CN101913763A - Glass composite for back surface field aluminum paste of solar battery and preparation method thereof - Google Patents
Glass composite for back surface field aluminum paste of solar battery and preparation method thereof Download PDFInfo
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- CN101913763A CN101913763A CN2010102640589A CN201010264058A CN101913763A CN 101913763 A CN101913763 A CN 101913763A CN 2010102640589 A CN2010102640589 A CN 2010102640589A CN 201010264058 A CN201010264058 A CN 201010264058A CN 101913763 A CN101913763 A CN 101913763A
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Abstract
The invention relates to a glass composite for back surface field aluminum paste of a solar battery, which is Bi-Si-B system glass of non-lead systems and comprises Bi2O3, SiO2, Al2O3, ZnO, B2O3 and CaO, and a modified additive comprises TiO2, ZrO2, V2O5, CaF, etc. The invention also relates to a method for preparing the glass composite for the back surface field aluminum paste of the solar battery. In the technical scheme of the invention, the provided glass composite for the back surface field aluminum paste of the solar battery utilizes the Bi-Si-B system glass of non-lead systems, thereby eliminating lead pollution in the glass composite, meanwhile, the glass composite has low-melting property equivalent to that of lead glass and good immersion property to silicon slices and aluminite powder, so that the prepared back surface field aluminum paste can form excellent ohmic contact with the silicon slices, has good performances of high adhesion force, low wrapping of battery plates and high battery conversion efficiency.
Description
Technical field
The present invention relates to the thick-film electronic slurry technical field of compositions, relate in particular to a kind of glass composite for back surface field aluminum paste 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 top 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 top efficiency value.And polycrystalline silicon solar cell is owing to exist a lot of crystal boundaries, the formed deathnium of these crystal boundaries, and the photovoltaic efficiency of conversion that has caused polysilicon is also well below silicon single crystal, and photoelectric transformation efficiency is 19.8%.Efficient is lower than laboratory efficient during suitability for industrialized production, the silicon single crystal 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 contacts 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 fine aluminum electrode slurry 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 (also being glass composition), additive, organic carrier.People's pay attention to day by day environmental protection at present, European Union has formulated " limit in the electronic and electrical equipment and use special harmful substance ROHS " environmental protection instruction for this reason specially, and especially clearly regulation does not allow to contain lead.Yet in the preparation process of the back surface field aluminum paste of solar battery of prior art, owing to the good low fusibleness of lead glass and to silicon chip and the good wetting property of aluminium powder, make lead glass be widely applied, wherein lead content causes very big harm to environment and human body inevitably up to more than 70%.
Summary of the invention
The purpose of this invention is to provide a kind of leadless environment-friendly, low warpage, high performance glass composite for back surface field aluminum paste.
In order to achieve the above object, technical scheme of the present invention proposes a kind of glass composite for back surface field aluminum paste of solar battery, and the quality proportioning of the composition that this glass composition comprises 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%; Property-modifying additive, 0-2%.
In the above-mentioned glass composite for back surface field aluminum paste of solar battery, the composition of described property-modifying additive comprises: TiO
2, ZrO
2, V
2O
5And CaF.
The softening temperature of above-mentioned glass composite for back surface field aluminum paste of solar battery is 500-560 ℃, and the coefficient of expansion is 55-60 * 10
-7/ K; Particle diameter is less than 3 μ m.
Technical scheme of the present invention also proposes a kind of method for preparing glass composite for back surface field aluminum paste of solar battery, comprising:
By following quality proportioning each composition is packed in the ceramic crucible: 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%; Property-modifying additive, 0-2%;
Described ceramic crucible is put into high temperature sintering furnace carry out melting;
Pour the clarifying glass metal of melting into the deionization quenching-in water;
The glass fragment of the quenching gained ceramic ball grinder that contains agate ball of packing into is carried out ball milling.
Among the preparation method of above-mentioned glass composition, described melting was carried out under 1200-1300 ℃ 1-2 hour; Described ball milling carried out 72 hours.
