CN103130413B - Glass raw material composition, inorganic glass powder, crystalline silicon solar battery aluminum conductive paste and preparation method of the crystalline silicon solar battery aluminum conductive paste - Google Patents

Glass raw material composition, inorganic glass powder, crystalline silicon solar battery aluminum conductive paste and preparation method of the crystalline silicon solar battery aluminum conductive paste Download PDF

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CN103130413B
CN103130413B CN201110377185.4A CN201110377185A CN103130413B CN 103130413 B CN103130413 B CN 103130413B CN 201110377185 A CN201110377185 A CN 201110377185A CN 103130413 B CN103130413 B CN 103130413B
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silicon solar
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谭伟华
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BYD Co Ltd
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Abstract

The invention provides a glass raw material composition. The glass raw material composition comprises, by weight, 35 to 60 parts of Bi2O3, 10 to 30 parts of B2O3, 10 to 20 parts of SiO2, 1 to 5 parts of CaO, 0.5 to 5 parts of MgO, 0 to 5 parts of Al2O3, 3 to 8 parts of Sb2O3 and Sb2O5, and a nitrate of which the content is 0.5 to 1.5 times the content of Sb2O3, wherein the nitrate is magnesium nitrate or calcium nitrate. The invention also provides inorganic glass powder prepared from the glass raw material composition, crystalline silicon solar battery aluminum conductive paste prepared from the inorganic glass powder, and a preparation method of the crystalline silicon solar battery aluminum conductive paste. The clear inorganic glass powder can be prepared from the glass raw material composition and thus a battery piece prepared from the crystalline silicon solar battery aluminum conductive paste containing the inorganic glass powder has high photoelectric conversion efficiency and high water boiling resistance.

Description

Frit composition, unorganic glass powder and crystal-silicon solar cell aluminum conductive electric slurry and preparation method thereof
Technical field
The invention belongs to filed of crystal silicon solaode technique, particularly relate to a kind of frit composition, glass powder and a kind of crystal-silicon solar cell aluminum conductive electric slurry and preparation method thereof.
Background technology
Aluminum conductive electric slurry belongs to one of electronic information material, is also the main subsidiary material making crystal-silicon solar cell simultaneously, in this battery material cost, occupies sizable proportion.Crystal-silicon solar cell is a kind of inexhaustible environmental protection renewable energy source, and current international research is very active.The one-tenth of aluminium paste is grouped into, make, print and sintering process all exists larger impact to the performance of crystal-silicon solar cell.At present, the aluminum conductive electric slurry that some Research Institute of international major company and China are comparatively ripe, be used on crystal-silicon solar cell, the basic electric property of the aluminium back surface field formed after sintering can meet industry requirement preferably, the photoelectric transformation efficiency of battery is also higher, and not leaded heavy metal such as grade, meets environmental requirement in slurry.Along with the technical development of sun power industry, to the electricity conversion of silicon solar cell and the requirement of cell piece water boiling resistance performance more and more higher.
A kind of synthesizing silicon solar energy cell back field aluminum electrocondution slurry is disclosed in CN1901234A, by adding Metallic Indium Powder in slurry in this aluminum conductive electric slurry, to improve electricity conversion, adopt the oxidation of boron powder, dimethyl siloxane and stearate, decomposition method acquisition frit simultaneously.Cell piece silicon chip after adopting this aluminum conductive electric slurry to sinter is not bending or bending little, and aluminium film surface is smooth, does not play aluminium pill, does not blister, and aluminium film is to silicon substrate adhere firmly.But in this aluminum conductive electric slurry, Metallic Indium Powder source is difficult and expensive, and cost of sizing agent is higher; Boron powder, dimethyl siloxane and stearate oxidation simultaneously, the complex process of decomposing, if reaction thoroughly can not introduce plurality of impurities, reduce the water boiling resistance performance of cell piece.
Summary of the invention
The invention solves that the aluminum conductive electric slurry cost existed in prior art is high, the electricity conversion of cell piece and the technical problem of water boiling resistance poor-performing.
