CN104952945A - Solar cell sheet and preparation method thereof and solar cell module with cell sheet - Google Patents
Solar cell sheet and preparation method thereof and solar cell module with cell sheet Download PDFInfo
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- CN104952945A CN104952945A CN201410126152.6A CN201410126152A CN104952945A CN 104952945 A CN104952945 A CN 104952945A CN 201410126152 A CN201410126152 A CN 201410126152A CN 104952945 A CN104952945 A CN 104952945A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a solar cell sheet and a preparation method thereof and a solar cell module with the cell sheet. The solar cell sheet comprises a silicon substrate sheet, an electrode seed gate wire layer which is arranged at the phototropic surface of the silicon substrate sheet, an electrode barrier layer which is arranged at the surface of the electrode seed gate wire layer, an electrode main body layer which is arranged at the surface of the electrode barrier layer, a back electric field which is arranged at the shady surface of the silicon substrate sheet and a shady surface electrode which is conducted with the back electric field. The electrode seed gate wire layer is a conductive silver paste sintering layer. The electrode barrier layer is at least one of a tin layer, a lead layer, a tin alloy layer and a lead alloy layer. The electrode barrier layer of the combined electrode is uniform and compact so that diffusion of copper atoms to the silicon substrate can be effectively prevented. Meanwhile, width of secondary gate wires is reduced, utilization rate of light is increased, and the phototropic surface electrode of the cell is prepared by adopting non-silver metal or metal with less silver so that cost of the cell is greatly reduced and competitiveness of solar cell power generation and conventional power generation can be increased.
Description
Technical field
The invention belongs to area of solar cell, particularly relate to a kind of solar battery sheet and preparation method thereof, solar module containing this cell piece.
Background technology
Solar energy is as a kind of green energy resource, inexhaustible with it, pollution-free, be not more and more subject to people's attention by the advantage such as resource advantage restriction.Existing silica-based solar cell, generally by being printed on silicon substrate by electrocondution slurry, adopts metallization process to prepare electrode and back of the body electric field.By phototropic face silver slurry, dry and sintering obtains phototropic face electrode, and this silver is starched and formed primarily of silver powder, unorganic glass powder, organic carrier mix and blend rolling.The silver slurry consumption of phototropic face electrode is more, along with the reduction of silicon materials price, the cost ratio of silver slurry cost in whole battery increases gradually, how to adopt the silver slurry that the material substitution of non-silver or few silver is current, and improve the depth-width ratio of the secondary grid line of electrode, increase the utilance of the light of battery, become emphasis and the focus of existing research silica-based solar cell.
Existing research is by first silk screen printing one deck Seed Layer silver slurry, carry out photoinduction plating (LIP) fine silver technique again, prepare the phototropic face electrode be jointly made up of seed silver layer and plating silver layer, the Seed Layer grid line of silk-screen is thin and short, as the conductive layer of plating fine silver after sintering, the electrode body resistance obtained is low, and fill factor, curve factor is high, the photoelectric conversion efficiency of battery has part in theory and promotes, and can reduce the consumption of silver slurry.The cost of the relatively silver-colored slurry of plating fine silver is low, also reduce electrode cost, but also there is many problems in preparation and the silk-screen of existing silver-colored Seed Layer, have impact on its practical application, the resolution of such as, silver-colored Seed Layer grid line after silk-screen not easily reaches designing requirement, the width of the secondary grid line of the electrode after photoinduction is electroplated increases excessive, shading-area increases, the short circuit current of battery is caused to decline, the photoelectric conversion efficiency of battery declines on the contrary, and the program still needs more noble silver, unfavorable to the cost reducing battery.
At present, also to have and reduce costs further, after printing-sintering obtains seed silver grating line, then adopt photoinduction electroplating technology on seed silver layer, to electroplate the thin metallic nickel of one deck as electrode barrier, then on electrode barrier plated metal copper as electrode body layer.The effect of electrode barrier stops metallic copper atom through sintering the seed silver layer obtained, and enters silicon substrate and the electrical property of battery is deteriorated.The method is because adopting plated metal nickel as electrode barrier, the hardness (or yield strength) of metallic nickel and metallic copper or argent widely different, therefore seed silver layer and electroless nickel layer, and the adhesive force between electroless nickel layer and copper electroplating layer does not often reach requirement, and the compactness of electronickelling is also poor, adopt the cell piece that this electrode fabrication obtains, be prepared in the Long-Time Service process of assembly follow-up, copper atom in electro-coppering electrode body layer easily enters silicon substrate through metal nickel dam and sintering silver layer, thus battery electrical property is declined.
Summary of the invention
The present invention is the defect that cost is high, battery performance is poor solving existing solar battery sheet phototropic face electrode, thus provide that a kind of cost is low, the solar battery sheet of good electrical property and preparation method thereof, solar module containing this cell piece.
The invention provides a kind of solar battery sheet, described solar battery sheet comprises:
Silica-based body piece;
Be arranged on the electrode seed grid line layer of described silica-based body piece phototropic face, be arranged on the electrode barrier on described electrode seed grid line layer surface and be arranged on the electrode body layer on described electrode barrier surface;
Be arranged on the back of the body electric field of described silica-based body piece shady face and the shady face electrode with the conducting of back of the body electric field;
Described electrode seed grid line layer is conductive silver paste sinter layer; Described electrode barrier is at least one in tin layers, lead layer, tin alloy layers and lead alloy layer.
