CN103514973B - Conductive paste for solar cell and preparation method thereof - Google Patents
Conductive paste for solar cell and preparation method thereof Download PDFInfo
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- CN103514973B CN103514973B CN201210209770.8A CN201210209770A CN103514973B CN 103514973 B CN103514973 B CN 103514973B CN 201210209770 A CN201210209770 A CN 201210209770A CN 103514973 B CN103514973 B CN 103514973B
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Abstract
The invention provides a kind of conductive paste for solar cell and preparation method thereof, electrocondution slurry comprises conductive metal powder, inorganic binder and organic carrier, and described inorganic binder comprises at least two kinds of unorganic glass powder. The aluminium back surface field electrocondution slurry of preparation, silk-screen is on silicon chip and after sintering, the smooth densification of metallic diaphragm obtaining, outward appearance is good, without blistering phenomenon and metallic particles phenomenon, the fill factor, curve factor of battery is high, photoelectric transformation efficiency is high, meanwhile, and the strong adhesion of metal film and silicon chip, cell piece angularity is low, can test by water boiling resistance.
Description
Technical field
The invention belongs to technical field of solar batteries, relate in particular to a kind of conductive paste for solar cell and preparation thereofMethod.
Background technology
Day by day the increasingly sharpening of exhaustion, problem of environmental pollution that is accompanied by traditional energy, the development and application of new forms of energyThrough becoming human research's focus. Solar energy inexhaustible, green non-pollution is new energy development utilizationOne of emphasis.
Electrocondution slurry is the important materials of making silica-based solar cell. Silica-based solar cell generally passes through conductive pasteMaterial is printed on silicon substrate, then dry and sintering preparation back of the body electric field and electrode. Existing electrocondution slurry is mainly by functional powderBody (metal powder), unorganic glass powder, organic carrier mix and blend rolling form. Wherein, metal powder is generally as conductive phase, and oneAs be aluminium powder or silver powder, unorganic glass powder as inorganic binder, strengthens the adhesion of metal powder and silicon base in the time of sintered moltenPower.
At present the glass dust of commercial solar cell electrocondution slurry is generally by the oxide melting water of bismuth oxide, boron oxide classThe ball milling again of quenching forms, and generally only uses a kind of glass dust, the median particle diameter D of glass dust50Be generally 1.0 ~ 5.0 μ m, use amount is logical2 ~ the 10wt% that often accounts for whole formula, use amount is larger, and unorganic glass powder is non-conductor, thereby causes solar battery sheetSheet resistance is larger, and battery series resistance is large, has reduced the electricity conversion of battery, makes the photoelectric transformation efficiency of solar battery sheetDo not reach desirable requirement.
Summary of the invention
When the present invention is applied to solar cell in order to solve existing electrocondution slurry, the sheet resistance of solar battery sheet is still larger,The technical problem that electricity conversion is undesirable, provide that one can prepare that sheet resistance is lower, fill factor, curve factor is high, electricity conversionElectrocondution slurry of high solar battery sheet and preparation method thereof, the metal film angularity that simultaneously prepared by electrocondution slurry is low, can lead toCross water boiling resistance test, the smooth densification of metallic diaphragm, with the strong adhesion of silicon chip, outward appearance is good.
First object of the present invention is to provide a kind of conductive paste for solar cell, comprises conductive metal powder, inorganicBinding agent and organic carrier, described inorganic binder comprises at least two kinds of unorganic glass powder.
Second object of the present invention is to provide the preparation method of above-mentioned electrocondution slurry, and step comprises: by least two kinds of nothingsMachine glass dust and conductive metal powder are scattered in organic carrier, grind to obtain electrocondution slurry.
The present inventor surprisingly finds, adopts multiple different unorganic glass powder to mix and leads as used for solar batteriesThe inorganic binder of electricity slurry, can reduce the total amount of glass dust, the metal film not only making and the strong adhesion of silicon base, andAnd the metal film density making is high, and outward appearance is good, without blistering phenomenon and metallic particles phenomenon. The solar cell of preparation simultaneouslyThe sheet resistance of sheet is lower, fill factor, curve factor is high, electricity conversion is high. Infer that reason may be current crystal-silicon solar cell metalMetallization processes is generally: the silicon chip of screen printing sizing agent is in the time crossing tunnel sintering furnace, and whole continuous tunnel furnace has along the direct of travel of silicon chipMultiple (9 or more than) temperature province, silicon chip advances to peak temperature (generally at 900 ~ 930 DEG C) again to room temperature from room temperature, temperatureDegree graded scope is very large, and the time of whole process also about 2 minutes, and the physical property of single glass powder is difficult toAdapt to this temperature situation jumpy, for example single glass powder be just difficult to take into account aluminium powder fusion point (660 DEG C of left and right) itBefore and after fusion point aluminium powder melted to erosion effect. Single glass powder average coefficient of linear expansion is in aluminium back surface field electrocondution slurry group simultaneously(coefficient of expansion is 232 × 10 to Cheng Zhongyu metallic aluminium-7/ DEG C, 20 ~ 300 DEG C) and silicon (coefficient of expansion is 26 × 10-7/℃，20~300DEG C) widely different, be difficult to the difference of balance metallic aluminium and silicon chip, adopt multiple hybrid glass powder, can effectively reduce silicon chip-BoThermal expansion gradient between glass powder-aluminium powder, thus the angularity of battery reduced on a large scale. A large amount of glass dust is also found in research simultaneouslyCan cause the angularity of cell piece to increase, fragmentation rate rises, and the present invention can reduce the total amount of glass dust greatly, also can be furtherReduce the angularity of battery, improve yield, reduce costs.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction withEmbodiment, is further elaborated to the present invention. Should be appreciated that specific embodiment described herein is only in order to explainThe present invention, is not intended to limit the present invention.
