CN102368411B - Preparation method of aluminum-boron alloy powder and aluminum-boron slurry of crystalline silicon cell - Google Patents
Preparation method of aluminum-boron alloy powder and aluminum-boron slurry of crystalline silicon cell Download PDFInfo
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Abstract
The invention relates to a preparation method of an aluminum-boron alloy powder and aluminum-boron slurry of a crystalline silicon cell. The preparation method comprises the following special implementation steps of: carrying out reduction reaction and gas atomization on a boron compound in molten liquid aluminum to prepare the aluminum-boron alloy; and mixing 72-82% of aluminum-boron alloy powder by mass, 0.1-10% of inorganic glass adhesion agent by mass, 15-25% of organic adhesion agent by mass and 1-5% of additive to prepare the aluminum-boron slurry. In a back surface field of the crystalline silicon cell which is prepared from the aluminum-boron slurry in the invention, a p-type doping concentration is one order of magnitude more than the p-type doping concentration of the back surface field prepared from the normal aluminum slurry at the same temperature, so that the inactivation effect on the back surface of the crystalline silicon cell is more excellent; and meanwhile, serial-connection resistance of the cell is reduced so that the photoelectric conversion efficiency of the solar cell is improved.
Description
Technical field
The present invention relates to a kind of preparation method of the aluminium boron slurry of processing by aluminum-boron alloy powder, unorganic glass binding agent, organic binder bond and additive; This aluminium boron slurry is mainly used in the back of the body surface field and the back electrode of preparation crystalline silicon (p type) solar cell; Also can be used for the n type crystalline silicon and prepare the pn knot, belong to crystal silicon solar energy battery manufacturing technology field.
Background technology
Solar energy distributes extensively, is a kind of nexhaustible clean energy resource, and solar cell is an electric energy with conversion of solar energy.At present, the whole world is crystal silicon solar energy battery above 80% solar cell, and the photoelectric conversion efficiency that further improves crystal silicon solar energy battery has huge social and economic benefit.
The mechanism of power generation of crystal silicon solar energy battery mainly depends on the pn knot, and p type and n type silicon realize through doping process that mainly doping process is that preparation has one of critical process of high-photoelectric transformation efficiency solar cell.The main doped chemical of p type crystalline silicon is the 3rd major element such as boron (B), aluminium (Al), gallium (Ga) etc.; The doped chemical of n type crystalline silicon is the 5th major element such as phosphorus (P), arsenic (As), antimony (Sb) etc., generally is doped to the master with P elements in the production.
The crystal silicon chip that is used for crystal silicon solar energy battery at present generally is a p type crystalline silicon sheet of mixing the B element, and wherein the doping content of B is usually less than 1 x 10
16Atoms/cm
3(every cubic centimetre atom number); The front surface of crystal silicon chip (phototropic face) forms the n+ type through under 850 ℃ temperature, carrying out phosphorous diffusion; Back of the body surface at crystal silicon chip then forms p+ type back of the body surface field (also claiming back of the body field) through the aluminium doping, so in fact p type crystalline silicon solar cell is exactly n+pp+ type structure.
In the back of the body surface field preparation technology of crystal silicon solar energy battery; Aluminium normally has certain thickness aluminium film at surface screen-printed one deck of crystalline silicon to the doping process of crystalline silicon; Carry out sintering then,, form aluminium-silicon eutectic between aluminium and the silicon when being heated to aluminium-silicon temperature of eutectic point (577 ℃) when above; Factors such as temperature, heat treatment time, aluminium film thickness confirm to generate the amount of aluminium-silicon eutectic, and temperature is confirmed the doping content of aluminium.Aluminium-silicon eutectic is in cooling procedure; Silicon is separated out from aluminium-silicon eutectic; And at the surface of crystalline silicon crystalline growth that does not fuse; A part of aluminium is stayed and is realized in the crystalline silicon lattice of separating out that aluminium mixes simultaneously, thereby obtains the p+ type crystalline silicon, and the doping content of aluminium is by the solid solubility decision of aluminium in crystalline silicon.Along with the further reduction of temperature, silicon is separated out crystallization from aluminium silicon eutectic more in cooling procedure.Under the heat treatment temperature of generally using in the current industry (750 ℃ ~ 820 ℃), the aluminium doping content that in crystalline silicon, can obtain is 2.8 x 10
18Atoms/cm
3Below, expect higher aluminium doping content, then need higher heat treatment temperature, and high treatment temperature there is destruction to the physical property of crystalline silicon, also consumes the more energy simultaneously, therefore in industry, is not used.