Present invention also offers the preparation method of described solar battery sheet, the method is included in silica-based body piece phototropic face and prepares phototropic face electrode, silica-based body piece shady face preparation back of the body electric field and the back electrode with the conducting of back of the body electric field; The preparation method of described phototropic face electrode is included in silica-based body piece phototropic face and prepares antireflective coating, then starch at the surface printing silver of antireflective coating and sinter and prepare electrode seed grid line layer, on electrode seed grid line layer, prepare electrode barrier again, finally on electrode barrier, prepare electrode body layer.
Solar battery sheet of the present invention, described electrode barrier even compact, thickness is little, effectively can stop the diffusion of copper atom, and the adhesion of electrode barrier and seed grid line layer and electrode body layer is good.Compare the solar cell that traditional silk-screened silver starches the phototropic face electrode obtained, the width of the secondary grid line of solar cell of the present invention decreases, the characteristic such as short circuit current, fill factor, curve factor, photoelectric conversion efficiency, electricity conversion decay, weld strength decay of battery, all with conventional batteries close to or promote to some extent, and the amount of the silver adopted reduces to some extent, the cost of battery reduces.
Present invention also offers a kind of solar module, described solar module comprises the backboard, sealant layer, cell piece, sealant layer and the photic zone that stack gradually; Described cell piece is solar battery sheet of the present invention.
The properties of the assembly that the properties of solar module of the present invention and traditional handicraft make remains basically stable, and the present invention adopts multi-layer composite electrode to substitute traditional printing silver and starches the electrode obtained, and reduces the material cost of battery largely.
Embodiment
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.
The invention provides a kind of solar battery sheet, described solar battery sheet comprises
Silica-based body piece;
Be arranged on the electrode seed grid line layer of described silica-based body piece phototropic face, be arranged on the electrode barrier on described electrode seed grid line layer surface and be arranged on the electrode body layer on described electrode barrier surface;
Be arranged on the back of the body electric field of described silica-based body piece shady face and the shady face electrode with the conducting of back of the body electric field;
Described electrode seed grid line layer is conductive silver paste sinter layer; Described electrode barrier is at least one in tin layers, lead layer, tin alloy layers and lead alloy layer.
In the present invention, seed grid line layer is because of reasons such as organic substance volatilizations in silver slurry, and retaining in the silver slurry residue after sintering has many microscopic pinholes, and as Direct Electroplating metallic copper or copper alloy on residue, then metallic copper atom can enter in silicon substrate through micropore.In the present invention, add an electrode barrier before electro-coppering or copper alloy, described electrode barrier is the one in tin layers, lead layer, tin alloy layers, lead alloy layer and leypewter layer; Described electrode body layer is layers of copper or Kufil layer gold.Electrode barrier even compact of the present invention, thickness is little, effectively can stop the diffusion of copper atom, and seed grid line layer and electrode barrier, adhesion between electrode barrier and electrode body layer are good.
According to solar battery sheet provided by the present invention, preferably, described electrode barrier is at least one in leypewter layer, sn-bi alloy layer, tin pewter layer, tin-nickel alloy layer, lead-antimony alloy layer, lead bismuth alloy layer, plumbous nickel alloy layer, tin plumbous nickel alloy layer, mischzinn layer and rose metal layer.
According to solar battery sheet provided by the present invention, preferably, the mass content of the tin element in described tin alloy layers is 40 ~ 80wt%; The mass content of the lead element in described lead alloy layer is 40 ~ 80wt%; The mass content of the tin element in described leypewter layer is 20 ~ 40wt%, and the mass content of lead element is 20 ~ 40wt%.
The material element of described electrode barrier, i.e. metallic element tin, lead, bismuth, antimony, nickel, for can not form the element of objectionable impurities to silicon substrate, even if infiltrate through in silicon substrate, for the silicon substrate of P type, also can not produce deep energy level wherein, therefore all can not cause adverse influence to the electrical property of battery and electrical property decay.Especially tin or lead content ashbury metal within the specific limits or the electrodeposited coating of lead alloy formation, its compactness is better than the electrodeposited coating of pure tin or pure lead, and therefore the thickness of this electrode barrier can do very thin.The ashbury metal of the present invention's plating also can not produce " tinplague " phenomenon at low temperatures, is also not easy to form the tin crystals of needle-like, therefore can copper atom be stoped the infiltration of silicon in temperature range widely.
According to solar battery sheet provided by the present invention, preferably, the thickness of described electrode seed grid line layer is 2.0 ~ 6.0mm, and width is 30 ~ 50mm.
According to solar battery sheet provided by the present invention, the resistivity of the metal such as tin, lead is more much bigger than the resistivity of silver, copper metal, and therefore, electrode barrier is when can effectively stop copper atom to spread, preferably do thinner as far as possible, so just can reduce the volume resistance of whole combination electrode.But, too thin, can not effectively stop the copper atom in electro-coppering or copper alloy to the infiltration of silicon, too thick, cause the increase of whole electrode body resistance.Preferably, the thickness of described electrode barrier is 0.20 ~ 2.00mm.