A kind of back surface field aluminum paste of solar battery of the also corresponding proposition of technical scheme of the present invention, the quality proportioning of the composition that this back field aluminum paste comprises and each composition is:
Aforesaid glass composition, 1-3%; Aluminium powder, 70-76%; Organic carrier, 20-30%.
In the above-mentioned back surface field aluminum paste of solar battery, the quality proportioning of the composition that described organic carrier comprises and each composition is: ethyl cellulose, 3-5%; The organic solvent Terpineol 350,30-45%; The Diethylene Glycol butyl ether, 20-40%; Diethylene Glycol-butyl ether acetic ester, 10-20%; The Yelkin TTS Ricinate, 0.2-1%.
In the above-mentioned back surface field aluminum paste of solar battery, the quality proportioning that described glass composition accounts for is 1-2.5%.
Technical scheme of the present invention also proposes a kind of method for preparing back surface field aluminum paste of solar battery, comprising:
Prepare each composition by following quality proportioning: aforesaid glass composition, 1-3%; Aluminium powder, 70-76%; Organic carrier, 20-30%;
Ready each composition is fully mixed, on three-roll grinder, grind then and be separated into fineness less than 15 μ m, viscosity back field aluminum paste composition at 28000-36000PaS.
The glass composite for back surface field aluminum paste of solar battery that technical solution of the present invention provides is by adopting a kind of Bi-Si-B system glass of nonlead system, thereby eliminated the pollution of lead in the glass composition, have simultaneously with the equal eutectic characteristic of lead glass and to the good imbibition characteristic of silicon chip and aluminium powder, make the back field aluminum paste of preparation to form good Ohmic contact, have the good characteristic that warpage is low, battery conversion efficiency is high of sticking power height, battery sheet with silicon chip.
Description of drawings
Fig. 1 prepares the method embodiment schema of glass composite for back surface field aluminum paste of solar battery for the present invention;
Fig. 2 prepares the method embodiment schema of back surface field aluminum paste of solar battery for the present invention;
Fig. 3 utilizes the solar cell that back field aluminum paste of the present invention makes and the performance data contrast synoptic 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 glass composite for back surface field aluminum paste of solar battery that the embodiment of the invention provides is the glass of the Bi-Si-B system of nonlead system, includes Bi
2O
3, SiO
2, B
2O
3, Al
2O
3, ZnOj and CaO, property-modifying additive then comprises TiO
2, ZrO
2, V
2O
5, CaF etc.Wherein, the quality proportioning of above-mentioned each composition is as follows: 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%; Property-modifying additive, 0-2%.And all kinds of technical indicators of this glass composition are as follows: softening temperature is 500-560 ℃; The coefficient of expansion is 55-60 * 10
-7/ K; Particle diameter D
50＜3 μ m.
The content of the glass composition of present embodiment (glassy bond phase) in back field aluminum paste is 1-3%, is preferably 1-2.5%, and its preparation method may further comprise the steps as shown in Figure 1:
S101, each composition is packed in the ceramic crucible by the quality proportioning;
Wherein, the quality proportioning of each composition is as follows: 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%; Property-modifying additive, 0-2%; As described above in Example, the property-modifying additive here comprises TiO
2, ZrO
2, V
2O
5, composition such as CaF.
S102, ceramic crucible is put into high temperature sintering furnace carry out melting;
Concrete melting condition can be at 1200-1300 ℃ of following melting 1-2 hour.
S103, pour the clarifying glass metal of melting into the deionization quenching-in water;
S104, the glass fragment of the quenching gained ceramic ball grinder that contains agate ball of packing into is carried out ball milling;
The ball milling of this step can carry out 72 hours, and the material that is obtained records particle diameter D
50＜3 μ m, softening temperature are that 525 ℃, the coefficient of expansion are 56 * 10
-7/ K takes out the material dry for standby, is the glass composition of finished product.
Particularly, the prepared sun power glass composite for back surface field aluminum paste of present embodiment has following performance perameter to require:
Particle diameter:, require the too little warpage that causes easily, too greatly then ashing easily in order to reach the requirement in filling aluminum particle gap less than 5 microns;
Softening temperature: anode slurry requires quite strict with the softening temperature of glass powder, if the softening temperature of glass powder is too high, in that be sintered under the peak temperature can not fusion, can occurs giving birth to and burn; If the softening temperature of glass powder is low excessively, then under firing temperature, causes the glass overcurrent and can not form normal membrane structure.