The invention provides a kind of conductive paste for solar cell, comprise conductive metal powder, inorganic binder and organicCarrier, described inorganic binder comprises at least two kinds of unorganic glass powder. Can reduce the total amount of glass dust, the metal not only makingThe strong adhesion of film and silicon base, and the metal film density making is high, and outward appearance is good, existing without blister phenomenon and metallic particlesResemble. The sheet resistance of the solar battery sheet of preparation is lower simultaneously, fill factor, curve factor is high, electricity conversion is high.
Between different multiple unorganic glass powder, composition is different, can be that composition is completely different, selects the glass of different seriesPowder, for example, can select Pd system, Bi-B-Si glass frit etc., and the present invention preferably different multiple unorganic glass powder is Bi-B-Si glass frit, but component difference in Bi-B-Si glass frit can be contained inorganic oxide species differences, alsoCan be the percentage composition difference of contained inorganic oxide, the present invention preferably unorganic glass powder not of the same race be by different hundredDivide the inorganic oxide melting of content to form.
Preferably, taking the total amount of every kind of unorganic glass powder as benchmark, multiple unorganic glass powder independently comprises respectively
The Bi of 40 ~ 60wt%2O3, the B of 15-25wt%2O3, the SiO of 10 ~ 20wt%2, the Sb of 1 ~ 8wt%2O3，1.0~5.0wt%BaO, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%2O3. Inorganic by different percentage compositionsOxide is smelted into different unorganic glass powder. Further preferably, inorganic binder comprises the first unorganic glass powder and the second nothingMachine glass dust, wherein, taking the total amount of the first unorganic glass powder as benchmark, the first unorganic glass powder comprises the Bi of 40 ~ 50wt%2O3，The B of 20 ~ 25wt%2O3, the SiO of 15 ~ 20wt%2, the Sb of 1 ~ 8wt%2O3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, 0.2The CaO of ~ 3.0wt% and the Al of 0 ~ 3.0wt%2O3; Taking the total amount of the second unorganic glass powder as benchmark, the second unorganic glass powder comprisesThe Bi of 50 ~ 60wt%2O3, the B of 15 ~ 20wt%2O3, the SiO of 10 ~ 15wt%2, the Sb of 1 ~ 8wt%2O3, the BaO of 1.0 ~ 5.0wt%, 0.5The MgO of ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%2O3. Further preferably above-mentioned the first unorganic glass powder and theThe weight ratio of two unorganic glass powder is 1:0.5 ~ 2.0. In better situation, also preferably inorganic binder comprises that first is inorganicGlass dust, the second unorganic glass powder and the 3rd unorganic glass powder, wherein, taking the total amount of the first unorganic glass powder as benchmark, firstUnorganic glass powder comprises the Bi of 40 ~ 50wt%2O3, the B of 20 ~ 25wt%2O3, the SiO of 15 ~ 20wt%2, the Sb of 1 ~ 8wt%2O3，1.0~The BaO of 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%2O3; With the second unorganic glass powderTotal amount be benchmark, the second unorganic glass powder comprises the Bi of 50 ~ 55wt%2O3, the B of 15 ~ 20wt%2O3, the SiO of 13 ~ 15wt%2，1~The Sb of 8wt%2O3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%2O3；Taking the total amount of the 3rd unorganic glass powder as benchmark, the 3rd unorganic glass powder comprises the Bi of 55 ~ 60wt%2O3, the B of 15 ~ 20wt%2O3，The SiO of 10 ~ 13wt%2, the Sb of 1 ~ 8wt%2O3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% andThe Al of 0 ~ 3.0wt%2O3. Further preferably, the weight of the first unorganic glass powder: the weight of the second unorganic glass powder: the 3rd is inorganicThe weight of glass dust is 1:0.5 ~ 2.0:0.5 ~ 2.0.