According to solar battery sheet provided by the present invention, preferably, described electrode body layer is Kufil layer gold, and in described Kufil layer gold, the mass content of silver is 0.1 ~ 5.0wt%.In the present invention, in the copper of described electrode body layer, add a small amount of silver, adopt Kufil as electrode body layer, then can reduce the resistivity of electrode body layer material further, reduce the volume resistance of whole electrode.In addition, electro-coppering ag alloy layer containing a small amount of silver is finer and close than plating pure copper layer, the high temperature resistance fade performance of battery is better, also better with the welding performance of photovoltaic welding belt, but the interpolation of silver then can increase the material cost of electrode to a certain extent, consider the Performance and Cost Modeling of body layer Kufil, the composition content of silver element of the present invention in Kufil accounts for 0.1 ~ 5.0wt%, more preferably 0.2 ~ 3.0wt%.
Solar battery sheet provided by the present invention, the thickness of the electrode body layer that described plating obtains need be controlled, too thick, can increase the time of plating, also can widen the width of the secondary grid line of electrode to a certain extent simultaneously; Too thin, the volume resistance of electrode can be increased, cause the hydraulic performance decline of battery.Preferably, the thickness of described electrode body layer is 5.0 ~ 20mm.
Present invention also offers a kind of preparation method of solar battery sheet,
The method is included in silica-based body piece phototropic face and prepares phototropic face electrode, silica-based body piece shady face preparation back of the body electric field and the back electrode with the conducting of back of the body electric field; The preparation method of described phototropic face electrode is included in silica-based body piece phototropic face and prepares antireflective coating, then starch at the surface printing silver of antireflective coating and sinter and prepare electrode seed grid line layer, on electrode seed grid line layer, prepare electrode barrier again, finally on electrode barrier, prepare electrode body layer.According to preparation method provided by the present invention, preferably, before described electrode seed grid line layer prepares electrode barrier, print anti-etching resist in the non-electrode seed grid line layer region on antireflective coating surface.In preparation method of the present invention, printing anti-etching resist can be to a certain extent, stop the cross growth of subsequent optical induction electroplated electrode barrier layer or electrode body layer, the width guaranteeing to electroplate the secondary grid line of electrode of rear formation is in certain scope, thus increases the utilance of incident light.
According to preparation method provided by the present invention, in order to the cross growth better stoping subsequent optical to induce electroplated electrode barrier layer or electrode body layer, preferably, the thickness of described anti-etching resist is 5.0 ~ 15mm.Described anti-etching resist is for stablize acid, and the series products can removed by alkali, this series products is by self-control or commercially available.
According to preparation method provided by the present invention, the weight in wet base of described printing seed grid line layer is 20 ~ 40mg.According to preparation method provided by the present invention, described method also comprises, and after electrode barrier is prepared electrode body layer, removes the step of anti-etching resist.Further preferably, the method for the anti-etching resist of described removing is: be immersed in the removing liquid of anti-etching resist by described cell piece, removes anti-etching resist; The removing liquid of described anti-etching resist is the aqueous solution of KOH and butyl carbitol, wherein KOH: butyl carbitol: volume ratio=1:4.0 ~ 5.0:40 ~ 60 of water, and described soak time is 30 ~ 60 seconds, soaks rear deionized water rinsing, then adopts hot blast drying.
According to preparation method provided by the present invention, the preparation method of described electrode barrier is photoinduction plating; The plating solution that described photoinduction electroplated electrode barrier layer is used, comprises main salt and additive; Described main salt comprises the first main salt, and contain or do not contain the second main salt, described first main salt is pink salt and/or lead salt, and described second main salt is at least one in bismuth salt, antimonic salt and nickel salt; Described additive is at least one in resorcinol, peach gum or albumen.Described main salt is at least one in the borofluoride of above-mentioned metal, sulfate, sulfamate, sulfocarbolate.Temperature during plating is 20 ~ 30 DEG C.The electroplate liquid that described main salt is formed, its composition is simple, and solution-stabilized, impurity tolerance is good, can operate under room temperature, and deposition velocity is fast, and Deposit appearance is good.
According to preparation method provided by the present invention, the described method preparing electrode body layer is photoinduction plating, described photoinduction electroplated electrode body layer, plating solution used is cyanide electroplate liquid, and when namely electrode body layer is layers of copper, plating solution is copper cyanider electroplate liquid, when electrode body layer is Kufil layer gold, plating solution is copper cyanider and silver cyanide mixing electroplate liquid, and described bath pH values is 8 ~ 10, and temperature during plating is 20 ~ 30 DEG C.
The present invention obtains the electrode barrier even compact of phototropic face electrode, thickness is little, effectively can stop the diffusion of copper atom, and adhesion between electrode barrier and seed silver layer and electrode body layer is good, the width of the secondary grid line of electrode reduces, the short circuit current of battery and fill factor, curve factor increase, and photoelectric conversion efficiency gets a promotion, and cost of manufacture is low.