The invention provides a kind of frit composition, containing following component: Bi in described frit composition 2o 335-60 weight part, B 2o 310-30 weight part, SiO 210-20 weight part, CaO 1-5 weight part, MgO 0.5-5 weight part, Al 2o 30-5 weight part;
Also containing Sb in described frit composition 2o 3, Sb 2o 5and nitrate, Sb 2o 3with Sb 2o 5total content be 3-8 weight part, described nitrate is magnesium nitrate or nitrocalcite, and the content of described nitrate is Sb 2o 3the 0.5-1.5 of content doubly.
Present invention also offers a kind of unorganic glass powder, described unorganic glass powder is founded by frit composition provided by the invention is first warming up to 500-600 DEG C, then be warming up to 1200-1300 DEG C to found, shrend obtains granulated glass sphere after filtering, and then granulated glass sphere is carried out ball milling and obtains.
Then, present invention also offers a kind of crystal-silicon solar cell aluminum conductive electric slurry, with the total mass of described crystal-silicon solar cell aluminum conductive electric slurry for benchmark, ball aluminum powder containing 70-80wt% in described crystal-silicon solar cell aluminum conductive electric slurry, the organic carrier of 10-25wt% and the unorganic glass powder of 1-5wt%; Wherein, described ball aluminum powder is the aluminium powder that Surface coating has aluminum oxide, and described unorganic glass powder is unorganic glass powder provided by the invention.
Finally, the invention provides the preparation method of described crystal-silicon solar cell aluminum conductive electric slurry, comprise and ball aluminum powder and unorganic glass powder are scattered in organic carrier in proportion, after grinding, namely obtain described crystal-silicon solar cell aluminum conductive electric slurry; Wherein, described ball aluminum powder is the aluminium powder that Surface coating has aluminum oxide, and described unorganic glass powder is unorganic glass powder provided by the invention.
In frit composition provided by the invention, by adding Sb again on existing frit basis 2o 3, Sb 2o 5and nitrate, wherein nitrate is magnesium nitrate or nitrocalcite, and in melting process, nitrate first decomposes releasing oxygen, and carry out small stirring to glass system and each component is uniformly distributed, the oxygen simultaneously generated is by Sb 2o 3be oxidized to Sb 2o 5; Temperature continues to raise, Sb 2o 5decomposition and inversion is Sb 2o 3and oxygen, increase the oxidation atmosphere in glass system, can effectively stop Bi in glass system 2o 3high temperature reduction, simultaneously can take the small bubbles produced in glass melting process out of in oxygen dispose procedure, small stirring action be played to glass system, unorganic glass powder of the present invention is more formed uniformly, thus obtain the unorganic glass powder clarified.
Meanwhile, in frit composition provided by the invention, by Sb 2o 3, Sb 2o 5content suitably select, make crystal-silicon solar cell aluminum conductive electric slurry of the present invention fire in the process forming aluminium back surface field, appropriate Sb 2o 3can compete with the alumina layer on ball aluminum powder surface with the aluminum oxide in unorganic glass powder, weaken the action intensity of melten glass and aluminum oxide, aluminium powder surface in the last aluminium back surface field formed is made still to remain with partial oxidation aluminium thin layer, stop pure aluminum and hydrothermal reaction, thus under ensureing to adopt the cell piece of this aluminum conductive electric slurry to have the prerequisite of higher electricity conversion, water boiling resistance performance is greatly enhanced.
Embodiment
The invention provides a kind of frit composition, containing following component: Bi in described frit composition 2o 335-60 weight part, B 2o 310-30 weight part, SiO 210-20 weight part, CaO 1-5 weight part, MgO 0.5-5 weight part, Al 2o 30-5 weight part;
Also containing Sb in described frit composition 2o 3, Sb 2o 5and nitrate, Sb 2o 3with Sb 2o 5total content be 3-8 weight part, described nitrate is magnesium nitrate or nitrocalcite, and the content of described nitrate is Sb 2o 3the 0.5-1.5 of content doubly.
In described frit composition, Bi 2o 3, B 2o 3, SiO 2, CaO, MgO and Al 2o 3be raw material powder conventional in the glass powder of prior art, its glass powder formed is Bi 2o 3-B 2o 3-SiO 2system.In described frit composition, B 2o 3, SiO 2for glass network former, form the skeleton structure of glass network; Bi 2o 3for Web Grafiti body, it can destroy the skeleton structure of glass network, causes " node " of silica framework collapse.This node is the place that aluminum-oxygen tetrahedron (i.e. aluminum oxide) repairs silica skeleton; The interstitial content of unit mass is more, and the effect of unorganic glass powder to the aluminum oxide on ball aluminum powder surface is stronger.