The theoretical maximum solid solution degree of boron in crystalline silicon is 6 * 10
20Atoms/cm
3, and the theoretical maximum solid solution degree of aluminium in crystalline silicon is 2 * 10
19Atoms/cm
-3, obviously, the solid solubility of boron in crystalline silicon is more much bigger than the solid solubility of aluminium in crystalline silicon.In general, the doping content that the element that solid solubility is high more can reach in crystalline silicon also will be high more.If in the process of above-mentioned preparation crystal silicon solar battery back surface field, can add the doping of boron element, so just can make under similar heat treatment temperature that the p property doping content in the crystalline silicon is significantly improved.But doped with boron often needs very high temperature in crystalline silicon, generally about 1000 ℃, carry out, and therefore very power consumption, the electrical property of crystalline silicon also is destroyed easily under such high temperature simultaneously.
Research paper (the P. Lolgen etc. that people such as Holland researcher Lolgen published on the international professional journals of periodical Applied Physics Letters by name in 1994; Boron doping of silicon using coalloy with aluminium; Applied Physics Letters; 1994 the 65th volumes, the 22nd phase, 2792-2794 page or leaf) in reported and in the commercial aluminum slurry that has prepared, added 1% pure boron powder; After mixing, adopt the aluminum slurry of screen printing technique, under 850 ℃ annealing temperature at this interpolation pure boron of monocrystalline silicon surface printing one deck powder; Through capacitance-voltage method (C-V) test, find that near the doping content of the boron of monocrystalline silicon surface reaches 3 * 10
19Atoms/cm
-3, and the resulting aluminium doping content of commercial aluminium paste that boron is not added in employing under similarity condition is 3 * 10
18Atoms/cm
-3Though both have all realized the effect that the p type mixes to crystalline silicon, obviously the former the p type doping content that obtains is 10 times of the latter.This result of study shows can be under relatively low temperature (adopt like people such as Lolgen 850 ℃) through aluminium silicon eutectic is that carrier is realized the doping of boron to crystalline silicon, and this result of study becomes the most important technical reference that solar-photovoltaic technology domain engineering technical staff development afterwards is used for the aluminium boron slurry of crystal silicon solar energy battery.
U.S. Ferro (translating into " Fu Lu " at home usually) company publication number at U. S. application in 2006 is that the publication number that US2007/0215202A1 patent and the said firm apply within Chinese territory the same year is to mention aluminium boron slurry in 101401189 patents; These two patents point out that mainly the boron source in its aluminium boron slurry is boron powder, boron alloy, boron salt, boric acid, organic metal boron, boron oxide compound and boron-containing glass, and the aluminium source is the alloy of aluminium or aluminium and boron, silicon, gallium, indium, antimony, tin, zinc and magnesium.The patent that the above-mentioned US publication of quoting is US2007/0215202A1 is also mentioned, and can to adopt the aluminum-boron alloy powder be that raw material prepares aluminium boron slurry, but any technology path or the process of preparation aluminum-boron alloy powder are not revealed or set forth to this patent.