Present invention also offers a kind of solar module, described solar module comprises the backboard, sealant layer, cell piece, sealant layer and the photic zone that stack gradually; Described cell piece is solar battery sheet of the present invention.
Backboard described above, sealant layer and photic zone are that this area is commonly used, and do not repeat them here.
Below by embodiment, the present invention is described further.
Embodiment 1
The preparation of step one, seed grid line layer
The polysilicon chip specification adopted is 156 × 156mm, and thickness is before 200mm(corrosion), before printing, thickness is 180mm.After silicon wafer wool making, PN junction processed, dephosphorization silex glass, employing PECVD are plated silicon nitride anti-reflecting film, adopt 200 object silk screen printing shady face conductive silver slurries (model is Du Pont PV505), three eight sections, line systems, printing weight in wet base is 35 ~ 45mg, dries; Adopt 200 object silk screen printing back field aluminum paste material (model is large standing grain 108C) again, printing weight in wet base is 1.30 ~ 1.50g, dries; Then adopt that 360 orders, live width are 25 μm, wire diameter is 16 μm, thickness is that (model is Du Pont 17A for the screen painting seed grid line layer silver slurry of 5 μm, adopt terpinol be diluted to solid containing for after 60wt% and get final product), printing weight in wet base is 30 ~ 40mg, enter in continuous tunnel furnace and dry sintering, preheat temperature is 200 ~ 400 DEG C, peak temperature is 950 DEG C, the whole time crossing continuous tunnel furnace is about 2 minutes, peak value sintering time is about 1 second, the shady face obtained has aluminium back surface field, back of the body silver electrode, and phototropic face has the silicon chip of electrode seed grid line layer.
The thickness that test obtains seed grid line layer is 2.0 ~ 3.0 μm, and secondary grid line width is 40 ~ 50 μm.
Step 2, print anti-etching resist
After obtaining seed grid line layer, adopt 400 object half tones, anti-etching resist (model is the XV-120082-1 that DOW company produces) is printed in the region beyond the seed grid line layer of phototropic face, and the thickness printing anti-etching resist is 10 ~ 12mm.
The preparation of step 3, electrode barrier
Adopt photoinduction electroplating technology on phototropic face seed silver grating line layer tin-lead alloy plating (wherein in alloy, tin mass percentage content is 60wt%) as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: adopt tin fluoborate (Sn (BF
4)
2) and lead fluoborate (Pb (BF
4)
2) provide plated metal ion, Sn in electroplate liquid
2+concentration is 52g/L, Pb
2+concentration is 30g/L, HBF
4(dissociating) concentration is 150g/L, resorcinol (stabilizer) concentration 1.3g/L, and albumen (brightener) concentration 5.0g/L, temperature is 25 DEG C, and current density is 1.50A/dm
2, anode adopts metal platinum (Pt) plate or leypewter plate (Theil indices is 60wt%), and electroplating time is 50 seconds.
The Theil indices tested in the electrode barrier alloy obtained is 60 ± 1.0wt%, and thickness of coating is 0.50 ± 0.10 μm.
The preparation of step 4, electrode body layer
Adopt photoinduction electroplating technology on electrode barrier electro-coppering ag alloy layer as electrode body layer.
Formula and the plating conditions of electroplate liquid are as follows: adopt copper cyanider (Cu (CN)
2) and silver cyanide (AgCN) provide plated metal ion, Cu in electroplate liquid
2+concentration is 19.5g/L, Ag
+concentration is 0.5g/L, and potassium pyrophosphate is 100g/L, and adopt quininic acid that the pH value of electroplate liquid is transferred to 9, the temperature of electroplate liquid is 25 DEG C, and current density is 0.50A/dm
2, the Kufil plate (argentiferous 2wt%) that anode adopts, electroplating time is 30min.
The silver content tested in the Kufil obtained is 2.0 ± 0.5wt%, and thickness of coating is 10 ± 1.0 μm.
Step 5, remove anti-etching resist
Silicon chip after electro-coppering ag alloy layer is put into the solution being equipped with and can removing anti-etching resist, this removing liquid is by KOH(mass concentration 45wt%): butyl carbitol: H
2volume ratio=the 1:4.2:52 of O is formulated, is soaked 35 ~ 40 seconds by battery, then use deionized water rinsing, after going out groove, cell piece is adopted hot blast drying, namely obtain the finished product solar battery sheet with compound phototropic face electrode of the present invention in the groove removing liquid.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 12 ~ 14 μm, and the width of secondary grid line is 50 ~ 60 μm.
The finished product solar battery sheet of the present embodiment is designated as S1.
Embodiment 2
Step one, two, four, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Adopt photoinduction electroplating technology on phototropic face seed silver grating line electroplated Sn-Bi alloy as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: adopt stannous sulfate (SnSO
4) and bismuth sulfate (Bi
2(SO
4)
3) plated metal ion is provided, in electroplate liquid, stannous sulfate addition is 43g/L, and bismuth sulfate addition is 0.7g/L, Sn in plating solution
2+concentration is 0.95g/L, and polyoxyethylene alkyl amine is 5mL/L, 1-naphthols is 0.1mL/L, and formaldehyde is 5mL/L, and acyl benzenetriol is 0.1mL/L, is transferred to by pH value and is less than 1, and the temperature of electroplate liquid is 25 DEG C, and current density is 3.0A/dm
2, anode adopts metal platinum (Pt) plate, and electroplating time is 30 seconds.
