can realize reducing the purpose of warpage.From prior art as can be known in the industry in order to pursue a kind of high-performance, often the proportioning to the material of main part aluminium powder adopts the closely packed principle design of spheroid in component design, the particle diameter ratio that is big or small spheroid is 0.414 o'clock, bead is just filled big ball and is piled up the space that is produced, therefore spheroid is piled up the tightst, using this principle configuration, to come the thickness aluminium powder to carry out the aluminium paste film of sintering gained the finest and close, thereby performance is also high.But, cause that silicon warp is big, fragment rate is high, and then increased cost just because thereby the too fine and close stress that produces is also big.And the aluminium powder particle diameter proportioning that the embodiment of the invention adopted, when taking into account close-packed principle, make the particle diameter proportioning of atomized aluminium and Grenaille be a bit larger tham closely packed ratio 0.414, like this will be owing to bead struts the space that the big ball of a part forms greatly, rather than just in time fill, thereby can in aluminium paste, produce certain space, make aluminium paste have living space to shrink and discharge stress, and then realize reducing the purpose of warpage in sintering process.
Further, the composition that comprises mutually of the glassy bond in the foregoing description back field aluminum paste composition of solar battery and the quality proportioning of each composition are: Bi
2O
3, 65-75%; SiO
2, 5-10%; B
2O
3, 6-8%; Al
2O
3, 0-2%; ZnO, 8-10%; CaO 0-2%.The content of above-mentioned glassy bond in the present embodiment aluminum paste composition is 1-3% as mentioned above, but is preferably 1-2.5%.And the preparation method of this glassy bond phase is as follows: by prior art with above-mentioned oxide by the default proportion speed weighing ceramic crucible of packing into, put into high temperature sintering furnace, at 1200-1300 ℃ of following melting 1-2 hour; Pour the glass metal of melting clarification into the deionization quenching-in water then; Again the glass fragment of quenching gained is packed in the ceramic ball grinder that contains agate ball ball milling 72 hours records particle diameter D
50＜3 μ m take out dry for standby, are the glassy bond phase of finished product.In the back field aluminum paste composition of solar battery of present embodiment by adopting the Bi-Si-B system glassy bond phase of nonlead system, thereby eliminated the lead contamination of traditional glass bonding in mutually.
The quality proportioning of the composition that the organic carrier in the foregoing description back field aluminum paste composition of solar battery comprises and each composition is: ethyl cellulose, 3-5%; Terpinol, 30-45%; The diethylene glycol butyl ether, 20-40%; Diethylene glycol-butyl ether acetic acid esters, 10-20%; Lecithin, 0.2-1%.Its preparation method is: mentioned component is dropped in the reactor by default proportion speed weighing, be warming up to 60-80 ℃ and constant temperature 3-5 hour under low whipping speed 80-120 rev/min the state; Mentioned component in the reactor is uniformly mixed and fully reaction, uses silk screen filter after the reactant cooling, promptly obtains the finished product organic carrier.In the back field aluminum paste composition of solar battery of present embodiment, adopt the double solvents system of terpinol, diethylene glycol butyl ether, diethylene glycol-butyl ether acetic acid esters, add lecithin, ethyl cellulose simultaneously and synthetic organic carrier, owing to adopt diethylene glycol-butyl ether acetic acid esters to replace traditional adjacent benzene kind solvent and plasticizer, thereby eliminated the environmental hazard of organic carrier.And, use the aluminium paste of above-mentioned organic carrier preparation to have good dispersiveness or suspension, not stratified, the not sedimentation of postpone aluminum slurry for a long time has even coating during printing, make the pressed powder in the aluminium paste have good adhesion strength after the drying, the stress that silicon chip is produced is little.
The preparation method of embodiment of the invention back field aluminum paste composition of solar battery may further comprise the steps as shown in Figure 1:
S101, prepare each composition by the weighing of quality proportion speed;
Wherein each composition and quality proportioning are as follows: aluminium powder, 70-76%; The glassy bond phase, 1-3%; Organic carrier, 20-30%.