In described frit composition, CaO, MgO make in glass high temperature melting process and play destruction to glass network, play congregation when temperature reduces.CaO, MgO containing trace in glass system, can reduce the beginning fusing point of glass slightly, reduces the viscosity under high temperature simultaneously, increases mobility and the wetting property of melten glass.
As the common practise of those skilled in the art, Al 2o 3effect is in glass different according to the difference of glass system.Particularly, when glass network in glass system destroys body (such as Bi 2o 3, CaO, MgO) content is more, and glass network former (such as B 2o 3, SiO 2) content less time, Al 2o 3occur with the form of glass-former in glass, ligancy is 4.And when glass network destruction body burden in glass system is less, and when glass network former is more, Al 2o 3occur with the form of glass intermediate in glass, ligancy is 6.
The present inventor is found by great many of experiments, and existing frit basis adds Sb again 2o 3, Sb 2o 5and nitrate, in melting process, nitrate first decomposes releasing oxygen, and carry out small stirring to glass system and each component is uniformly distributed, the oxygen simultaneously generated is by Sb 2o 3be oxidized to Sb 2o 5.Temperature continues to raise, Sb 2o 5decomposition and inversion is Sb 2o 3and oxygen, increase the oxidation atmosphere in glass system, can effectively stop Bi in glass system 2o 3high temperature reduction, simultaneously can take the small bubbles produced in glass melting process out of in oxygen dispose procedure, small stirring action be played to glass system, unorganic glass powder of the present invention is more formed uniformly, thus obtain the unorganic glass powder clarified.
The present inventor is found by further experiment, in the present invention, and described Sb 2o 5content need carry out according to the difference of fusion cast glass amount adaptation adjustment.Trace it to its cause and be, if Sb in frit composition 2o 5content is too low, and its oxygen produced when subsequent high temperature decomposes is less, not obvious to the stirring action of glass system, is difficult to the vitreum ensureing finally evenly to form clarification; Meanwhile, when disposable amount of glass of founding is larger, its addition should be lower; Otherwise can cause producing too much oxygen during pyrolytic decomposition, cause melten glass hydrorrhea to go out crucible.The present inventor is determined by experiment, in the present invention, and Sb 2o 3with Sb 2o 5total content when being 3-8 weight part, the glass obtaining clarifying can be ensured, can prevent again glass metal from overflowing crucible.
More preferably in situation, for ensureing in glass melting process, the reaction of oxidizing reaction Sum decomposition slowly and continue to carry out, described Sb 2o 3and Sb 2o 5particle all can not be too little.Under preferable case, described Sb 2o 3and Sb 2o 5median particle diameter be 1.0-5.0 μm.
Meanwhile, in the present invention, the oxide compound produced after described nitrates decompose can fuse one with the oxide compound in frit composition, can not introduce other impurity in glass.According to SODIUMNITRATE as nitrate of the present invention, because sodium ion particle diameter is less, easily move about in glass, and its High temperature diffusion coefficient is much larger than aluminium, formed in aluminium back surface field process at follow-up aluminum conductive electric slurry sintering, very easily diffuse in silicon chip, cause the impurity of P-type silicon, the serious electricity conversion reducing cell piece.And when adopting nitrocalcite or magnesium nitrate, then can not produce foregoing problems.Therefore, in the present invention, described nitrate is only limitted to nitrocalcite or magnesium nitrate.
Therefore, the invention provides a kind of unorganic glass powder, described unorganic glass powder is founded by frit composition provided by the invention is first warming up to 500-600 DEG C, is then warming up to 1200-1300 DEG C and founds, shrend obtains granulated glass sphere after filtering, and then granulated glass sphere is carried out ball milling and obtains.
Particularly, in temperature-rise period, when being warming up to 500-600 DEG C, namely there is the decomposition course of nitrate, produce O 2.The O generated 2playing small stirring action to glass system on the one hand, is that in glass system, each component is uniformly distributed, the O simultaneously generated 2can by frit composition by Sb 2o 3be oxidized to Sb 2o 5.