The test Theil indices obtained in electrode barrier alloy is 60 ± 2.0wt%, and thickness of coating is 1.50 ± 0.10 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 14 ~ 16 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S2.
Embodiment 3
Step one, two, four, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Adopt photoinduction electroplating technology on phototropic face seed silver grating line electrotinning nickel alloy as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: adopt stannous sulfate (SnSO
4) and six hydration nickel sulfate (NiSO
4× 6H
2o) provide plated metal ion, in electroplate liquid, stannous sulfate concentration is 40g/L, and concentration of nickel sulfate is 150g/L, ammonium citrate ((NH
4)
3c
6h
4o
7) concentration is 150g/L, sulfamic acid sodium 70g/L, resorcinol concentration is 10ml/L, and pH value is 4, and temperature is 40 DEG C, and current density is 3.50A/dm
2, anode adopts high-purity metal nickel plate, and electroplating time is 35 seconds.
The Theil indices tested in the electrode barrier alloy obtained is 65 ± 2.0wt%, and thickness of coating is 1.50 ± 0.10 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 14 ~ 16 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S3.
Embodiment 4
Step one, two, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Except being except 3min by electroplating time, all the other are identical with embodiment 1.
The Theil indices testing the leypewter electrode barrier obtained is 60 ± 1.0wt%, and thickness is at 2.0 ± 0.1 μm.
The preparation of step 4, electrode body layer
Except being except 40 min by electroplating time, all the other are identical with embodiment 1.
The silver content that the Kufil electrode body layer obtained is electroplated in test is 2.0 ± 0.5wt%, and thickness of coating is 15 ± 1.0 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 20 ~ 23 μm, and the width of secondary grid line is 55 ~ 65 μm.
The battery sample that the present embodiment obtains is designated as S4.
Embodiment 5
Step one, two, three, five identical with embodiment 1, difference is:
The preparation of step 4, electrode body layer
Adopt photoinduction electroplating technology on electrode barrier electro-coppering as electrode body layer.
Formula and the plating conditions of electroplate liquid are as follows: adopt copper cyanider (Cu (CN)
2) provide plated metal ion, Cu in electroplate liquid
2+concentration is 18.7g/L, potassium pyrophosphate 100g/L, and adopt quininic acid that the pH value of electroplate liquid is transferred to 9, the temperature of electroplate liquid is 20 DEG C, and current density is 0.55A/dm
2, the high-purity copper plates that anode adopts, electroplating time is 30min.
Testing the copper electroplating layer thickness obtained is 10 ± 1.0 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 12 ~ 14 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S5.
Embodiment 6
Step one, two, four, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Adopt photoinduction electroplating technology on phototropic face seed silver grating line electroplating lead tin alloy (wherein in alloy, plumbous mass percentage is 60wt%) as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: adopt tin fluoborate (Sn (BF
4)
2) and lead fluoborate (Pb (BF
4)
2) provide plated metal ion, Pb in electroplate liquid
2+concentration is 44g/L, Sn
2+concentration is 35g/L, HBF
4(dissociating) concentration is 150g/L, resorcinol (stabilizer) concentration 1.3g/L, and albumen (brightener) concentration 5.0g/L, temperature is 25 DEG C, and current density is 1.5A/dm
2, anode adopts metal platinum (Pt) plate or terne metal plate (Theil indices is 60 ± 2.0wt%), and electroplating time is 50 seconds.
The lead content tested in the electrode barrier alloy obtained is 60 ± 2.0wt%, and thickness of coating is 0.50 ± 0.10 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 14 ~ 16 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S6.
Embodiment 7
Step one, two, four, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Adopt photoinduction electroplating technology on phototropic face seed silver grating line lead plating antimony alloy as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: tin fluoborate (Sn (BF
4)
2) and lead fluoborate (Sb (BF
4)
2) provide plated metal ion, Pb in electroplate liquid
2+concentration is 231.4g/L, Sb
2+concentration is 11.8g/L, HBF
4(dissociating) concentration is 74.1g/L, resorcinol (stabilizer) concentration 0.23g/L, and albumen (brightener) concentration 0.23g/L, temperature is 27 DEG C, and current density is 3.0A/dm
2, anode adopts pure lead or lead-antimony alloy plate (wherein in alloy, lead content is 80 ± 2.0wt%), and electroplating time is 35 seconds.
The lead content tested in the electrode barrier alloy obtained is 80 ± 2.0wt%, and thickness of coating is 0.50 ± 0.10 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 14 ~ 16 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S7.