The coefficient of expansion: the coefficient of expansion of glass composition is preferably near the coefficient of expansion of silicon, otherwise occurs warpage easily;
Foreign matter content: answer alkali-free metal and heavy metal etc. in the glass powder, otherwise the impurity element that can cause p-n junction to puncture or can cause photoelectric transformation efficiency to reduce;
Content in aluminium paste: what of glassy bond phase content are very big to the influence of the electrical property of aluminium paste in the aluminium paste, when guaranteeing processing performance, should lack as much as possible.
Below the research and development mechanism of present embodiment glass composition is carried out explained in detail.
The vital role of glass composition in back surface field aluminum paste of solar battery is the pellumina on dissolving aluminium powder surface, thereby makes aluminium powder be connected to form the continuous conduction film, and concrete mechanism is as described below.The chemical property of metallic aluminium is active in the aluminum electrode slurry; the surface of aluminium powder has layer oxide film usually; the oxide film chemical property is stable, is difficult for destroyed at normal temperatures and has protected aluminum particle not continued oxidation, is equivalent to the aluminium powder surface and has coated one deck dielectric.And at high temperature, because the solubleness of oxygen in aluminium constantly increases, oxide film constantly thickens, to a certain degree being tending towards saturated.Therefore, be nonconducting behind the slurry sintering by aluminium powder and organic carrier preparation.And why solar cell back electrode aluminum electrode slurry shows good electrical conductivity behind high temperature sintering, is because the glass powder in the aluminum electrode slurry has played main effect.In the sintering process, the oxide compound of aluminum metal particle surface is by the glass powder corrode on the one hand, on the other hand, the continuous again and airborne oxygen generation redox reaction of aluminum particulate, when dissolution rate during greater than oxidized speed, aluminum particulate will expose, and directly contacts mutually, at this moment aluminum particulate mutually clinkering and can improve the adhesion strength of conducting film and substrate together.In process of cooling, vitreum shrinks, and the contact of aluminum particulate is tightr, thereby forms conductive network.
The binding agent of selecting for use in the aluminum current electrode slurry mostly is the flint glass powder greatly, in order to develop the novel environment friendly lead free aluminum electrode slurry, at first must understand the formation mechanism of lead-free glass powder.Low-melting point lead-less glasses refers generally to the crown glass that fusing point is lower than 600 ℃.Traditional low melting glass is generally high lead content glass, and the reduction of lead content will cause the rising of glass fusing point.Therefore develop the key that low-melting crown glass is the unleaded solar cell back electrode aluminum electrode slurry of exploitation.
Negatively charged ion has determined the structure and the character thereof of material to a great extent to cationic shielding.In general, Ionic polarizability is high more, and the temperature of fusion of material is just low more, and Ionic polarizability also can be regarded the ability that makes ionic Elektronenschale generation deformation as, in the hope of guaranteeing the shielding to nucleus the best.Outermost layer is by 18 electronics (Zn
2+) or 18+2 electronics (P
3+, As
3+, Bi
3+) compound that waits the positively charged ion of formation to form, have same radius with positively charged ion, but with outermost layer be by 8 electronics (Ca
2+, Sr
2+, Ba
2+, Mg
2+) the indifferent gas build compound formed compares, the former is owing to have bigger polarizability, and its temperature of fusion will be lower than the latter.In addition, increase negatively charged ion and cationic ratio and also can improve cationic shielding degree, thereby also reduce the temperature of fusion of material.Therefore, one of composition characteristic of low-melting point lead-less glasses is exactly that the cations that polarizability is big in forming is quite high, and its content is often greater than glass-former.From the periodic table of elements, decision glass fusible composition can be some heavy metal ion, contain 18 or more electron rich outermost electronic shell ion, easily deformation heavy ion and with the ion of little electric charge.The effect of different glass component is as follows:
SiO
2Be a kind of component that forms glass, it is a key factor to forming stable glass.SiO in the glass
2Content is less than 0.1wt%, and it is unstable that glass can become, in rational content range, along with SiO
2The softening temperature of the increase glass of content can uprise, and it is big that viscosity becomes, and the chemical stability of glass and thermostability increase, and acid resistance strengthens, and physical strength increases, and smelting temperature increases.