When sintering temperature continues to be increased to 1200-1300 DEG C, now Sb 2o 5sb can be converted into by pyrolytic decomposition 2o 3and O 2.The O now produced 2the oxidation atmosphere in glass system can be increased, stop Bi in glass system on the one hand 2o 3high temperature reduction, on the other hand take the small bubbles produced in glass melting process out of, small stirring action played to glass system.
The present inventor also finds by experiment, in the present invention, can not adopt Sb 2o 5whole replacement Sb 2o 3, its reason is: if only adopt Sb 2o 5, then frit composition Sb 2o 5used in amounts be greater than Sb in the present invention 2o 5and Sb 2o 3total content, otherwise formed unorganic glass powder in Sb 2o 3content can reduce; And Sb 2o 5consumption is once increase, and in glass system, the content of other component can corresponding reduction, and the performance of unorganic glass powder can be a greater impact.And in the present invention, by adopting Sb 2o 3, Sb 2o 5mixture, be convenient to the content controlling each component in glass system, small stirring action can be played to glass in glass smelting early stage and later stage, be convenient to glass and evenly formed thus the glass obtaining clarification.
In the present invention, for ensureing that nitrate all decomposes, Sb 2o 3all be converted into Sb 2o 5, 500-600 DEG C of time of founding is 0.2-0.8h.Meanwhile, for ensureing Sb 2o 5all be converted into Sb 2o 3, ensure to adopt the cell piece of this unorganic glass powder to have higher electricity conversion, 1200-1300 DEG C of time of founding is 0.5-2.5h.
According to method of the present invention, after frit composition has been founded, carry out shrend filtration, obtained granulated glass sphere.The particle diameter of granulated glass sphere is comparatively large, therefore needs to carry out being milled to required particle diameter, can obtain unorganic glass powder of the present invention.
Under preferable case, in the present invention, ball milling is carried out to granulated glass sphere, dry grind after comprising first wet-milling.Wherein, the wet-milling time is 5-8h, is preferably 6.5h.More preferably, in situation, during wet-milling, the mass ratio of zirconia ball, granulated glass sphere and deionized water is 4:0.8-1.2:0.5-0.8.The dry grinding time is 0.2-1h.During dry grinding, the mass ratio of zirconia ball and granulated glass sphere is 1:1.8-2.5.
By above-mentioned steps, unorganic glass powder provided by the invention can be obtained.The median particle diameter of described unorganic glass powder is 0.2-3 μm.The initial melting temperature of described unorganic glass powder is 580-620 DEG C.
Present invention also offers a kind of crystal-silicon solar cell aluminum conductive electric slurry, with the total mass of described crystal-silicon solar cell aluminum conductive electric slurry for benchmark, ball aluminum powder containing 70-80wt% in described crystal-silicon solar cell aluminum conductive electric slurry, the organic carrier of 10-25wt% and the unorganic glass powder of 1-5wt%; Wherein, described ball aluminum powder is the aluminium powder that Surface coating has aluminum oxide, and described unorganic glass powder is unorganic glass powder provided by the invention.
As the common practise of those skilled in the art, in aluminum conductive electric slurry sintering process, glass powder disperse is around ball aluminum powder, in sintering process, the alumina layer on glass powder meeting corrosion ball aluminum powder surface, molten aluminum simple substance diffuses in silicon wafer layer, thus forms described aluminium back surface field.Therefore, the Main Function of glass powder in aluminum conductive electric slurry is the alumina layer that ball aluminum powder surface is fallen in corrosion, impels pure aluminum to spread in silicon wafer layer.
In the present invention, by introducing appropriate Sb at frit composition 2o 3, Sb 2o 5, make crystal-silicon solar cell aluminum conductive electric slurry of the present invention fire in the process forming aluminium back surface field, Sb contained in unorganic glass powder 2o 3compete with the alumina layer on ball aluminum powder surface, weaken the action intensity of melten glass and aluminum oxide, aluminium powder surface in the last aluminium back surface field formed is made still to remain with partial oxidation aluminium thin layer, stop pure aluminum and hydrothermal reaction, thus under ensureing to adopt the cell piece of this aluminum conductive electric slurry to have the prerequisite of higher electricity conversion, water boiling resistance performance is greatly enhanced.