Domestic 2011 disclosed publication numbers are the aluminium boron slurry of mentioning in the patent of 101937947A and 101944555A; Its aluminium boron slurry is through in the conventional aluminium paste that has prepared, directly adding boron source (boric acid, boron oxide, pure boron and other boron-containing compound etc.), mixes then and gets.The embodiment method of these patents is: at first buy the aluminium paste that has prepared from domestic and international aluminium paste manufacturer, add boron oxide, pure boron or potassium borate then, make aluminium boron slurry through mixing.These methods possibly make that p type doping content obtains raising to a certain degree in the back of the body surface field of crystal silicon solar energy battery; But because separate with the boron source fully in the aluminium source in this aluminium boron slurry; Such boron source is free in the battery sintering process outside aluminium-silicon eutectic usually; Be difficult for being incorporated into forming effectively in the aluminium silicon eutectic and mix, obviously this belongs to indirect boron doping way, and its doping effect is lower.
Summary of the invention
The objective of the invention is to provide the preparation method of a kind of aluminum-boron alloy powder and crystal silicon solar energy battery aluminium boron slurry to the deficiency of prior art; Compare with traditional aluminium boron slurry; The doping of boron in crystalline silicon in the aluminium boron slurry of the present invention's preparation belongs to direct doping; Can obtain the p type doping content of higher concentration; Therefore, can effectively eliminate the crooked of ultra thin silicon wafers in the back of the body the sintering process or the bending of ultra thin silicon wafers is minimized and the doping content that more effectively improves the back of the body, thereby improve the reliability and the photoelectric properties of the solar cell of preparation thus.
Preparation aluminum-boron alloy powder, and be that the method that primary raw material prepares aluminium boron slurry may further comprise the steps and content with this aluminum-boron alloy powder:
1, to adopt purity be 99.99% aluminium powder with purity is that one or more boron compounds in 99.99% boron oxide, boric acid, the borax evenly mix, and wherein the content of boron compound is 0.5%-10% (wt), and all the other are aluminium; Adopt Frequency Induction Heating or resistance heating mode in 800-1200 ℃ of temperature range with the fusion in crucible of this mixture; Reduction reaction at high temperature takes place boron is reduced into the pure boron atom from boron compound in boron compound and aluminium; This pure boron atom is scattered in the liquid aluminium, that is forms aluminium boron mixed liquor; With the boron oxide is example, and its reaction equation is B
2O
3+ Al → B+Al
2O
3, reactive metal aluminium produces the pure boron atom with the displacement of the boron element in the boron oxide, and the aluminium oxide that produce this moment is separated out with slag mutually, and floats to the surface of mixed liquor, can it be dragged for and remove or filter; Under 1200 ℃, be incubated 20 minutes, prepare the aluminum-boron alloy powder through gas atomization under the selected temperature in 800-1200 ℃ of scope then, Fig. 1 is the equipment sketch map; Blanketing with inert gas in the fusion process; Aluminium boron mixed liquor is from the flow nozzle of leting slip a remark of smelting furnace; High-voltage high-speed argon gas at atomisation tower moderate purity>=99.99% impacts flow through nozzle; Flow is by the bump drop that nebulizes, and drop cools off in the landing process and is frozen into particle diameter≤10 μ m aluminum-boron alloy powder;
2, mass percent is respectively aluminum-boron alloy powder, unorganic glass binding agent, organic binder bond and four kinds of materials mixing of additive of 72-82%, 0.1-10%, 15-25%, 1-5%; Mix the back and be bundled into particle diameter≤15 μ m with the three-high mill roller, viscosity is the conductive aluminum boron slurry of 30000-40000mPas;
3, said unorganic glass binding agent is a lead-free glass powder, by pressing a mole mark Bi
2O
322-26%, SiO
247-50%, B
2O
37.3-7.8%, TiO
22.2-2.7%, Li
2O2.9-3.3%, K
2O13.1-14.2% forms;
The manufacture method of said unorganic glass binding agent is: oxide mixes, and in the crucible of packing into, puts into high temperature furnace; Be warming up to 1000-1200 ℃, melting 0.5-2 hour, with the ball grinder of packing into after the quenching of the glass after the fusing; Behind the ball milling 24 hours, obtain the glass dust of granularity≤10 μ m;
4, said organic binder bond consists of by mass percent: ethyl cellulose 23%, cellaburate 1-6%, organic solvent 87-94%, Ricinate 0.2-1%, antifoaming agent 1-3%;
The preparation method of described organic binder bond is: composition is dropped in the agitated reactor according to preset proportioning weighing, be warming up to 80-120 ℃ and constant temperature 2-5 hour under low whipping speed 80-120 rev/min the state; Mentioned component in the agitated reactor is uniformly mixed and fully reaction, uses silk screen filter after the reactant cooling, promptly obtains the organic carrier of finished product;
5, said additive consists of by mass percent: silica sol 9.1-9.8%, wetting agent 62-68%, coalescents 21-27%.