Embodiment 8
Step one, two, four, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Adopt the plumbous nickel alloy of photoinduction electroplating technology electrotinning on phototropic face seed silver grating line as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: adopt tin fluoborate (Sn (BF
4)
2), lead fluoborate (Pb (BF
4)
2), nickel fluoborate (Ni (BF
4)
2) provide plated metal ion, Sn in electroplate liquid
2+concentration is 34g/L, Pb
2+concentration is 25.4g/L, Ni
2+concentration 16g/L, HBF
4(dissociating) concentration is 180g/L, resorcinol (stabilizer) concentration 3.0g/L, and albumen (brightener) concentration 3.5g/L, temperature is 25 DEG C, and current density is 1.5A/dm
2, anode adopts metal platinum (Pt) plate, and electroplating time is 50 seconds.
Test is electroplated in the plumbous nickel alloy layer of the tin obtained, and wherein Theil indices is 40 ± 1.0wt%, and lead content is 40 ± 1.0wt%, and remainder is nickel, and thickness of coating is 0.50 ± 0.10 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 14 ~ 16 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S8.
Embodiment 9
Step one, two, four, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Adopt photoinduction electroplating technology on phototropic face seed silver grating line electrotinning lead bismuth alloy as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: adopt stannous sulfate (SnSO
4), lead sulfate (PbSO
4), bismuth sulfate (Bi
2(SO
4)
3) plated metal ion is provided, in electroplate liquid, the addition of stannous sulfate is 40g/L, and the addition of lead sulfate is 32g/L, the addition of bismuth sulfate is 0.3g/L, Sn in plating solution
2+concentration is 0.85g/L, Pb
2+concentration is 0.34g/L, and polyoxyethylene alkyl amine is 8mL/L, 1-naphthols is 0.25mL/L, and formaldehyde is 6mL/L, and acyl benzenetriol is 0.10mL/L, is transferred to by pH value and is less than 1, and the temperature of electroplate liquid is 25 DEG C, and current density is 1.5A/dm
2, anode adopts metal platinum (Pt) plate, and electroplating time is 45 seconds.
Test plating obtains in the plumbous nickel alloy layer of tin, and wherein Theil indices is 40 ± 1.0wt%, and lead content is 20 ± 1.0wt%, and remainder is bismuth, and thickness of coating is 0.20 ± 0.10 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 14 ~ 16 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S9.
Embodiment 10
Step one, two, four, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Adopt photoinduction electroplating technology on phototropic face seed silver grating line Tin plating as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: adopt tin fluoborate (Sn (BF
4)
2) provide plated metal ion, Sn in plating solution
2+concentration is 50g/L, HBF
4(dissociating) concentration is 120g/L, resorcinol (stabilizer) concentration 0.20g/L, and albumen (brightener) concentration 0.22g/L, temperature is 25 DEG C, and current density is 3.0A/dm
2, anode adopts high pure metal sheet tin, and electroplating time is 30 seconds.
Testing the electrode barrier thickness of coating obtained is 0.50 ± 0.10 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 14 ~ 16 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S10.
Embodiment 11
Step one, two, four, five identical with embodiment 1, difference is:
The preparation of step 3, electrode barrier
Photoinduction electroplating technology is adopted to electroplate pure lead as electrode barrier on phototropic face seed silver grating line.
Formula and the plating conditions of electroplate liquid are as follows: adopt lead fluoborate (Pb (BF
4)
2) provide plated metal ion, Pb in plating solution
2+concentration is 38g/L, HBF
4(dissociating) concentration is 120g/L, resorcinol (stabilizer) concentration 0.25g/L, and albumen (brightener) concentration 0.20g/L, temperature is 25 DEG C, and current density is 3.0A/dm
2, anode adopts high pure metal stereotype, and electroplating time is 35 seconds.
The thickness testing the electrode barrier obtained is 0.50 ± 0.10 μm.
The general thickness of testing the secondary grid line of this cell piece phototropic face combination electrode is 14 ~ 16 μm, and the width of secondary grid line is 50 ~ 60 μm.
The battery sample that the present embodiment obtains is designated as S11.
Comparative example 1
The polysilicon chip specification adopted is 156 × 156mm, and thickness is before 200mm(corrosion), before printing, thickness is 180mm.By silicon wafer wool making, PN junction processed, dephosphorization silex glass, after adopting PECVD to plate silicon nitride anti-reflecting film, adopt 200 object silk screen printing shady face conductive silver slurries (model is Du Pont PV505), three eight sections, line systems, printing weight in wet base is 35 ~ 45mg, dry, adopt 200 object silk screen printing back field aluminum paste material (model is large standing grain 108C) again, printing weight in wet base is 1.30 ~ 1.50g, dry, then 360 orders are adopted, live width is 50 μm, wire diameter is 16 μm, thickness is screen painting phototropic face silver slurry (model is Du Pont 17F) of 5 μm, printing weight in wet base is 90 ~ 110mg, enter in continuous tunnel furnace and dry sintering, preheat temperature is 200 ~ 400 DEG C, peak temperature is 950 DEG C, the whole time crossing continuous tunnel furnace is about 2 minutes, peak value sintering time is about 1 second, obtain possessing aluminium back surface field, the cell piece of silver back electrode line and silver-colored phototropic face electrode wires.
The thickness testing the secondary grid line of this resultant battery sheet phototropic face silver electrode is 15 ~ 18 μm, and the width of secondary grid line is 60 ~ 70 μm.
The finished product solar battery sheet of this comparative example is designated as D1.