In the present invention, described ball aluminum powder directly can adopt various atomizing aluminium powders conventional in prior art.Under preferable case, the median particle diameter of described ball aluminum powder is 4.5-5.0 μm.
In the present invention, described ball aluminum powder is nucleocapsid structure, and kernel is aluminium simple substance, and shell is aluminum oxide.Under preferable case, the thickness of the surface alumina oxide of described ball aluminum powder is 10-20nm.More preferably, in situation, the thickness of the surface alumina oxide of described ball aluminum powder is 15-17nm.
Described organic carrier is organic system conventional in the aluminum conductive electric slurry of prior art, specifically comprises thickening material, auxiliary agent and organic solvent.Wherein, described thickening material is selected from least one of ethyl cellulose, modified phenolic resins or epoxy resin.Described organic solvent is selected from Terpineol 350, dibutyl phthalate, diethylene glycol monobutyl ether, turps, butyl glycol ether, diethylene glycol monobutyl ether acetic ester, ethylene glycol ether acetate, tributyl citrate, at least two kinds in butyl carbitol acetate, dibutyl phthalate, tributyl phosphate.Described auxiliary agent is selected from least one in lubricant, thixotropic agent.More preferably in situation, described lubricant is hexadecanol, and described thixotropic agent is modified hydrogenated Viscotrol C or polyamide wax powder.
In described organic carrier, the content of each component is in the usual range of this area, and the present invention does not have special stipulation.Such as, with the total mass of organic carrier for benchmark, wherein the content of organic resin is 4-10wt%, and the content of auxiliary agent is 1-5wt%, and the content of organic solvent is 85-95wt%.
As a kind of preferred implementation of the present invention, described organic solvent is the mixture of Terpineol 350, ethylene glycol ether acetate and diethylene glycol monobutyl ether.More preferably in situation, with the organic solvent of 100 weight parts for benchmark, wherein the content of Terpineol 350 is 55-65 weight part, and the content of ethylene glycol ether acetate is 15-25 weight part, and the content of diethylene glycol monobutyl ether is 15-25 weight part.
Finally, the invention provides the preparation method of described crystal-silicon solar cell aluminum conductive electric slurry, comprise and ball aluminum powder and unorganic glass powder are scattered in organic carrier in proportion, after grinding, namely obtain described crystal-silicon solar cell aluminum conductive electric slurry; Wherein, described ball aluminum powder is the aluminium powder that Surface coating has aluminum oxide, and described unorganic glass powder is unorganic glass powder provided by the invention.
By the mode that ball aluminum powder, unorganic glass powder are scattered in organic carrier be: directly ball aluminum powder, unorganic glass powder are added in organic carrier, stir; Or, first unorganic glass powder is added in organic carrier, stirs, then adding ball aluminum powder in batches, often criticizing ball aluminum powder and add and first to stir afterwards, then add next batch ball aluminum powder, after all adding, high-speed stirring makes each component in slurry system dispersed.
In the present invention, for ensureing slickness, the planeness on the aluminium back surface field surface formed, also need to grind slurry system.Under preferable case, be ground to described crystal-silicon solar cell aluminum conductive electric slurry fineness < 20 μm.Described grinding can adopt the three-roll grinder of 150 to carry out, and more preferably in situation, grinding number of times is 15-20 time.
The cell piece aluminium film adopting crystal-silicon solar cell aluminum conductive electric slurry provided by the invention obtained is smooth, and sticking power is good, and water boiling resistance performance is high, has higher electricity conversion simultaneously.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
(1) preparation of unorganic glass powder:
Take 50 weight part Bi 2o 3, 24 weight part B 2o 3, 15 weight part SiO 2, 2 weight part Sb 2o 3(median particle diameter D 50be 2.5 μm), 3 weight part Sb 2o 5(median particle diameter D 50be 2.5 μm), 3.5 weight part CaO, 1.5 weight part MgO, 1.0 weight part Al 2o 3, 2 weight part Mg (NO 3) 2, adopt V-Mixer to be mixed by each oxide powder, proceed in corundum crucible, and be placed in silicon carbide rod furnace.To be warming up to 550 DEG C in silicon carbide rod furnace, insulation 0.5h, then be warming up to 1250 DEG C, insulation 2h, shrend is filtered and is obtained granulated glass sphere.By granulated glass sphere load ball grinder, in mass ratio zirconia ball: granulated glass sphere: deionized water=4:1:0.7, tank speed 300 revs/min, wet-milling 6.5h, filter post-drying, then the 0.5h that dry grinds, during dry grinding, the mass ratio of zirconia ball and glass powder is 1:2.By above-mentioned steps, obtain the unorganic glass powder S1 of the present embodiment.