The mode of the aluminium boron slurry that makes through silk screen printing is coated in crystal silicon cell back of the body surface uniformly, and after the oven dry, 750-820 ℃ of Fast Sintering, the time is no more than 3min, and the back of the body electric field of preparation crystal silicon solar energy battery has excellent photoelectric performance.
The invention has the beneficial effects as follows: the aluminum slurry with existing used for solar batteries is compared, and the prepared aluminium boron slurry of the present invention has following significant technique effect:
(1) adopts the crystal silicon solar battery back surface field of the aluminium boron pulp preparation that the present invention obtains; The p type doping content of the back of the body surface field of conventional aluminium paste preparation is wanted more than the high one magnitude under the concentration ratio uniform temp that the p type mixes; Thereby more excellent passivation effect can be arranged to the back of the body surface of crystal silicon solar energy battery; Reduce the series resistance of battery simultaneously, reached the target that improves the solar cell photoelectric conversion efficiency;
(2) because the prepared aluminium boron slurry of the present invention can reach the back of the body surface field doping content higher than conventional aluminium paste; Therefore under equal conditions the slurry use amount of every battery can obviously reduce; Therefore can reduce the angularity of crystal silicon solar energy battery effectively; Thereby reduce the percentage of damage of battery, reduce the overall manufacturing and the use cost of solar cell, further enlarge its application scale;
(3) preparation method of the present invention is simple, and its production cost is suitable with conventional aluminium paste, therefore has bigger competitive advantage and application prospect.
Description of drawings
Accompanying drawing 1 is a Medium frequency induction vacuum melting atomization plant sketch map;
1-feeder among the figure, 2-heater coil, 3-vacuum melting chamber, 4-high-vacuum pump, 5-heating power supply, 6-atomizer, 7-vacuum atomizing tower, 8-high pressure argon bottle, 9-powder catcher.
Embodiment
1) high-purity aluminium powder of mixed uniformly 99.99% and high-purity boron oxide of 99.99%; Adopt Frequency Induction Heating or resistance heating mode in 800-1200 ℃ of temperature range with the fusion in crucible of this mixture; Wherein the content of boron oxide is 1.57% (wt), and all the other are aluminium.Carry out redox reaction: B
2O
3+ Al → B+Al
2O
3Reactive metal aluminium produces the pure boron atom with the displacement of the boron element in the boron oxide, and the aluminium oxide that produce this moment is separated out with slag mutually, and floats to the surface of mixed liquor; Can it be dragged for and remove or filter, will obtain this moment not having slag mutually and boron element quality percentage composition be 0.5% aluminium boron melt liquid.Under 1200 ℃, insulation 20min; Through gas atomization, adopt high vacuum Medium frequency induction melting atomising device to prepare the Al-B alloy powder, Fig. 1 is the equipment sketch map.Blanketing with inert gas in the fusion process; The alloy solution atomizing is carried out in the spray chamber of equipment; Atomization temperature is 800 ℃, and the Al-B mixed liquor impacts flow at atomisation tower mesohigh high speed argon gas (purity>=99.99%) through nozzle by the flow nozzle of leting slip a remark in the holding furnace; Flow is by the bump drop that nebulizes, drop cooling and be frozen into particle diameter≤10 μ m aluminum-boron alloy powder in the landing interlude;
2) aluminum-boron alloy powder, unorganic glass binding agent, organic binder bond and four kinds of materials of additive of mass percent being respectively 72-82%, 0.1-10%, 15-25%, 1-5% mix; Mix the back and roll particle diameter≤15 μ m with the three-high mill roller, viscosity is the conductive aluminum boron slurry of 30000-40000mPas;
3) printing and the sintering of affected layer, the making of pn knot, edge etching, silicon nitride film deposition, back of the body surface field and positive counterelectrode removed in silicon chip cleaning, acid; The preparation method who wherein carries on the back surface field is; Adopting aluminium boron slurry that the present invention makes and conventional aluminium paste (AL840 of the Fu Lu company conduct electricity aluminium paste) mode through silk screen printing to be coated in crystal silicon cell respectively uniformly carries on the back surperficial; After the oven dry, at 800 ℃ of sintering, the time is no more than 3min respectively.