Preferably, the median particle diameter D of multiple unorganic glass powder50Be independently respectively 0.1 ~ 1.0 μ m, multiple unorganic glass powderParticle diameter can be the same or different, the median particle diameter difference of preferred multiple unorganic glass powder, further improve conductive metal powder,The intergranular interaction such as glass dust, makes filling effect better. The present invention surprisingly finds to adopt particle diameter to be less than 1 micron multipleThe mixed powder of glass dust, the metal film square resistance forming after silk-screen sintering is less, and the series resistance of cell piece is lower, and photoelectricity turnsChange efficiency higher, meanwhile, the adhesive force of metal film and silicon chip is fine, and the angularity of cell piece is little, can test by water boiling resistance. Push awaySurveying reason may be for being the relation of particle diameter cube according to spheroid mass, and particle diameter diminishes, and powder number number becomes cube exponent increase.Fall the aluminium oxide on aluminium powder surface with glass dust molten corrosive, aluminium simple substance is at high temperature infiltrated in silicon chip, form silico-aluminum layer to beExample, in theory, glass dust spheroid can form effective corrosion to eight ball aluminum powder around, reduces the volume of single glass dust(reducing particle diameter) scheme can effectively reduce total consumption of glass dust, thereby reduces non-conductor glass dust to solar battery sheetThe impact of sheet resistance, particle diameter of the present invention also can further avoid glass dust to exaggerate to the corrosion of aluminium oxide simultaneously, avoids aluminium filmPoach only.
Preferably, the softening point temperature Ts of multiple unorganic glass powder is independently 500 ~ 600 DEG C respectively, average coefficient of linear expansionBe independently respectively 50 × 10-7~100×10-7/ DEG C, proportion is independently respectively 3.0 ~ 4.0g/cm3, generally inorganic glass not of the same raceThe physical parameter differences such as the softening point temperature Ts of glass powder, average coefficient of linear expansion, proportion, by preferred multiple softening point temperatureThe further balance electrocondution slurry of unorganic glass powder of Ts, average coefficient of linear expansion, proportion is various in the time of solar battery sheet sinteringThe variation of situation, makes performance the best of solar battery sheet.
Preferably, taking the total amount of electrocondution slurry as benchmark, described electrocondution slurry comprises the conductive metal powder of 75 ~ 79wt%, 0.1 ~The inorganic binder of 1.0wt% and the organic carrier of 20 ~ 24wt%. Wherein, the consumption of non-conductor inorganic binder is few, only needsCan reach the preparation requirement of solar cell less than 1.0wt%, the metallic diaphragm strong adhesion of preparation, and metal film densityHeight, outward appearance is good, without blistering phenomenon and metallic particles phenomenon.
Preferably, conductive metal powder is aluminium powder, and wherein, aluminium powder comprises the spherical aluminium of two or more different median particle diametersPowder, the median particle diameter D of the ball aluminum powder of multiple different median particle diameters50Be independently respectively 1.0 ~ 8.0 μ m. Not only further optimizeDensity degree and the outward appearance of metal film, and can optimize the interaction between conducting metal powder, reduce bulk resistor.
The preferred ball aluminum powder of the present invention is nucleocapsid structure, and kernel is aluminium simple substance, and shell is aluminium oxide. Under preferable case, ballThe thickness of the surface alumina oxide of shape aluminium powder is 10-20nm, further optimizes the interaction between itself and glass dust, further optimizesThe performance of solar battery sheet.
Organic carrier is organic system conventional in the electrocondution slurry of prior art, taking the total amount of organic carrier as benchmark,Specifically can be preferred, organic carrier comprises the ethyl cellulose of 5.0 ~ 20wt%, the auxiliary agent of 0.1 ~ 5.0wt% and the mixing of 75 ~ 90wt%Solvent; Described auxiliary agent be one or more mixing in polyamide powder, modified hydrogenated castor oil, hexadecanol or 18 alcohol andBecome; Described mixed solvent is by terpinol, dibutyl phthalate (DBP), BC, turpentine oil, butyl glycol ether, fourthTwo or more in base carbitol acetate, ethylene glycol ether acetate, ATBC and tributyl phosphate mixesClose and form. Also can contain other property-modifying additives, the present invention is not particularly limited, and can select according to actual conditions. CanAlso can configure voluntarily with commercial, collocation method can be dissolved in by terpinol or other organic by ethyl cellulose and auxiliary agentIn the mixed solvent that solvent forms, at 60 ~ 80 DEG C, make it fully dissolve and stir, obtain having of transparent homogeneous airborneBody.
Meanwhile, the invention provides the preparation method of above-mentioned conductive paste for solar cell, step comprises: by least twoPlant unorganic glass powder and conductive metal powder and be scattered in organic carrier, grind to obtain electrocondution slurry, method is simple and easy to realize.
