Background technology
Fossil energy (coal, oil, natural gas) is the main body of current global Energy Consumption structure.Along with the mankind's continuous exploitation, the exhaustion of fossil energy is inevitable.In addition, fossil energy in use can produce a large amount of greenhouse gas CO
2, causing global warming, polar glacier melts, and sea level rise waits serious environmental problem day by day.Therefore, non-pollution of renewable energy such as exploitation solar energy, wind energy, geothermal energy and water ability will become developing direction from now on, and this wherein has only solar energy can uniquely guarantee human energy demand endlessly again.Thus, national governments all pay much attention to, and have put into effect relevant policies to encourage and to help the development of photovoltaic industry.Germany took the lead in having released the regenerative resource feeding method in 2000, power company must be to be higher than the purchasing price payment solar power generation person of original generating.U.S. senate in 2008 also formally reduces system through 18,000,000,000 dollars of regenerative resource investment taxes and prolongs bill, and wherein dwelling house and commercial building use solar power generation, and 30% investment tax reduces system and will prolong 8 years.2009, Japan also reactivated domestic solar TRT subsidy policy.Point out in " the new forms of energy industry rejuvenation and development planning (draft) " of China, solar power generation installation scale, the year two thousand twenty in 2011 with reaching 2,000,000 KW and 2,000 ten thousand KW respectively.
At present, crystal silicon solar energy battery is high because of its electricity conversion, and material itself does not impact environment, and material is convenient to industrialization and material property is stable, at the area of solar cell dominate.Silk screen print method because have the efficient height, cost is low and the characteristics of equipment simple and durable; As the method for suitability for industrialized production electrode of solar battery; Yet; The silver slurry that the screen printing crystalline silicon solar cell front electrode is used influences very big to the performance of battery like series resistance Rs, open circuit voltage Uoc, filling FF, transformation efficiency Eta.In recent years, China's photovoltaic industry development is rapid, and industry size and technical merit all have corresponding raising; But special-purpose raw-material production domesticization degree is not high; Kind is incomplete, has realized that the material and the component capabilities that domesticize are on the low side, and wherein photovoltaic silver slurry market is occupied by external producer such as Dupont, Ferro, Heraeus basically; This has significantly increased production cost, is unfavorable for the development of photovoltaic industry.In addition, main use is boron-silicon-lead-aluminium, bismuth-silicon-glass systems such as lead in the market, and its common feature is leaded; Be unfavorable for environmental protection; According to RoHS and WEEE environmental protection instruction that European Union proposes, the leaded slurry of this type is inevitable restricted in follow-up large-scale production, and then is eliminated.
Summary of the invention
The object of the present invention is to provide a kind of silicon solar cell that adopts Hydrothermal Preparation with silver slurry and technology thereof; Silver-colored slurry obtained by this method can have been realized the positive lead-free and cadmium-freeization with the silver slurry of silicon solar cell under the prerequisite that satisfies the silicon solar cell electrical property.