Above-mentioned aluminium powder is mixed by default quality proportioning by the atomized aluminium of particle diameter 3-5 μ m and the Grenaille of particle diameter 6-8 μ m, and the size ratio of atomized aluminium and Grenaille is greater than 0.414.And the preferred mass proportioning of above-mentioned atomized aluminium and Grenaille is 4: 6.In addition, atomized aluminium and Grenaille also preferably be purity greater than 99%, oxygen content is less than the ball aluminum powder of 600ppm.
In addition, the mass component of above-mentioned glassy bond phase and organic carrier is as follows respectively.Glassy bond phase: Bi
2O
3, 65-75%; SiO
2, 5-10%; B
2O
3, 6-8%; Al
2O
3, 0-2%; ZnO, 8-10%; CaO 0-2%.Organic carrier: ethyl cellulose, 3-5%; The organic solvent terpinol, 30-45%; The diethylene glycol butyl ether, 20-40%; Diethylene glycol-butyl ether acetic acid esters, 10-20%; The lecithin Ricinate, 0.2-1%.
S102, load weighted each composition is fully mixed;
S103, mixed material ground on three-roll grinder be separated into back field aluminum paste composition;
The back field aluminum paste composition fineness of finished product is less than 15 μ m, and viscosity is then between 28000-36000PaS.
The aluminum paste composition leadless environment-friendly of the embodiment of the invention, meet the RoHS of European Union (Restriction of Hazardous Substances, " about being limited in the instruction of using some harmful components in the electronic and electrical equipment "), U.S. REACH (REGULATION concerning the Registration, Evaluation, Authorization and Restriction of Chemicals, " chemicals registration, assessment, the permission and the restriction ") environmental requirement, the softening point of glass dust is lower during sintering, caking property is good, makes the aluminium powder layer firmly be attached on the silicon chip; The coefficient of expansion is less behind the sintering, and the battery bending tablet is little, and fragment rate reduces.
Aluminum paste composition with the present embodiment preparation, through 320 order stainless steel wire reticulated printings to the solar battery back surface, number to be printed 0.9 gram, with positive silver electrode together at belt speed 4650mm, high temperature 920 degree sintering, the standard solar cells plate performance parameter comparative result of resulting solar cell and test usefulness as shown in Figure 2.By diagram as can be seen, on every index, all demonstrate the characteristic that is better than the testing standard sheet by the prepared solar cell of the aluminum paste composition of present embodiment.
In sum, back field aluminum paste composition of solar battery that the embodiment of the invention provides and preparation method thereof, by the particle diameter proportioning of appropriate design thickness aluminium powder, the stress minimum that makes the sintering process generation, thus realization reduces the purpose of warpage.Further, it is by adopting the Bi-Si-B system glassy bond phase of nonlead system, adopt diethylene glycol-butyl ether acetic acid esters to replace traditional adjacent benzene class simultaneously, thereby eliminated the lead contamination of glassy bond phase and the environmental hazard of organic carrier in the aluminum paste composition as solvent in the organic carrier and plasticizer.
More than be preferred forms of the present invention, according to content disclosed by the invention, those of ordinary skill in the art can expect some identical, replacement schemes apparently, all should fall into the scope of protection of the invention.
Claims (10)
1. back field aluminum paste composition of solar battery, its composition comprises that aluminium powder, glassy bond reach organic carrier mutually, it is characterized in that, the quality proportioning of described each composition is:
Aluminium powder, 70-76%; The glassy bond phase, 1-3%; Organic carrier, 20-30%;
Wherein, described aluminium powder is mixed by default quality proportioning by the atomized aluminium of particle diameter 3-5 μ m and the Grenaille of particle diameter 6-8 μ m, and the size ratio of described atomized aluminium and described Grenaille is greater than 0.414.
2. back field aluminum paste composition of solar battery as claimed in claim 1 is characterized in that, the quality proportioning of described atomized aluminium and described Grenaille is 4: 6.
3. back field aluminum paste composition of solar battery as claimed in claim 2 is characterized in that, described atomized aluminium and described Grenaille be purity greater than 99%, oxygen content is less than the ball aluminum powder of 600ppm.