Be scattered in organic carrier and adopt and well known to a person skilled in the art various process for dispersing, can be by conductive metal powderAnd multiple glass dust adds in organic carrier and mix respectively, after also can mixing in whole or in part, add together in organic carrierMix, can once add, also can add in batches, the present invention does not limit, the method adding and the method the present invention who mixesRestriction, in the time that conductive metal powder is selected the ball aluminum powder of multiple particle diameter, is not specifically as follows selected in better situationThe ball aluminum powder of multiple glass dust and multiple particle diameter adopts respectively V-Mixer to mix, and obtains hybrid glass powder and mixingAluminium powder, is placed in organic carrier the stainless cylinder of steel of high speed dispersor, stirs on one side, adds hybrid glass powder on one side, stirs evenly; PointRepeatedly add mixing aluminium powder, add first and stir evenly at every turn, then add next time; After all adding, stir evenly at a high speed; Use againThreeRoller mill grinds 15 ~ 20 times, and fineness of grind, to < 20 μ m, can make aluminium back surface field electrocondution slurry.
Preferably, at least two kinds of unorganic glass powder pass through the inorganic oxide of the different component of every kind of unorganic glass powder of compositionMelting forms. In better situation, preferably the inorganic oxide of every kind of unorganic glass powder of composition is mixed, at 550 ~ 600 DEG C, protectTemperature 0.5 ~ 1h, after at 1250 ~ 1300 DEG C, be incubated 1 ~ 2h, rear shrend obtains every kind of unorganic glass powder. Mix and adopt art technologyThe known various mixed methods of personnel, for example, adopt V-Mixer that the oxide powder of every kind of unorganic glass powder of each composition is mixedClose evenly. Insulation can adopt and well known to a person skilled in the art various sintering furnaces, for example, can put into corundum crucible, juxtapositionIn silicon carbide rod furnace, will in silicon carbide rod furnace, be warming up to 550 ~ 600 DEG C, insulation 0.5 ~ 1h, then be warming up to 1250 ~ 1300 DEG C, insulation 1~ 2h. After general shrend, obtain bead, bead is separated, the rear glass dust of pulverizing to obtain, the method for separation adopts this area skillThe known various separation methods of art personnel, for example, filter.
Preferably, the method for pulverizing, for dry grinding, is specifically as follows in better situation and packs bead into ball grinder, in mass ratioZirconia ball: bead: deionized water=4:0.5 ~ 2:0.5 ~ 1.5,300 ~ 400 revs/min of tank speed, wet-milling 6 ~ 8h, dries after filteringDry, then the 0.5 ~ 3h that dry grinds, when dry grinding, the mass ratio of zirconia ball and glass dust is 1:1 ~ 3. Optimize the particle diameter of glass dust, improve and burnKnot is active and softening point is low.
Below by specific embodiment, the invention will be further described.
Embodiment 1
The present embodiment is used for preparing aluminium back surface field electrocondution slurry.
(1) preparation of unorganic glass powder
Get the Bi of 49wt%2O3, the B of 25wt%2O3, the SiO of 16wt%2, the Sb of 4wt%2O3, the BaO of 2.0wt%, 2.0wt%'sThe CaO of MgO, 1.0wt%, the Al of 1.0wt%2O3, adopt V-Mixer to mix, pack in porcelain crucible, put into silicon carbide rod furnace,Intensification is preheating to 550 DEG C, insulation 0.5h, then rise to 1250 DEG C, and melting 1.0h, shrend is filtered, and will obtain bead and pack ball milling intoTank, controls mass ratio, zirconia ball: bead: deionized water=4:1:0.5, tank speed 100/ minute, wet-milling ball milling 7h, mistakeFilter, dries, then the 2.5h that dry grinds, and when dry grinding, the mass ratio of zirconia ball and bead is 1:2, makes unorganic glass powder A11.
Adopt BT-2003 type laser fineness gage (Dandong Bai Te company produces, lower same), adopt water as dispersionMedium, records the median particle diameter D of the unorganic glass powder A11 of above-mentioned preparation50Be 0.65 μ m, proportion (adopt the test of 10ml specific gravity bottle,Lower same) be 3.65g/cm3, softening point (adopt Germany to produce STA449PC/STA409PC simultaneous thermal analysis instrument and carry out DTA test, underWith) be 588 DEG C, average coefficient of linear expansion (adopts thermomechanical analyzer to test, temperature range: be warmed up to tested from 20 DEG CThe fusing of examination glass dust, lower same) DEG C) be 57 × 10-7/℃。
Get the Bi of 59wt%2O3, the B of 19wt%2O3, the SiO of 12wt%2, the Sb of 5wt%2O3, the BaO of 3.0wt%, 1.0wt%'sThe CaO of MgO and 1.0wt%. The manufacture craft of glass dust is identical with A11 unorganic glass powder, makes unorganic glass powder A12. Record itMedian particle diameter D50Be 0.64 μ m, proportion is 3.23g/cm3, softening point is 532 DEG C, average coefficient of linear expansion is 84 × 10-7/℃。
Adopt V-Mixer by unorganic glass powder A11 and A12,1:1 mixes in mass ratio, obtains hybrid glass powderA1。
(2) configuration of organic carrier
According to quality than terpinol: BC: BC acetate=50:40:10 mixes organic solvent allEven, the mixed solvent of composition electrocondution slurry. Taking organic carrier total amount as benchmark, get the mixed solvent of 89.5wt%, add 8.8wt%Ethyl cellulose STD-4 (Tao Shi produces, and viscosity is 4), the rilanit special of 1.2wt%, 0.5wt% 18 alcohol, are heated to 65 DEG C, makeIt fully dissolves, and stirs, and obtains the organic carrier solution of homogeneous clarification.