Technical problem to be solved by this invention, realize by the following technical programs:
A kind of concrete steps of Hydrothermal Preparation Organic fluoride doped silicon used for solar batteries silver sizing process method comprise:
A, be dissolved in the deionized water separately according to mol ratio 1:1 silver nitrate and potassium hydroxide respectively; Solution concentration is 0.5 ~ 3mol/L; Then liquor argenti nitratis ophthalmicus is slowly added in the potassium hydroxide solution, stirring reaction 1 ~ 2 hour made Ag in 4 ~ 8 hours 95 ~ 110 ℃ of oven dry
2The O powder;
B, with perfluoroethylene-propylene (FEP) emulsion, 1 ~ 4wt%; Tetrafluoroethene and perfluor n-propyl vinyl ether copolymer (PFA) emulsion, 1.5 ~ 6wt %; Ag
2The O powder, 75 ~ 86wt%; Cu (NO
3)
25H
2O, 0 ~ 10wt%; Ba (NO
3)
2, 0 ~ 8wt%; H
3PO
4, 0 ~ 10wt%; Ni (NO
3)
26H
2O, 0 ~ 5wt%; NH
4VO
3, 0 ~ 10wt%; Zn (NO
3)
26H
2O, 0 ~ 5wt%; Zr (NO
3)
45H
2O, the ball mill of packing into after 0 ~ 5wt% mixes, the deionized water and the weight that add 1 ~ 4 times of volume of mixture simultaneously are the ball-milling medium of 2 ~ 3 times in mixture, at rotation 160 ~ 280rpm, under revolution 120 ~ 240rpm, planetary ball mill got mixed emulsion in 4 ~ 12 hours;
C, with the autoclave of packing into of the mixed emulsion behind the ball milling, the Capacity Ratio that mixed emulsion accounts for autoclave is controlled at 60% ~ 70%, adds the molecular guide agent of 0.8 ~ 10wt% earlier, adds press effectively to reduce part amount of substance and Ag in the reducing agent again
2Ag among the O
+The reducing agent of amount of substance 1.1 ~ 1.5:1 ratio preparation, then autoclave is warmed up to 120 ~ 200 ℃ with the programming rate of 0.5 ~ 3 ℃/min, be incubated 4 ~ 24 hours, controlling pressure simultaneously is 2 ~ 4MPa;
D, will go out still through the mixed emulsion after the step C temperature reaction after; Filter with vacuum filter, with deionized water wash 2 ~ 4 times, use absolute ethanol washing again 1 ~ 2 time earlier; Dry under 50 ~ 60 ℃ in vacuum drying chamber then, obtain the silver powder particles that ultra-fine fluoro containing polymers coats;
After E, the silver powder particles that step D is made and organic binder bond mix with the weight ratio of 17:3 ~ 9:1; Using three-roll grinder to be ground to granularity with the rotating speed of 10rpm is 1 ~ 10 μ m; Viscosity is 600 ± 60Pas, promptly gets solid content and is 79 ~ 90% silicon solar cell and use silver paste.
The solid content of perfluoroethylene-propylene described in the step B (FEP) emulsion is 50%.
The solid content of tetrafluoroethene described in the step B and perfluor n-propyl vinyl ether copolymer is 30%.
The said ball-milling medium of step B is a zirconia ball.
The agent of molecular guide described in the step C is a diisopropylamine; Or a kind of composition in diisopropylamine and PVP (PVP) or the disodium ethylene diamine tetraacetate, concrete ratio is diisopropylamine 0.8 ~ 10wt%, PVP (PVP) 0 ~ 9.2 wt%, disodium ethylene diamine tetraacetate 0 ~ 9.2wt%.
Reducing agent described in the step C is made up of in diethanol, glycerine, diethanol amine, triethanolamine, ascorbic acid, the glucose one or more.
Consumption when deionized water described in the step D or absolute ethyl alcohol wash at every turn is 2 ~ 3 times of volumes of solid content.
Silver powder particles described in the step D is the superfine spherical of φ 0.1 ~ 1 μ m, and its tap density is 3.8 ~ 4.5g/cm
3
Organic binder bond described in the step e is formed by high polymer binder, auxiliary agent and solvent.
Said high polymer binder is made up of epoxy resin and ethyl cellulose.
Said auxiliary agent is a dibutyl phthalate (DBP).
Said solvent is selected from carbitol; Perhaps by at least a composition the in carbitol and terpinol or the turpentine oil.
The percentage by weight of each concrete material (wt%) is as follows in the said organic binder bond:
Epoxy resin 5 ~ 20, ethyl cellulose 15 ~ 25, dibutyl phthalate (DBP) 40 ~ 50, terpinol 0 ~ 50, turpentine oil 0 ~ 50, carbitol 10 ~ 50.