Draw the various performance parameters of measured solar cell in the table 1.
Efficient after battery efficiency and conventional aluminium paste burnt till after table 1 aluminium boron of the present invention slurry burnt till relatively
| Slurry | V OC（mV） | J SC（mA/cm 2） | FF（%） | E FFEfficient (%) | Doping content (atoms/cm 3） |
| Aluminium boron slurry (the present invention) | 611 | 35.2 | 75.3 | 16.2 | 1.9×10 19 |
| Conventional slurry | 603 | 34.8 | 74.9 | 15.7 | 2.1×10 18 |
(in table 1, expression V
OCThe open circuit voltage of when 0 output current, measuring, J
SCThe expression current density, FF representes fill factor, curve factor, E
FFExpression cell photoelectric conversion efficiency)
1) high-purity aluminium powder of mixed uniformly 99.99% and high-purity boron oxide of 99.99%; Adopt Frequency Induction Heating or resistance heating mode in 800-1200 ℃ of temperature range with the fusion in crucible of this mixture; Wherein the content of boron oxide is 3.08% (wt), and all the other are aluminium.Carry out redox reaction: B
2O
3+ Al → B+Al
2O
3Reactive metal aluminium produces the pure boron atom with the displacement of the boron element in the boron oxide, and the aluminium oxide that produce this moment is separated out with slag mutually, and floats to the surface of mixed liquor; Can it be dragged for and remove or filter, will obtain this moment not having slag mutually and boron element quality percentage composition be 1% aluminium boron melt liquid.Under 1200 ℃, insulation 20min; Through gas atomization, adopt high vacuum Medium frequency induction melting atomising device to prepare the Al-B alloy powder, Fig. 1 is the equipment sketch map.Blanketing with inert gas in the fusion process; The alloy solution atomizing is carried out in the spray chamber of equipment; Atomization temperature is 900 ℃, and the Al-B mixed liquor impacts flow at atomisation tower mesohigh high speed argon gas (purity>=99.99%) through nozzle by the flow nozzle of leting slip a remark in the holding furnace; Flow is by the bump drop that nebulizes, drop cooling and be frozen into particle diameter≤10 μ m aluminum-boron alloy powder in the landing interlude;
2) aluminum-boron alloy powder, unorganic glass binding agent, organic binder bond and four kinds of materials of additive of mass percent being respectively 72-82%, 0.1-10%, 15-25%, 1-5% mix; Mix the back and roll particle diameter≤15 μ m with the three-high mill roller, viscosity is the conductive aluminum boron slurry of 30000-40000mPas;
3) silicon chip cleans, affected layer is removed in acid, makings of pn knot, edge etching, silicon nitride film deposition, the back of the body and the just printing and the sintering of counterelectrode; The preparation method who wherein carries on the back surface field is; Adopting aluminium boron slurry that the present invention makes and conventional aluminium paste (AL840 of the Fu Lu company conduct electricity aluminium paste) mode through silk screen printing to be coated in crystal silicon cell respectively uniformly carries on the back surperficial; After the oven dry, at 800 ℃ of sintering, the time is no more than 3min respectively.
Draw the various performance parameters of measured solar cell in the table 2.