Comparative example 2
The preparation of step one, seed silver grating line
The polysilicon chip specification adopted is 156 × 156mm, and thickness is before 200mm(corrosion), before printing, thickness is 180mm.By silicon wafer wool making, PN junction processed, dephosphorization silex glass, after adopting PECVD to plate silicon nitride anti-reflecting film, adopt 200 object silk screen printing shady face conductive silver slurries (model is Du Pont PV505), three eight sections, line systems, printing weight in wet base is 35 ~ 45mg, dry, adopt 200 object silk screen printing back field aluminum paste material (model is large standing grain 108C) again, printing weight in wet base is 1.30 ~ 1.50g, dry, then 360 orders are adopted, live width is the screen painting phototropic face silver slurry (model is Du Pont 17A silver slurry) of 50 μm, printing weight in wet base is 80 ~ 90mg, enter in continuous tunnel furnace and dry sintering, preheat temperature is 200 ~ 400 DEG C, peak temperature is 955 DEG C, the whole time crossing continuous tunnel furnace is about 2min, peak value sintering time is about 1 second, the shady face obtained has aluminium back surface field, back of the body silver electrode, phototropic face has the solar battery sheet of seed silver grating line.
The thickness that test obtains the secondary grid line of this seed silver electrode is 8.0 ~ 10 μm, and width is 60 ~ 70 μm.
The preparation of step 2, plating silver layer
Adopt photoinduction electroplating technology to carry out photoinduction plated metal fine silver to the seed silver electrode sintered, electroplate liquid is silver nitrate (AgNO
3) aqueous solution, Ag
+concentration is 30g/L, cathode-current density 4.0A/dm
2, temperature is 35 DEG C, and electroplating time is 3.5min, and the electrosilvering layer thickness obtained is 5.0 ± 1.0 μm.After going out groove, cell piece is adopted hot blast drying, namely obtain finished product solar battery sheet.
The general thickness of testing the secondary grid line of the phototropic face combination electrode of this comparative example solar battery sheet is 12 ~ 15 μm, and the width of secondary grid line is 70 ~ 80 μm.
The finished product solar battery sheet of this comparative example is designated as D2.
Comparative example 3
The preparation of step one, seed grid line layer
This step is identical with embodiment 1.
The preparation of step 2, electrode barrier
Adopt photoinduction electroplating technology on phototropic face seed grid line layer plated metal nickel as electrode barrier.
Formula and the plating conditions of electroplate liquid are as follows: adopt nickel sulfamic acid (Ni (NH
2sO
3)
2× 4H
2o) the aqueous solution provides plated metal ion, wherein Ni
2+concentration is 105g/L, current density 3.3A/dm
2, temperature is 45 DEG C, and electroplating time is 48 seconds.Anode adopts high-purity metal nickel plate, and the thickness of coating obtained is 0.50 ± 0.1 μm.
The preparation of step 3, electrode body layer
Adopt photoinduction electroplating technology on metallic nickel electrode barrier plated metal copper as electrode body layer.
Formula and the plating conditions of electroplate liquid are as follows: adopt copper sulphate (CuSO
4× 5H
2o) aqueous solution provides plated metal ion, wherein Cu
2+concentration is 120g/L, cathode-current density 4.5A/dm
2, temperature is 45 DEG C, and anode adopts fine copper metallic plate, and electroplating time is 8.5min, and the pure copper layer thickness obtained is 10 ± 1.0 μm.
The general thickness of testing the secondary grid line of this comparative example solar battery sheet phototropic face combination electrode is 12 ~ 15 μm, and the width of secondary grid line is 75 ~ 85 μm.
The finished product solar battery sheet of this comparative example is designated as D3.
performance test
1, short circuit current I
sc(A)
,series resistance R
s(m Ω), fill factor, curve factor FF, electricity conversion Eta: adopt single flash operation simulation test instrument to carry out test to each cell piece and obtain.Test condition is standard test condition (STC): light intensity: 1000W/m
2; Spectrum: AM1.5; Temperature: 25 DEG C.The results are shown in Table 1.
2, weld strength σ (N/mm): select victory footpath between fields, Shanghai 2*0.2mm tin lead welding band, soaks post-drying with Henkel X32-10I type scaling powder, then carries out manual welding 330 DEG C of main gate line to electrode.After cell piece cools naturally, the electrode using mountain degree SH-100 puller system to connect along 45 ° of direction butt welding carries out tensile test.The results are shown in Table 1.
3, electricity conversion decay (Eta
after decay): baking oven resultant battery sheet being put into 200 DEG C, takes out after 120 days, tests its photoelectric conversion efficiency attenuation.The results are shown in Table 1.
4, weld strength decay (σ
after decay, N/mm): adopt photovoltaic welding belt to weld with the phototropic face electrode of battery, then cell piece is put into the baking oven of 200 DEG C, take out after 120 days, test the attenuation of its weld strength.The results are shown in Table 1.