Useful technique effect of the present invention mainly shows:
1, adopt Hydrothermal Preparation Organic fluoride doped silicon used for solar batteries silver slurry, disperse more evenly than conventional method, bulk density is bigger, silver-colored uniform particles in the slurry that makes, and compact structure, purity is high, and not leaded, cadmium in the slurry, compliance with environmental protection requirements.
2, adopt Hydrothermal Preparation Organic fluoride doped silicon used for solar batteries silver slurry, the fluoride ability etch silicon nitride layer in its slurry makes silver-colored line and N type layer form good Ohmic contact.
3, adopt Hydrothermal Preparation Organic fluoride doped silicon used for solar batteries silver slurry, its slurry is applied to the silicon solar cell front gate line electrode, and the outward appearance printing quality is good, and the string resistance reduces, strong adhesion, and solderability is good, is the ideal substitute of traditional leaded slurry.
Embodiment
Embodiment 1
A, with AgNO
3586.31g add in the 2L deionized water, process liquor argenti nitratis ophthalmicus, again KOH 241.97g is added in the 2L deionized water; Process potassium hydroxide solution; Then liquor argenti nitratis ophthalmicus is slowly added in the potassium hydroxide solution, stirring reaction 1 hour made Ag in 5 hours 100 ℃ of oven dry
2O 400g powder;
B, with perfluoroethylene-propylene (FEP) emulsion, 1.9wt%; Tetrafluoroethene and perfluor n-propyl vinyl ether copolymer (PFA) emulsion, 3.9wt%; Ag
2The O powder, 84wt%; NH
4VO
3, 2.6wt%; H
3PO
4(80%), 3.2wt%; Ni (NO
3)
26H
2O, 2.7wt%; Zr (NO
3)
45H
2The planetary ball mill of packing into after O, 1.7wt% mix adds deionized water and the 1000g zirconia ball of 800ml simultaneously, and at rotation 280rpm, under the revolution 180rpm, planetary ball mill 6 hours must mixed emulsion;
C, be the autoclave of 2L with the capacity of packing into of the mixed emulsion behind the ball milling; Add diisopropylamine 120g, PVP (PVP) 20g, glycerine 200ml again; Then autoclave is warmed up to 150 ℃ with the programming rate of 0.5 ℃/min; Be incubated 4 hours, controlling pressure simultaneously is 2MPa;
D, will go out still through the mixed emulsion after the step C temperature reaction after; Filter with vacuum filter, at every turn with the deionized water wash of 3 times of volumes 3 times, use absolute ethanol washing again 1 time earlier; Dry under 50 ℃ in vacuum drying chamber then, obtain the silver powder particles that ultra-fine fluoro containing polymers coats;
E, select for use dibutyl phthalate (DBP), terpinol, carbitol, ethyl cellulose, epoxy resin to be mixed and made into organic binder bond with the weight ratio of 8:4:2:3:1; After silver powder particles that step D is made and organic binder bond mix with the weight ratio of 22:3; Using three-roll grinder to be ground to granularity with the rotating speed of 10 rpm is below the 10 μ m; Viscosity is 600 ± 10Pas, promptly gets solid content and is 87% silicon solar cell and use silver paste.
The silver paste of gained is done the front electrode printing respectively with 325 order silk screens seal on 156 polysilicon chips and 125 monocrystalline silicon pieces, get into tunnel kiln sintering, actual measurement sintering curre peak temperature is 820 ℃.Appearance qualities such as the empty seal of positive nothing, the disconnected grid of nothing behind the sintering.Recording its average photoelectric conversion efficient is 15.95% and 17.78%, with similar imported product correction data such as table 1.