Efficient after battery efficiency and conventional aluminium paste burnt till after table 2 aluminium boron of the present invention slurry burnt till relatively
| Slurry | V OC（mV） | J SC（mA/cm 2） | FF（%） | E FFEfficient (%) | Doping content (atoms/cm 3） |
| Aluminium boron slurry (the present invention) | 617 | 35.6 | 75.8 | 16.6 | 2.1×10 19 |
| Conventional slurry | 603 | 34.8 | 74.9 | 15.7 | 2.1×10 18 |
(in table 2, expression V
OCThe open circuit voltage of when 0 output current, measuring, J
SCThe expression current density, FF representes fill factor, curve factor, E
FFExpression cell photoelectric conversion efficiency)
Instance 3
1) high-purity aluminium powder of mixed uniformly 99.99% and high-purity boron oxide of 99.99%; Adopt Frequency Induction Heating or resistance heating mode in 800-1200 ℃ of temperature range with the fusion in crucible of this mixture; Wherein the content of boron oxide is 5.88% (wt), and all the other are aluminium.Carry out redox reaction: B
2O
3+ Al → B+Al
2O
3Reactive metal aluminium produces the pure boron atom with the displacement of the boron element in the boron oxide, and the aluminium oxide that produce this moment is separated out with slag mutually, and floats to the surface of mixed liquor; Can it be dragged for and remove or filter, will obtain this moment not having slag mutually and boron element quality percentage composition be 2% aluminium boron melt liquid.Under 1200 ℃, insulation 20min; Through gas atomization, adopt high vacuum Medium frequency induction melting atomising device to prepare the Al-B alloy powder, Fig. 1 is the equipment sketch map.Blanketing with inert gas in the fusion process; The alloy solution atomizing is carried out in the spray chamber of equipment; Atomization temperature is 1000 ℃, and the Al-B mixed liquor impacts flow at atomisation tower mesohigh high speed argon gas (purity>=99.99%) through nozzle by the flow nozzle of leting slip a remark in the holding furnace; Flow is by the bump drop that nebulizes, drop cooling and be frozen into particle diameter≤10 μ m aluminum-boron alloy powder in the landing interlude;
2) aluminum-boron alloy powder, unorganic glass binding agent, organic binder bond and four kinds of materials of additive of mass percent being respectively 72-82%, 0.1-10%, 15-25%, 1-5% mix; Mix the back and roll particle diameter≤15 μ m with the three-high mill roller, viscosity is the conductive aluminum boron slurry of 30000-40000mPas;
3) silicon chip cleans, affected layer is removed in acid, makings of pn knot, edge etching, silicon nitride film deposition, the back of the body and the just printing and the sintering of counterelectrode; The preparation method who wherein carries on the back surface field is; Adopting aluminium boron slurry that the present invention makes and conventional aluminium paste (AL840 of the Fu Lu company conduct electricity aluminium paste) mode through silk screen printing to be coated in crystal silicon cell respectively uniformly carries on the back surperficial; After the oven dry, at 800 ℃ of sintering, the time is no more than 3min respectively.
Draw the various performance parameters of measured solar cell in the table 3.