Table 1
。
As can be seen from Table 1, the present invention prepares the electrode barrier even compact of compound phototropic face electrode, and thickness is little, effectively can stop the diffusion of copper atom, and electrode barrier and seed silver layer, the adhesion of electrode barrier and electrode body layer is good.Compare traditional silk-screened silver and starch the phototropic face electrode obtained, the width of the secondary grid line of electrode of the present invention reduces to some extent, the characteristic that the short circuit current of battery, fill factor, curve factor, photoelectric conversion efficiency, electricity conversion decay, weld strength decay, all be close with traditional polysilicon solar cell or slightly promote, but the more important thing is, the amount of the noble silver that combination electrode prepared by the present invention adopts will be lacked, the material cost of battery reduces, and adds the competitiveness of crystal silicon solar energy battery generating and conventional electric power generation.
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 (16)
1. a solar battery sheet, is characterized in that, described solar battery sheet comprises:
Silica-based body piece;
Be arranged on the electrode seed grid line layer of described silica-based body piece phototropic face, be arranged on the electrode barrier on described electrode seed grid line layer surface and be arranged on the electrode body layer on described electrode barrier surface;
Be arranged on the back of the body electric field of described silica-based body piece shady face and the shady face electrode with the conducting of back of the body electric field;
Described electrode seed grid line layer is conductive silver paste sinter layer; Described electrode barrier is at least one in tin layers, lead layer, tin alloy layers and lead alloy layer.
2. solar battery sheet according to claim 1, it is characterized in that, described electrode barrier is at least one in leypewter layer, sn-bi alloy layer, tin pewter layer, tin-nickel alloy layer, lead-antimony alloy layer, lead bismuth alloy layer, plumbous nickel alloy layer, tin plumbous nickel alloy layer, mischzinn layer and rose metal layer.
3. solar battery sheet according to claim 2, is characterized in that, the mass content of the tin element in described tin alloy layers is 40 ~ 80wt%; The mass content of the lead element in described lead alloy layer is 40 ~ 80wt%; The mass content of the tin element in described leypewter layer is 20 ~ 40wt%, and the mass content of lead element is 20 ~ 40wt%.
4. solar battery sheet according to claim 3, is characterized in that, the thickness of described electrode seed grid line layer is 2.0 ~ 6.0mm, and width is 30 ~ 50mm.
5. solar battery sheet according to claim 4, is characterized in that, the thickness of described electrode barrier is 0.20 ~ 2.00mm.
6. solar battery sheet according to claim 5, is characterized in that, the thickness of described electrode body layer is 5.0 ~ 20mm.
7. solar battery sheet according to claim 6, is characterized in that, described electrode body layer is layers of copper or Kufil layer gold.
8. solar battery sheet according to claim 7, is characterized in that, described electrode body layer is Kufil layer gold, and in described Kufil layer gold, the mass content of silver is 0.1 ~ 5.0wt%.
9. a preparation method for the solar battery sheet described in claim 1-8 any one, is characterized in that, the method is included in silica-based body piece phototropic face and prepares phototropic face electrode, silica-based body piece shady face preparation back of the body electric field and the back electrode with the conducting of back of the body electric field; The preparation method of described phototropic face electrode is included in silica-based body piece phototropic face and prepares antireflective coating, then starch at the surface printing silver of antireflective coating and sinter and prepare electrode seed grid line layer, on electrode seed grid line layer, prepare electrode barrier again, finally on electrode barrier, prepare electrode body layer.
10. preparation method according to claim 9, is characterized in that, described on electrode seed grid line layer, prepare electrode barrier before, print anti-etching resist in the non-electrode seed grid line layer region on antireflective coating surface.
11. preparation methods according to claim 10, is characterized in that, the thickness of described anti-etching resist is 5.0 ~ 15mm.
12. preparation methods according to claim 11, is characterized in that, described method removes the step of anti-etching resist after being also included in and electrode barrier preparing electrode body layer.
13. preparation methods according to claim 12, is characterized in that, the method for the anti-etching resist of described removing is: be immersed in by described cell piece in the removing liquid of anti-etching resist and remove anti-etching resist; The removing liquid of described anti-etching resist is the aqueous solution of KOH and butyl carbitol, wherein KOH: butyl carbitol: volume ratio=1:4.0 ~ 5.0:40 ~ 60 of water.
14. preparation methods according to claim 9, is characterized in that, the preparation method of described electrode barrier is photoinduction plating; Described photoinduction electroplated electrode barrier layer plating solution used comprises main salt and additive; Described main salt comprises the first main salt, and contain or do not contain the second main salt, described first main salt is pink salt and/or lead salt, and described second main salt is at least one in bismuth salt, antimonic salt and nickel salt; Described additive is at least one in resorcinol, peach gum and albumen.
15. preparation methods according to claim 9, it is characterized in that, the described method preparing electrode body layer is photoinduction plating, described photoinduction electroplated electrode body layer plating solution used is copper cyanider electroplate liquid, or the mixing electroplate liquid of copper cyanider and silver cyanide, described bath pH value is 8 ~ 10, and temperature during plating is 20 ~ 30 DEG C.
16. 1 kinds of solar modules, is characterized in that, described solar module comprises the backboard, sealant layer, cell piece, sealant layer and the photic zone that stack gradually; Described cell piece is the solar battery sheet described in claim 1-8 any one.
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