Al
2O
3Replaceable part Si O
2, chemical stability, thermostability and the acid resistance of increase glass reduce crystallization, and general add-on is SiO
2Half weight or still less (), and make the Al of glass
2O
3Content is no more than 5wt%, Al
2O
3Content surpasses 5wt% can cause instability.
B
2O
3Be to be similar to SiO
2The component of formation glass.B
2O
3Make glass be easy to fusing, and suppress the undue increase of thermal expansion coefficient of glass, and make glass when roasting, have suitable flowability.Along with B
2O
3The increase of content, softening temperature reduces, the B of glass
2O
3If content is less than 1wt%, it is unstable that glass can become; If content is higher than 20%, it is extremely unstable that glass softening point can become.
ZnO has the reduction glass softening point, makes glass have the effect that suitable mobile and adjusting glass makes it to have the appropriate thermal coefficient of expansion when fusing.Effect is not obvious if ZnO content is lower than 1wt%; Be higher than 20wt%, it is unstable that glass can become.
Bi
2O
3Have the reduction glass softening point, make glass when fusing, have suitable flowability and the effect of regulating thermal expansion coefficient of glass, also increase the proportion of glass.Bi in the glass
2O
3If content very little, it is not enough that these effects can become; If this content is too high, it is too high that thermal expansivity may become.
The main effect of CaO is the chemical stability that improves glass, and the migration of the alkali metal impurity that raw material is introduced simultaneously plays restraining effect.
Property-modifying additive TiO
2, ZrO
2, V
2O
5, CaF etc. effect be the stability that improves glass, because self-field is powerful, form nucleus of crystal simultaneously, make glass in to a certain degree crystallization, thereby reduced the coefficient of expansion, make that silicon warp reduces behind the sintering.Its content 0-2%, preferred 1-2%; Less than 1%, enough nucleus of crystals can not be provided, thereby make that the glass crystallization degree is not enough, the coefficient of expansion is very big, causes the angularity of silicon chip very big; Greater than 2%, then can make the glass excessive crystallization to cause softening temperature too high, under equal sintering temperature, can not provide enough liquid phase dissolved pelluminas, cause the electrical characteristic of silicon chip very low.
Utilize the composition that the back surface field aluminum paste of solar battery of the glass composition preparation of the foregoing description comprises and the quality proportioning of each composition to be: above-mentioned glass composition, 1-3% is preferably 1-2.5%; Aluminium powder, 70-76%; Organic carrier, 20-30%.Wherein the quality proportioning of the composition that organic carrier comprised and each composition is respectively again: ethyl cellulose, 3-5%; The organic solvent Terpineol 350,3045%; The Diethylene Glycol butyl ether, 20-40%; Diethylene Glycol-butyl ether acetic ester, 10-20%; The Yelkin TTS Ricinate, 0.2-1%.
Correspondingly, the preparation method of above-mentioned back surface field aluminum paste of solar battery may further comprise the steps as shown in Figure 2:
S201, prepare each composition by the weighing of quality proportion speed;
Each composition and quality proportioning are as follows: above-mentioned glass composition, 1-3%; Aluminium powder, 70-76%; Organic carrier, 20-30%.The organic carrier here as mentioned above, mass component is as follows: ethyl cellulose, 3-5%; The organic solvent Terpineol 350,30-45%; The Diethylene Glycol butyl ether, 20-40%; Diethylene Glycol-butyl ether acetic ester, 10-20%; The Yelkin TTS Ricinate, 0.2-1%.
S202, load weighted each composition is fully mixed;
S203, mixture 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.