(3) preparation of electrocondution slurry
Get and account for electrocondution slurry total amount 63wt%, median particle diameter D50Be 5.0 ~ 6.0 μ m and account for slurry total amount 15wt%, middle particle diameterD50Be that (ocean, Henan Chinalco produces common aluminium powder, aluminium oxide for the ball aluminum powder of two kinds of different median particle diameters of 1.0 ~ 2.0 μ mThickness is at 13 ~ 15nm) be mixed to get mixing aluminium powder. Get again the above-mentioned organic carrier solution that accounts for electrocondution slurry total amount 21.40wt%,Be placed in the stainless cylinder of steel of high speed dispersor, stir on one side, add the above-mentioned hybrid glass making that accounts for total amount 0.60wt% on one sidePowder A1, stirs, and then adds mixing aluminium powder obtained above, and wherein aluminium powder adds several times, and add first and stir evenly at every turn, thenAdd next time; After all adding, stir evenly at a high speed; Grind 15 times with three-roll grinder again, detect and make its fineness be less than 20 μ m,Obtain aluminium back surface field electrocondution slurry sample S1.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S2, different is unorganic glass powder A11 and nothingThe mass ratio of machine glass dust A12 is 1:0.5, makes hybrid glass powder A2, adopts hybrid glass powder A2 to make aluminium back surface field conductive pasteMaterial S2.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S3, different is unorganic glass powder A11 and nothingThe mass ratio of machine glass dust A12 is 1:2, makes hybrid glass powder A3, adopts hybrid glass powder A3 to make aluminium back surface field electrocondution slurryS3。
Embodiment 4
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S4, different is unorganic glass powder A11 and nothingThe mass ratio of machine glass dust A12 is 1:4, makes hybrid glass powder A4, adopts hybrid glass powder A4 to make aluminium back surface field electrocondution slurryS4。
Embodiment 5
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S5, different is in the preparation of electrocondution slurryThe amount of the hybrid glass powder A1 adding is 1.00wt%, and the amount of organic carrier is 21.00wt%.
Embodiment 6
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S6, different is in the preparation of electrocondution slurryThe amount of the hybrid glass powder A1 adding is 0.10wt%, and the amount of organic carrier is 21.90wt%.
Embodiment 7
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S7, different is two kinds of unorganic glass powderIn preparation, the dry grinding time is 1.5h, makes unorganic glass powder A71, A72, adopts the method identical with embodiment 1 to record inorganicThe particle diameter of glass dust A71, A72 is 0.96 μ m, by unorganic glass powder A71 and A72 in mass ratio 1:1 be mixed to get hybrid glass powderA7, adopts hybrid glass powder A7 to make aluminium back surface field electrocondution slurry S7.
Embodiment 8
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S8, different employing hybrid glass powder A8 systemsObtain aluminium back surface field electrocondution slurry S8, wherein hybrid glass powder A8 adopts V-Mixer by unorganic glass powder A81, A82 and A83, by matterAmount mixes and makes than 1:1:1.