(2) preparation of organic carrier:
By Terpineol 350: ethylene glycol ether acetate: diethylene glycol monobutyl ether mixes for 60:20:20 in mass ratio, obtain organic solvent.Take the organic solvent of 89 weight parts, 9 weight part ethyl cellulose STD-4 (it is 4 that Tao Shi produces viscosity), 1.5 part by weight modified hydrogenated castor oils and 0.5 weight part hexadecanol is added in this organic solvent, be heated to 65 DEG C and make abundant dissolving, and stir, obtain organic carrier.
(3) preparation of aluminum conductive electric slurry:
Take the organic carrier of the step (2) of 22.5 weight parts, be placed in the stainless cylinder of steel of high speed dispersor, add the unorganic glass powder S1 that the step (1) of 2.5 weight parts is obtained under whipped state, stir.Add the ball aluminum powder of 75 weight parts again, the median particle diameter D of this ball aluminum powder in batches 50be 4.5 μm, the alumina layer thickness of surface coverage is 15nm; Every batch of ball aluminum powder adds and first to stir evenly afterwards, then adds next batch, and after all adding, high-speed stirring is even.Carry out grinding 15 times with the three-roll grinder of 150 again, be ground to slurry fineness < 20 μm, obtain the crystal-silicon solar cell aluminum conductive electric slurry of the present embodiment, be designated as S10.
Embodiment 2
Adopt the step identical with embodiment 1 to prepare unorganic glass powder S2 and the crystal-silicon solar cell aluminum conductive electric slurry S20 of the present embodiment, difference is:
In step (1), take 52 weight part Bi 2o 3, 24 weight part B 2o 3, 15 weight part SiO 2, 1 weight part Sb 2o 3(median particle diameter D 50be 3 μm), 2 weight part Sb 2o 5(median particle diameter D 50be 2.5 μm), 3.5 weight part CaO, 1.5 weight part MgO, 1.0 weight part Al 2o 3, 0.5 weight part Mg (NO 3) 2.
Embodiment 3
Adopt the step identical with embodiment 1 to prepare unorganic glass powder S3 and the crystal-silicon solar cell aluminum conductive electric slurry S30 of the present embodiment, difference is:
In step (1), take 50 weight part Bi 2o 3, 24 weight part B 2o 3, 15 weight part SiO 2, 3 weight part Sb 2o 3(median particle diameter D 50be 2 μm), 5 weight part Sb 2o 5(median particle diameter D 50be 2 μm), 3.5 weight part CaO, 1.5 weight part MgO, 1.0 weight part Al 2o 3, 4.5 weight part Ca (NO 3) 2.
Embodiment 4
Adopt the step identical with embodiment 1 to prepare unorganic glass powder S4 and the crystal-silicon solar cell aluminum conductive electric slurry S40 of the present embodiment, difference is:
In step (1), be warming up to 500 DEG C, insulation 0.5h; Then 1200 DEG C are warming up to, insulation 0.5h; And the time of wet-milling is 5h.
Embodiment 5
Adopt the crystal-silicon solar cell aluminum conductive electric slurry S50 preparing the present embodiment with the unorganic glass powder S1 in embodiment 1, difference is:
In step (3), organic carrier consumption is 25 weight parts, and the consumption of unorganic glass powder S1 is 5 weight parts, and the consumption of ball aluminum powder is 70 weight parts, the median particle diameter D of this ball aluminum powder 50be 5 μm, the alumina layer thickness of surface coverage is 17nm.
Comparative example 1
Method disclosed in CN1901234A embodiment 1 is adopted to prepare aluminum conductive electric slurry, as the crystal-silicon solar cell aluminum conductive electric slurry DS10 of this comparative example.