4. as each described back field aluminum paste composition of solar battery of claim 1～3, it is characterized in that the quality proportioning of the composition that described glassy bond comprises mutually and each composition is:
Bi
2O
3，65-75％；SiO
2，5-10％；B
2O
3，6-8％；Al
2O
3，0-2％；ZnO，8-10％；CaO?0-2％。
5. as each described back field aluminum paste composition of solar battery of claim 1～3, it is characterized in that the quality proportioning of the composition that described organic carrier comprises and each composition is:
Ethyl cellulose, 3-5%; Terpinol, 30-45%; The diethylene glycol butyl ether, 20-40%; Diethylene glycol-butyl ether acetic acid esters, 10-20%; Lecithin, 0.2-1%.
6. the preparation method of a back field aluminum paste composition of solar battery is characterized in that, may further comprise the steps:
Prepare each composition by following quality proportioning: aluminium powder, 70-76%; The glassy bond phase, 1-3%; Organic carrier, 20-30%; Wherein, described aluminium powder is mixed by default quality proportioning by the atomized aluminium of particle diameter 3-5 μ m and the Grenaille of particle diameter 6-8 μ m, and the size ratio of described atomized aluminium and described Grenaille is greater than 0.414;
Ready described each composition is fully mixed, obtain aluminum paste composition through grinding then.
7. the preparation method of back field aluminum paste composition of solar battery as claimed in claim 6 is characterized in that, the quality proportioning of described atomized aluminium and described Grenaille is 4: 6.
8. as the preparation method of claim 6 or 7 described back field aluminum paste composition of solar battery, it is characterized in that the quality proportioning of the composition that described glassy bond comprises mutually and each composition is:
Bi
2O
3，65-75％；SiO
2，5-10％；B
2O
3，6-8％；Al
2O
3，0-2％；ZnO，8-10％；CaO?0-2％。
9. as the preparation method of claim 6 or 7 described back field aluminum paste composition of solar battery, it is characterized in that the quality proportioning of the composition that described organic carrier comprises and each composition is:
Ethyl cellulose, 3-5%; Terpinol, 30-45%; The diethylene glycol butyl ether, 20-40%; Diethylene glycol-butyl ether acetic acid esters, 10-20%; Lecithin, 0.2-1%.
10. as the preparation method of claim 6 or 7 described back field aluminum paste composition of solar battery, it is characterized in that, describedly obtain aluminum paste composition and specifically comprise: on three-roll grinder, grind and be separated into fineness less than 15 μ m, viscosity aluminum paste composition at 28000-36000PaS through grinding.
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| CN103065702A (en) * | 2012-12-28 | 2013-04-24 | 东方电气集团东方汽轮机有限公司 | Crystalline silicon solar energy battery aluminium paste and preparation method thereof |
| CN103065702B (en) * | 2012-12-28 | 2016-04-20 | 东方电气集团东方汽轮机有限公司 | A kind of crystal silicon solar energy battery aluminium paste and preparation method thereof |
| WO2015014032A1 (en) * | 2013-07-29 | 2015-02-05 | 广州市儒兴科技开发有限公司 | Aluminium paste dedicated for local aluminium back surface field crystalline silicon solar cell and preparation method therefor |
| CN103824653A (en) * | 2014-03-18 | 2014-05-28 | 山西盛驰科技有限公司 | Method for preparing back-field slurry of high-performance crystal silicon solar cell |
| CN103824653B (en) * | 2014-03-18 | 2016-01-20 | 山西盛驰科技有限公司 | The preparation method of a kind of high-performance crystal silicon solar battery back field slurry |
| CN105225722A (en) * | 2015-10-22 | 2016-01-06 | 江苏泓源光电科技股份有限公司 | A kind of crystal silicon solar batteries aluminium paste of high conduction performance |
| CN110544549A (en) * | 2018-05-29 | 2019-12-06 | 磐采股份有限公司 | Aluminum paste for local back surface field solar cell and local back surface field solar cell using same |
| CN110544549B (en) * | 2018-05-29 | 2021-07-30 | 磐采股份有限公司 | Aluminum paste for local back surface field solar cell and local back surface field solar cell using same |
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| CN101916610B (en) | 2012-02-22 |
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