Efficient after battery efficiency and conventional aluminium paste burnt till after table 3 aluminium boron of the present invention slurry burnt till relatively
| Slurry | V OC（mV） | J SC（mA/cm 2） | FF（%） | E FFEfficient (%) | Doping content (atoms/cm 3） |
| Aluminium boron slurry (the present invention) | 620 | 35.7 | 75.8 | 16.8 | 2.2×10 19 |
| Conventional slurry | 603 | 34.8 | 74.9 | 15.7 | 2.1×10 18 |
(in table 3, expression V
OCThe open circuit voltage of when 0 output current, measuring, J
SCThe expression current density, FF representes fill factor, curve factor, E
FFExpression cell photoelectric conversion efficiency)
1) high-purity aluminium powder of mixed uniformly 99.99% and high-purity boron oxide of 99.99%; Adopt Frequency Induction Heating or resistance heating mode in 800-1200 ℃ of temperature range with the fusion in crucible of this mixture; Wherein the content of boron oxide is 5.88% (wt), and all the other are aluminium.Carry out redox reaction: B
2O
3+ Al → B+Al
2O
3Reactive metal aluminium produces the pure boron atom with the displacement of the boron element in the boron oxide, and the aluminium oxide that produce this moment is separated out with slag mutually, and floats to the surface of mixed liquor; Can it be dragged for and remove or filter, will obtain this moment not having slag mutually and boron element quality percentage composition be 2% aluminium boron melt liquid.Under 1200 ℃, insulation 20min; Through gas atomization, adopt high vacuum Medium frequency induction melting atomising device to prepare the Al-B alloy powder, Fig. 1 is the equipment sketch map.Blanketing with inert gas in the fusion process; The alloy solution atomizing is carried out in the spray chamber of equipment; Atomization temperature is 1000 ℃, and the Al-B mixed liquor impacts flow at atomisation tower mesohigh high speed argon gas (purity>=99.99%) through nozzle by the flow nozzle of leting slip a remark in the holding furnace; Flow is by the bump drop that nebulizes, drop cooling and be frozen into particle diameter≤10 μ m aluminum-boron alloy powder in the landing interlude;
2) aluminum-boron alloy powder, unorganic glass binding agent, organic binder bond and four kinds of materials of additive of mass percent being respectively 72-82%, 0.1-10%, 15-25%, 1-5% mix; Mix the back and roll particle diameter≤15 μ m with the three-high mill roller, viscosity is the conductive aluminum boron slurry of 30000-40000mPas;
3) silicon chip cleans, affected layer is removed in acid, makings of pn knot, edge etching, silicon nitride film deposition, the back of the body and the just printing and the sintering of counterelectrode; The preparation method who wherein carries on the back surface field is; Adopting aluminium boron slurry that the present invention makes and conventional aluminium paste (AL840 of the Fu Lu company conduct electricity aluminium paste) mode through silk screen printing to be coated in crystal silicon cell respectively uniformly carries on the back surperficial; After the oven dry, at 818 ℃ of sintering, the time is no more than 3min respectively.
Draw the various performance parameters of measured solar cell in the table 4.
Efficient after battery efficiency and conventional aluminium paste burnt till after table 4 aluminium boron of the present invention slurry burnt till relatively
| Slurry | V OC（mV） | J SC（mA/cm 2） | FF（%） | E FFEfficient (%) | Doping content (atoms/cm 3） |
| Aluminium boron slurry (the present invention) | 622 | 36.3 | 76.1 | 17.2 | 2.5×10 19 |
| Conventional slurry | 607 | 34.9 | 75.2 | 15.9 | 2.3×10 18 |
(in table 4, expression V
OCThe open circuit voltage of when 0 output current, measuring, J
SCThe expression current density, FF representes fill factor, curve factor, E
FFExpression cell photoelectric conversion efficiency)
Claims (3)
1. the preparation method of an aluminum-boron alloy powder; It is characterized in that: to adopt purity be 99.99% aluminium powder with purity is that one or more boron compounds in 99.99% boron oxide, boric acid, the borax evenly mix; Wherein the content of boron compound is 0.5 wt %-10 wt %, and all the other are aluminium; Adopt Frequency Induction Heating or resistance heating mode in 800-1200 ℃ of temperature range with the fusion in crucible of this mixture; Reduction reaction at high temperature takes place boron is reduced into the pure boron atom from boron compound in boron compound and aluminium; This pure boron atom is scattered in the liquid aluminium, that is forms aluminium boron mixed liquor; The aluminium oxide that produce this moment is separated out with slag mutually, and floats to the surface of mixed liquor, it is dragged for remove or filter; Under 1200 ℃; Be incubated 20 minutes, prepare the aluminum-boron alloy powder through gas atomization under the selected temperature in 800-1200 ℃ of scope then, blanketing with inert gas in the fusion process; Aluminium boron mixed liquor is from the flow nozzle of leting slip a remark of smelting furnace; High-voltage high-speed argon gas at atomisation tower moderate purity>=99.99% impacts flow through nozzle, and flow is by the bump drop that nebulizes, and drop cools off in the landing process and is frozen into particle diameter≤10 μ m aluminum-boron alloy powder.