Wherein, get the Bi of 47wt%2O3, the B of 24wt%2O3, the SiO of 17wt%2, the Sb of 5.0wt%2O3, the BaO of 3.0wt%,The MgO of 2.0wt% and the CaO of 2.0wt%. The manufacture craft of glass dust is identical with A11 unorganic glass powder, and wet-milling Ball-milling Time is8h, makes unorganic glass powder A81. Record its median particle diameter D50Be 0.48 μ m, proportion is 3.28g/cm3, softening point is 582 DEG C,Average coefficient of linear expansion is 51 × 10-7/℃。
Get the Bi of 53.5wt%2O3, the B of 19wt%2O3, the SiO of 14.5wt%2, the Sb of 6.0wt%2O3, the BaO of 3.0wt%,The MgO of 2.0wt% and the CaO of 1.0wt%, the Al of 1.0wt%2O3. The manufacture craft of glass dust is identical with inorganic A11 glass dust, wetAbrading-ball time consuming, for 7h, makes unorganic glass powder A82. Record its median particle diameter D50Be 0.65 μ m, proportion is 3.64g/cm3, softChanging point is 550 DEG C, and average coefficient of linear expansion is 65 × 10-7/℃。
Get the Bi of 59wt%2O3, the B of 17wt%2O3, the SiO of 12wt%2, the Sb of 5wt%2O3, the BaO of 3.0wt%, 2.0wt%'sMgO, the CaO of 2.0wt%. The manufacture craft of glass dust is identical with inorganic A11 glass dust, and wet-milling Ball-milling Time is 6h, makes inorganicGlass dust A83. Record its median particle diameter D50Be 0.87 μ m, proportion is 3.87g/cm3, softening point is 522 DEG C, average line expands and isNumber is 83 × 10-7/℃。
Comparative example 1
Adopt the method identical with embodiment 1 to prepare unorganic glass powder A11, organic carrier, different is electrocondution slurryPreparation: get and account for electrocondution slurry total amount 63wt%, median particle diameter D50Be 5.0 ~ 6.0 μ m and account for slurry total amount 15wt%, middle particle diameter D50For(ocean, Henan Chinalco produces common aluminium powder to the ball aluminum powder of two kinds of different median particle diameters of 1.0 ~ 2.0 μ m, aluminium oxide thicknessAt 13 ~ 15nm) be mixed to get mixing aluminium powder. Get again the above-mentioned organic carrier solution that accounts for electrocondution slurry total amount 20.70wt%, be placed inIn the stainless cylinder of steel of high speed dispersor, stir on one side, add the unorganic glass powder A11 that accounts for total amount 1.30wt% on one side, stir allEven, then add mixing aluminium powder obtained above, wherein aluminium powder adds several times, adds first and stirs evenly at every turn, then add next time; EntirelyAfter portion adds, stir evenly at a high speed; Grind 15 times with three-roll grinder again, detect and make its fineness be less than 20 μ m, obtain aluminium back surface field and leadElectricity slurry sample DS1.
Comparative example 2
(1) preparation of unorganic glass powder
Get the Bi of 55wt%2O3, the B of 22wt%2O3, the SiO of 17wt%2, the Sb of 2.0wt%2O3, the Al of 2.0wt%2O3，The ZnO of 1.0wt%, the CaO of 1wt%, adopts V-Mixer to mix, and packs in porcelain crucible, puts into silicon carbide rod furnace, heats up pre-Heat, to 550 DEG C, is incubated 0.5h, then rises to 1250 DEG C, melting 1.0h, and shrend is filtered, and will obtain bead and pack ball grinder into, controlsMass ratio, zirconia ball: bead: deionized water=4:1:0.5, tank speed 100/ minute, wet-milling ball milling 5.5h, filters, and driesDry, then the 1.0h that dry grinds, when dry grinding, the mass ratio of zirconia ball and bead is 1:2, makes unorganic glass powder D2.
Record the median particle diameter D of the unorganic glass powder D2 of above-mentioned preparation50Be 1.45 μ m, proportion is 3.47g/cm3, softening pointBe 605 DEG C, average coefficient of linear expansion is 43 × 10-7/℃。
(2) configuration of organic carrier
Adopt the method identical with embodiment 1 to prepare organic carrier.
(3) preparation of electrocondution slurry
Get and account for electrocondution slurry total amount 76wt%, median particle diameter D50Be ball aluminum powder (ocean, the Henan Aluminum public affairs of 4.0 ~ 5.0 μ mDepartment produces common aluminium powder, and aluminium oxide thickness is at 13 ~ 15nm), then get that to account for the above-mentioned organic carrier of electrocondution slurry total amount 21.5wt% moltenLiquid, is placed in the stainless cylinder of steel of high speed dispersor, stirs on one side, adds the above-mentioned inorganic glass making that accounts for total amount 2.5wt% on one sideGlass powder D2, stirs, and then adds aluminium powder above, and wherein aluminium powder adds several times, adds first and stirs evenly at every turn, then add nextInferior; After all adding, stir evenly at a high speed; Grind 15 times with three-roll grinder again, detect and make its fineness be less than 20 μ m, obtain the aluminium back of the bodyField electrocondution slurry sample DS2.
Comparative example 3
Adopt the method identical with comparative example 2 to prepare unorganic glass powder D2, organic carrier, different is the system of electrocondution slurryStandby: to get and account for electrocondution slurry total amount 63wt%, median particle diameter D50Be 5.0 ~ 6.0 μ m and account for slurry total amount 15wt%, middle particle diameter D50For(ocean, Henan Chinalco produces common aluminium powder to the ball aluminum powder of two kinds of different median particle diameters of 1.0 ~ 2.0 μ m, aluminium oxide thicknessAt 13 ~ 15nm) be mixed to get mixing aluminium powder. Get again the above-mentioned organic carrier solution that accounts for electrocondution slurry total amount 21.40wt%, be placed inIn the stainless cylinder of steel of high speed dispersor, stir on one side, add the unorganic glass powder D2 that accounts for total amount 0.60wt% on one side, stir,Then add mixing aluminium powder obtained above, wherein aluminium powder adds several times, adds first and stirs evenly at every turn, then add next time; AllAfter adding, stir evenly at a high speed; Grind 15 times with three-roll grinder again, detect and make its fineness be less than 20 μ m, obtain aluminium back surface field conductionSlurry sample DS3.