Comparative example 2
Adopt the step identical with embodiment 1 to prepare unorganic glass powder and the crystal-silicon solar cell aluminum conductive electric slurry DS20 of this comparative example, difference is:
In step (1), take 50 weight part Bi 2o 3, 24 weight part B 2o 3, 15 weight part SiO 2, 5 weight part Sb 2o 3(median particle diameter D 50be 2.5 μm), 3.5 weight part CaO, 1.5 weight part MgO, 1.0 weight part Al 2o 3.
Comparative example 3
Adopt the step identical with embodiment 1 to prepare unorganic glass powder and the crystal-silicon solar cell aluminum conductive electric slurry DS30 of this comparative example, difference is:
In step (1), take 50 weight part Bi 2o 3, 24 weight part B 2o 3, 15 weight part SiO 2, 5 weight part Sb 2o 5(median particle diameter D 50be 2.5 μm), 3.5 weight part CaO, 1.5 weight part MgO, 1.0 weight part Al 2o 3.
Performance test:
1, unorganic glass powder performance test:
Adopt median particle diameter D50 and the beginning fusing point of BT-2003 laser particle size analyzer (Dandong hundred special product) dry method test unorganic glass powder sample S1-S5.Test result is as shown in table 1.
2, crystal-silicon solar cell aluminum conductive electric slurry performance test:
Aluminum conductive electric slurry S10-S50 and DS10-DS30 prepared by embodiment 1-5 and comparative example 1-3 adopts 280 order web plate silk screen printings respectively on monocrystalline silicon piece, monocrystalline silicon piece specification: 125 × 125mm, and before corrosion, thickness is 200 μm, and before printing, thickness is 180 μm.Printing weight is every sheet slurry 1.3g, and bake out temperature is 135 DEG C, and drying time is 4min, and proceed to continuous tunnel furnace sintering, preheating temperature is 350-500 DEG C, and sintering time is 55s, and peak temperature is 915 DEG C, and the time is 2s; Obtain solar battery sheet after coming out of the stove, be designated as S11-S55 and DS11-DS33 successively.
(1) estimate cell piece aluminium film surface situation, smooth surface, does not play aluminium pill, without blistering, being designated as OK, otherwise being designated as NG;
(2) sticking power test: soak solar battery sheet 7 days with tap water under room temperature, aluminium film does not come off, gently scrapes aluminium film with blunt and does not still come off and be designated as OK, otherwise be designated as NG;
(3) water boiling resistance performance test: dropped into by cell piece in the hot water of 75 DEG C and soak 15min, aluminium film surface does not produce bubble, before and after poach, aluminium film outward appearance is without considerable change, is designated as OK, otherwise is designated as NG;
(4) electricity conversion test: method adopts single flash operation simulator to test solar battery sheet disclosed in IEC904-1, and test condition is standard test condition (STC): light intensity: 1000W/m 2; Spectrum: AM1.5; Temperature: 25 DEG C, records the electricity conversion of each solar battery sheet.
Test result is as shown in table 2.
Table 1
Test item S1 S2 S3 S4
Median particle diameter D 50 1.50μm 1.51μm 1.52μm 2.18μm
Beginning fusing point 600℃ 595℃ 595℃ 610℃
Table 2
From the test result of upper table 1, the median particle diameter of the unorganic glass powder adopting frit composition of the present invention to obtain is 0.2-3 μm, and the beginning fusing point of described unorganic glass powder is 580-620 DEG C.
From the test result of upper table 2, adopt the cell piece of crystal-silicon solar cell aluminum conductive electric slurry provided by the invention at maintenance electricity conversion higher than under the prerequisite of more than 18.20%, aluminium film surface is smooth, do not play aluminium pill, do not blister, aluminium film and monocrystalline silicon piece sticking power high, there is higher water boiling resistance performance simultaneously.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (14)

1. a frit composition, is characterized in that, containing following component: Bi in described frit composition 2o 335-60 weight part, B 2o 310-30 weight part, SiO 210-20 weight part, CaO 1-5 weight part, MgO 0.5-5 weight part, Al 2o 30-5 weight part;
Also containing Sb in described frit composition 2o 3, Sb 2o 5and nitrate, Sb 2o 3with Sb 2o 5total content be 3-8 weight part, described nitrate is magnesium nitrate or nitrocalcite, and the content of described nitrate is Sb 2o 3the 0.5-1.5 of content doubly.