By the unorganic glass of the present invention bonding above-mentioned aluminum paste composition leadless environment-friendly of preparation mutually, meet the RoHS of European Union (Restriction of Hazardous Substances, " about being limited in the instruction of using some objectionable constituent in the electronic and electrical equipment "), U.S. REACH (REGULATIONconcerning the Registration, Evaluation, Authorization and Restriction of Chemicals, " chemical registration, assessment, the permission and the restriction ") environmental requirement, the softening temperature of glass powder is lower during sintering, cohesiveness is good, makes the aluminium powder layer firmly be attached on the silicon chip; Sintering after coefficient is less, and the battery bending tablet is little, and fragmentation rate reduces.
Back field 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 perameter comparative result of resulting solar cell and test usefulness as shown in Figure 3.By diagram as can be seen, on every index, all show the characteristic that is better than the testing standard sheet by the prepared solar cell of the back field aluminum paste of present embodiment.
In sum, the glass composite for back surface field aluminum paste of solar battery that technical solution of the present invention provides is by adopting a kind of Bi-Si-B system glass of nonlead system, thereby eliminated the pollution of lead in the glass composition, have simultaneously with the equal eutectic characteristic of lead glass and to the good imbibition characteristic of silicon chip and aluminium powder, make the back field aluminum paste of preparation to form good Ohmic contact, have the good characteristic that warpage is low, battery conversion efficiency is high of sticking power height, battery sheet with silicon chip.Show the monocrystaline silicon solar cell transformation efficiency that utilizes embodiment of the invention preparation more than 17.3% through practice, polysilicon solar cell transformation efficiency transformation efficiency all reaches or has exceeded the similar level of prior art more than 16%.
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. a glass composite for back surface field aluminum paste of solar battery is characterized in that, the quality proportioning of the composition that this glass composition comprises 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%; Property-modifying additive, 0-2%.
2. glass composite for back surface field aluminum paste of solar battery according to claim 1 is characterized in that the composition of described property-modifying additive comprises: TiO
2, ZrO
2, V
2O
5And CaF.
3. as glass composite for back surface field aluminum paste of solar battery as described in the claim 2, it is characterized in that the softening temperature of this glass composition is 500-560 ℃, the coefficient of expansion is 55-60 * 10
-7/ K; Particle diameter is less than 3 μ m.
4. a method for preparing glass composite for back surface field aluminum paste of solar battery is characterized in that, comprising:
By following quality proportioning each composition is packed in the ceramic crucible: 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%; Property-modifying additive, 0-2%;
Described ceramic crucible is put into high temperature sintering furnace carry out melting;
Pour the clarifying glass metal of melting into the deionization quenching-in water;
The glass fragment of the quenching gained ceramic ball grinder that contains agate ball of packing into is carried out ball milling.
5. method as claimed in claim 4 is characterized in that, described melting was carried out under 1200-1300 ℃ 1-2 hour.
6. method as claimed in claim 4 is characterized in that, described ball milling carried out 72 hours.
7. a back surface field aluminum paste of solar battery is characterized in that, the quality proportioning of the composition that this back field aluminum paste comprises and each composition is:
As each described glass composition of claim 1～3,1-3%; Aluminium powder, 70-76%; Organic carrier, 20-30%.
8. back surface field aluminum paste of solar battery as claimed in claim 7 is characterized in that, the quality proportioning of the composition that described organic carrier comprises and each composition is: ethyl cellulose, 3-5%; The organic solvent Terpineol 350,30-45%; The Diethylene Glycol butyl ether, 20-40%; Diethylene Glycol-butyl ether acetic ester, 10-20%; The Yelkin TTS Ricinate, 0.2-1%.
9. back surface field aluminum paste of solar battery as claimed in claim 8 is characterized in that, the quality proportioning that described glass composition accounts for is 1-2.5%.
10. a method for preparing back surface field aluminum paste of solar battery is characterized in that, comprising:
Prepare each composition by following quality proportioning: as each described glass composition of claim 1～3,1-3%; Aluminium powder, 70-76%; Organic carrier, 20-30%;
Ready each composition is fully mixed, on three-roll grinder, grind then and be separated into fineness less than 15 μ m, viscosity back field aluminum paste composition at 28000-36000PaS.
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Application publication date: 20101215 |