Performance test
The solar battery aluminum back of the body electric field electrocondution slurry S1-S8 that above-described embodiment 1-8 and comparative example 1-3 are made andDS1-DS3 is used for respectively preparing solar battery sheet. Polysilicon chip specification: 156 × 156mm, before thickness is 200 μ m(corrosion),Before printing, thickness is 180 μ m. First adopt 200 object serigraphy back silver electrode slurrys (PV505 of Du Pont), dry, then adopt280 object meshcounts print respectively S1-S8 and DS1-DS3, printing weight be every with slurry 1.5 grams, bake out temperature is 125DEG C, drying time is 4min, then adopts 200 object serigraphy front silver electrode pastes (16C of Du Pont), crosses continuous tunnel furnace and dries burningKnot, continuous tunnel furnace temperature gradient distribution, the time that crosses continuous tunnel furnace is 2min, and sintering peak temperature is 910 ± 10 DEG C, and the time is a 1s left sideThe right side, obtains corresponding cell piece and is designated as respectively S10-S80 and DS10-DS30 after coming out of the stove.
Adopt respectively 200 cell pieces to test, test obtains data and gets its mean value.
Surface appearance: estimate the back surface field surface appearance of each solar cell piece, smooth, without aluminium pill or metallic particles, without blistering,Be designated as OK, otherwise be designated as NG.
Water boiling resistance test: cell piece dropped in the hot water of 70 ~ 80 DEG C and stop 10 ~ 15min, whether observing aluminium film surfaceReact with water and produce bubble, and before and after observing poach, whether aluminium film outward appearance there is significant change. If do not produced bubble, and outward appearance withoutSignificant change, is designated as OK, otherwise is designated as NG.
Adhesive force: photovoltaic glass, EVA, cell piece, EVA and TPT are stacked in order, and carry out lamination, use graduating with cutter 1cmWide is rectangular, uses mountain degree SH-100 pull and push dynamometer, along 45 ° of directions, it is carried out to tensile test, surveys average on its unit widthPeeling force, unit is N/cm.
Flexibility: by each solar cell piece degree of crook vernier caliper measurement, unit is mm.
Fill factor, curve factor, electricity conversion: adopt single flash operation simulator according to the disclosed method of IEC904-1 to each electricityPond sheet carries out electrochemical property test. Test condition is standard test condition (STC): light intensity: 1000W/m2; Spectrum: AM1.5;Temperature: 25 DEG C.
Test result is as table 1.
Table 1
As can be seen from the table, the aluminium back surface field electrocondution slurry that adopts hybrid glass powder of the present invention to prepare, silk-screen is at silicon chipAfter upper and sintering, the smooth densification of metallic diaphragm obtaining, outward appearance is good, without blistering phenomenon and metallic particles phenomenon, the filling out of batteryFill the factor high, photoelectric transformation efficiency is high, meanwhile, the strong adhesion of metal film and silicon chip, cell piece angularity is low, can be by water-fastBoil test.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all in essence of the present inventionAny amendment of doing within god and principle, be equal to replacement and improvement etc., within protection scope of the present invention all should be included in.
Claims (16)
1. a conductive paste for solar cell, is characterized in that, comprises conductive metal powder, inorganic binder and has airborneBody, described inorganic binder comprises at least two kinds of unorganic glass powder; It is glass that multiple described unorganic glass powder is Bi-B-SiPowder, unorganic glass powder not of the same race is prepared from by the inorganic oxide of different component; With the total amount of every kind of unorganic glass powderFor benchmark, multiple unorganic glass powder independently comprises respectively the Bi of 40～60wt%2O3, the B of 15～25wt%2O3，10～The SiO of 20wt%2, the Sb of 1～8wt%2O3, the BaO of 1.0～5.0wt%, the MgO of 0.5～5.0wt%, 0.2～3.0wt%CaO and the Al of 0～3.0wt%2O3。
2. electrocondution slurry according to claim 1, is characterized in that, the composition difference between multiple described unorganic glass powder.
3. electrocondution slurry according to claim 1, is characterized in that, the median particle diameter D of multiple unorganic glass powder50Respectively solelyThat vertical is 0.1～1.0 μ m.