2. frit composition according to claim 1, is characterized in that, described Sb 2o 3and Sb 2o 5median particle diameter be 1.0-5.0 μm.
3. a unorganic glass powder, it is characterized in that, described unorganic glass powder is founded by frit composition according to claim 1 is first warming up to 500-600 DEG C, is then warming up to 1200-1300 DEG C and founds, shrend obtains granulated glass sphere after filtering, and then granulated glass sphere is carried out ball milling and obtains.
4. unorganic glass powder according to claim 3, is characterized in that, 500-600 DEG C of time of founding is 0.2-0.8h, 1200-1300 DEG C of time of founding is 0.5-2.5h.
5. unorganic glass powder according to claim 3, is characterized in that, described ball milling is dry grinded after comprising first wet-milling, and the wet-milling time is 5-8h, and the dry grinding time is 0. 2-1h.
6. unorganic glass powder according to claim 5, is characterized in that, during wet-milling, the mass ratio of zirconia ball, granulated glass sphere and deionized water is 4:0.8-1.2:0.5-0.8; During dry grinding, the mass ratio of zirconia ball and granulated glass sphere is 1:1.8-2.5.
7. a crystal-silicon solar cell aluminum conductive electric slurry, it is characterized in that, with the total mass of described crystal-silicon solar cell aluminum conductive electric slurry for benchmark, ball aluminum powder containing 70-80wt% in described crystal-silicon solar cell aluminum conductive electric slurry, the organic carrier of 10-25wt% and the unorganic glass powder of 1-5wt%; Wherein, described ball aluminum powder is the aluminium powder that Surface coating has aluminum oxide, and described unorganic glass powder is the unorganic glass powder described in any one of claim 3-6.
8. crystal-silicon solar cell aluminum conductive electric slurry according to claim 7, is characterized in that, described ball aluminum powder is atomizing aluminium powder, and the median particle diameter of described ball aluminum powder is 4.5-5.0 μm.
9. the crystal-silicon solar cell aluminum conductive electric slurry according to claim 7 or 8, is characterized in that, the thickness of the surface alumina oxide of described ball aluminum powder is 10-20nm.
10. crystal-silicon solar cell aluminum conductive electric slurry according to claim 7, is characterized in that, containing thickening material, auxiliary agent and organic solvent in described organic carrier; Described thickening material is selected from least one of ethyl cellulose, modified phenolic resins or epoxy resin; Described auxiliary agent is selected from least one in lubricant, thixotropic agent; Described organic solvent is selected from Terpineol 350, dibutyl phthalate, diethylene glycol monobutyl ether, turps, butyl glycol ether, diethylene glycol monobutyl ether acetic ester, ethylene glycol ether acetate, tributyl citrate, at least two kinds in butyl carbitol acetate, dibutyl phthalate, tributyl phosphate.
11. crystal-silicon solar cell aluminum conductive electric slurries according to claim 10, is characterized in that, described lubricant is hexadecanol, and described thixotropic agent is modified hydrogenated Viscotrol C or polyamide wax powder.
12. crystal-silicon solar cell aluminum conductive electric slurries according to claim 10, is characterized in that, described organic solvent is the mixture of Terpineol 350, ethylene glycol ether acetate and diethylene glycol monobutyl ether; With the organic solvent of 100 weight parts for benchmark, wherein the content of Terpineol 350 is 55-65 weight part, and the content of ethylene glycol ether acetate is 15-25 weight part, and the content of diethylene glycol monobutyl ether is 15-25 weight part.
The preparation method of 13. crystal-silicon solar cell aluminum conductive electric slurries according to claim 7, is characterized in that, comprises and ball aluminum powder and unorganic glass powder being scattered in proportion in organic carrier, namely obtains described crystal-silicon solar cell aluminum conductive electric slurry after grinding; Wherein, described ball aluminum powder is the aluminium powder that Surface coating has aluminum oxide, and described unorganic glass powder is the unorganic glass powder described in any one of claim 3-6.
14. preparation methods according to claim 13, is characterized in that, are ground to described crystal-silicon solar cell aluminum conductive electric slurry fineness < 20 μm.
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