2. the preparation method of crystal silicon solar energy battery aluminium boron slurry; It is characterized in that: it be 99.99% aluminium powder with purity is that one or more boron compounds in 99.99% boron oxide, boric acid, the borax evenly mix that purity is adopted in (1); Wherein the content of boron compound is 0.5 wt %-10 wt %, and all the other are aluminium; Adopt Frequency Induction Heating or resistance heating mode in 800-1200 ℃ of temperature range with the fusion in crucible of this mixture; Reduction reaction at high temperature takes place boron is reduced into the pure boron atom from boron compound in boron compound and aluminium; This pure boron atom is scattered in the liquid aluminium, that is forms aluminium boron mixed liquor; The aluminium oxide that produce this moment is separated out with slag mutually, and floats to the surface of mixed liquor, it is dragged for remove or filter; Under 1200 ℃; Be incubated 20 minutes, prepare the aluminum-boron alloy powder through gas atomization under the selected temperature in 800-1200 ℃ of scope then, blanketing with inert gas in the fusion process; Aluminium boron mixed liquor is from the flow nozzle of leting slip a remark of smelting furnace; High-voltage high-speed argon gas at atomisation tower moderate purity>=99.99% impacts flow through nozzle, and flow is by the bump drop that nebulizes, and drop cools off in the landing process and is frozen into particle diameter≤10 μ m aluminum-boron alloy powder;
(2) aluminum-boron alloy powder, unorganic glass binding agent, organic binder bond and four kinds of materials of additive of mass percent being respectively 72-82%, 0.1-10%, 15-25%, 1-5% mix; Mix the back and be bundled into particle diameter≤15 μ m with the three-high mill roller, viscosity is the conductive aluminum boron slurry of 30000-40000mPas.
3. the preparation method of a kind of crystal silicon solar energy battery aluminium boron slurry according to claim 2, it is characterized in that: said unorganic glass binding agent is a lead-free glass powder, by pressing a mole mark Bi
2O
322-26%, SiO
247-50%, B
2O
37.3-7.8%, TiO
22.2-2.7%, Li
2O2.9-3.3%, K
2O13.1-14.2% forms;
The manufacture method of said unorganic glass binding agent is: oxide mixes, and in the crucible of packing into, puts into high temperature furnace; Be warming up to 1000-1200 ℃, melting 0.5-2 hour, with the ball grinder of packing into after the quenching of the glass after the fusing; Behind the ball milling 24 hours, obtain the glass dust of granularity≤10 μ m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110328105 CN102368411B (en) | 2011-10-26 | 2011-10-26 | Preparation method of aluminum-boron alloy powder and aluminum-boron slurry of crystalline silicon cell |
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|---|---|---|---|
| CN 201110328105 CN102368411B (en) | 2011-10-26 | 2011-10-26 | Preparation method of aluminum-boron alloy powder and aluminum-boron slurry of crystalline silicon cell |
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| Publication Number | Publication Date |
|---|---|
| CN102368411A CN102368411A (en) | 2012-03-07 |
| CN102368411B true CN102368411B (en) | 2012-12-26 |
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| CN103531265B (en) * | 2013-10-18 | 2014-12-03 | 南通天盛新能源科技有限公司 | Back field local contact aluminum slurry of crystalline silicon solar cell and preparation method of back field local contact aluminum slurry |
| CN103769595A (en) * | 2013-11-26 | 2014-05-07 | 王利民 | Method for preparing microcrystal and amorphous state powder material |
| CN106448805B (en) * | 2016-09-30 | 2018-01-02 | 江苏瑞德新能源科技有限公司 | A kind of solar energy aluminum conductor slurry and preparation method thereof |
| CN110459621B (en) * | 2019-07-26 | 2021-07-20 | 南昌大学 | Soldering paste for replacing low-temperature silver paste to prepare electrode grid line of solar cell and preparation method thereof |
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