4. electrocondution slurry according to claim 1, is characterized in that, the softening point temperature Ts of multiple unorganic glass powder respectivelyBe independently 500～600 DEG C, average coefficient of linear expansion is independently respectively 50 × 10-7～100×10-7/ DEG C, proportion is respectively solelyThat vertical is 3.0～4.0g/cm3。
5. electrocondution slurry according to claim 1, is characterized in that, described inorganic binder comprises the first unorganic glass powderWith the second unorganic glass powder, taking the total amount of the first unorganic glass powder as benchmark, described the first unorganic glass powder comprises 40～The Bi of 50wt%2O3, the B of 20～25wt%2O3, the SiO of 15～20wt%2, the Sb of 1～8wt%2O3, 1.0～5.0wt%'sBaO, the MgO of 0.5～5.0wt%, the CaO of 0.2～3.0wt% and the Al of 0～3.0wt%2O3；
Taking the total amount of the second unorganic glass powder as benchmark, described the second unorganic glass powder comprises the Bi of 50～60wt%2O3，15～The B of 20wt%2O3, the SiO of 10～15wt%2, the Sb of 1～8wt%2O3, the BaO of 1.0～5.0wt%, 0.5～5.0wt%'sMgO, the CaO of 0.2～3.0wt% and the Al of 0～3.0wt%2O3。
6. electrocondution slurry according to claim 5, is characterized in that, described the first unorganic glass powder and the second unorganic glassThe weight ratio of powder is 1:0.5～2.0.
7. electrocondution slurry according to claim 1, is characterized in that, described inorganic binder comprises the first unorganic glassPowder, the second unorganic glass powder and the 3rd unorganic glass powder, taking the total amount of the first unorganic glass powder as benchmark, described the first inorganic glassGlass powder comprises the Bi of 40～50wt%2O3, the B of 20～25wt%2O3, the SiO of 15～20wt%2, the Sb of 1～8wt%2O3，1.0The BaO of～5.0wt%, the MgO of 0.5～5.0wt%, the CaO of 0.2～3.0wt% and the Al of 0～3.0wt%2O3；
Taking the total amount of the second unorganic glass powder as benchmark, described the second unorganic glass powder comprises the Bi of 50～55wt%2O3，15～The B of 20wt%2O3, the SiO of 13～15wt%2, the Sb of 1～8wt%2O3, the BaO of 1.0～5.0wt%, 0.5～5.0wt%'sMgO, the CaO of 0.2～3.0wt% and the Al of 0～3.0wt%2O3；
Taking the total amount of the 3rd unorganic glass powder as benchmark, described the 3rd unorganic glass powder comprises the Bi of 55～60wt%2O3，15～The B of 20wt%2O3, the SiO of 10～13wt%2, the Sb of 1～8wt%2O3, the BaO of 1.0～5.0wt%, 0.5～5.0wt%'sMgO, the CaO of 0.2～3.0wt% and the Al of 0～3.0wt%2O3。
8. electrocondution slurry according to claim 7, is characterized in that, the weight of described the first unorganic glass powder: the second nothingThe weight of machine glass dust: weight 1:0.5～2.0:0.5～2.0 of the 3rd unorganic glass powder.
9. electrocondution slurry according to claim 1, is characterized in that, taking the total amount of electrocondution slurry as benchmark, and described conductionSlurry comprises the conductive metal powder of 75～79wt%, and having of the inorganic binder of 0.1～1.0wt% and 20～24wt% is airborneBody.
10. electrocondution slurry according to claim 1, is characterized in that, described conductive metal powder is aluminium powder, described aluminium powder bagDraw together the ball aluminum powder of two or more different median particle diameters, the median particle diameter D of the ball aluminum powder of multiple different median particle diameters50Be independently respectively 1.0～8.0 μ m.
11. electrocondution slurries according to claim 10, is characterized in that, described ball aluminum powder is nucleocapsid structure, and kernel isAluminium simple substance, shell is aluminium oxide, the thickness of described aluminium oxide is 10～20nm.
12. electrocondution slurries according to claim 1, is characterized in that, taking the total amount of organic carrier as benchmark, described organicCarrier comprises the ethyl cellulose of 5.0～20wt%, the auxiliary agent of 0.1～5.0wt% and the mixed solvent of 75～90wt%; DescribedAuxiliary agent is that one or more in polyamide powder, modified hydrogenated castor oil, hexadecanol or 18 alcohol mix; Described mixingSolvent is by terpinol, dibutyl phthalate (DBP), BC, turpentine oil, butyl glycol ether, BC vinegarTwo or more in acid esters, ethylene glycol ether acetate, ATBC and tributyl phosphate mixes.
The preparation method of 13. 1 kinds of conductive paste for solar cell as claimed in claim 1, is characterized in that, step bagDraw together: at least two kinds of unorganic glass powder and conductive metal powder are scattered in organic carrier, grind to obtain electrocondution slurry.
14. preparation methods according to claim 13, is characterized in that, described at least two kinds of unorganic glass powder pass through groupBecome the inorganic oxide melting of the different component of every kind of unorganic glass powder to form.
15. preparation methods according to claim 14, is characterized in that, by the inorganic oxide of every kind of unorganic glass powder of compositionThing mixes, and at 550～600 DEG C, is incubated 0.5～1h, after at 1250～1300 DEG C, be incubated 1～2h, rear shrend, pulverize oftenPlant unorganic glass powder.
16. preparation methods according to claim 15, is characterized in that, the method for described pulverizing is dry grinding.
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