Embodiment 2
A, with AgNO
3586.31g add in the 2L deionized water, process liquor argenti nitratis ophthalmicus, again KOH 241.97g is added in the 2L deionized water; Process potassium hydroxide solution; Then liquor argenti nitratis ophthalmicus is slowly added in the potassium hydroxide solution, stirring reaction 1 hour made Ag in 5 hours 110 ℃ of oven dry
2The O powder;
B, with perfluoroethylene-propylene (FEP) emulsion, 2.9wt%; Tetrafluoroethene and perfluor n-propyl vinyl ether copolymer (PFA) emulsion, 4.3wt%; Ag
2The O powder, 82wt%; NH
4VO
3, 1.9wt%; H
3PO
4(80%), 3.8wt%; Ni (NO
3)
26H
2O, 2.3wt%; Zr (NO
3)
45H
2The planetary ball mill of packing into after O, 2.8wt% mix adds deionized water and the 1000g zirconia ball of 800ml simultaneously, and at rotation 240rpm, under the revolution 120rpm, planetary ball mill 6 hours must mixed emulsion;
C, be the autoclave of 2L with the capacity of packing into of the mixed emulsion behind the ball milling, add diisopropylamine 150g, diethanol amine 200ml again, then autoclave is warmed up to 160 ℃ with the programming rate of 0.5 ℃/min, be incubated 4 hours, controlling pressure simultaneously is 3MPa;
D, will go out still through the mixed emulsion after the step C temperature reaction after; Filter with vacuum filter, spend earlier the deionised water 2 times of 3 times of volumes at every turn, use absolute ethanol washing again 2 times; Then in vacuum drying chamber 60 ℃ dry 5 hours down, obtain the silver powder particles that ultra-fine fluoro containing polymers coats;
E, select for use dibutyl phthalate (DBP), carbitol, ethyl cellulose, epoxy resin to be mixed and made into organic binder bond with the weight ratio of 8:7:3:1; After silver powder particles that step D is made and organic binder bond mix with the weight ratio of 22:3; Using three-roll grinder to be ground to granularity with the rotating speed of 10 rpm is below the 10 μ m; Viscosity is 600 ± 10Pas, promptly gets solid content and is 86% silicon solar cell and use silver paste.
The silver paste of gained is done the front electrode printing respectively with 325 order silk screens seal on 156 polysilicon chips and 125 monocrystalline silicon pieces, get into tunnel kiln sintering, actual measurement sintering curre peak temperature is 815 ℃.Appearance qualities such as the empty seal of positive nothing, the disconnected grid of nothing behind the sintering.Recording its average photoelectric conversion efficient is 15.91% and 17.71%, with similar imported product correction data such as table 1.
Embodiment 3
A, with AgNO
3586.31g add in the 2L deionized water, process liquor argenti nitratis ophthalmicus, again KOH 241.97g is added in the 2L deionized water; Process potassium hydroxide solution; Then liquor argenti nitratis ophthalmicus is slowly added in the potassium hydroxide solution, stirring reaction 1 hour made Ag in 4 hours 110 ℃ of oven dry
2The O powder;
B, with perfluoroethylene-propylene (FEP) emulsion, 1.4wt%; Tetrafluoroethene and perfluor n-propyl vinyl ether copolymer (PFA) emulsion; 3.9wt%, Ag
2The O powder, 81%wt%; NH
4VO
3, 2.5wt%; H
3PO
4(80%), 3.7wt%; Ni (NO
3)
26H
2O, 2.1wt%; Zr (NO
3)
45H
2O, 2.6wt%; Zn (NO
3)
26H
2The planetary ball mill of packing into after O, 2.8wt% mix adds deionized water and the 1000g zirconia ball of 800ml simultaneously, and at rotation 160rpm, under the revolution 180rpm, planetary ball mill 8 hours must mixed emulsion;
C, be the autoclave of 2L with the capacity of packing into of the mixed emulsion behind the ball milling; Add diisopropylamine 150g, PVP (PVP) 10g, glycerine 100ml, diethanol amine 100ml again; Then autoclave is warmed up to 150 ℃ with the programming rate of 0.5 ℃/min; Be incubated 6 hours, controlling pressure simultaneously is 3MPa;
D, will go out still through the mixed emulsion after the step C temperature reaction after; Filter with vacuum filter, at every turn with the deionized water wash of 3 times of volumes 3 times, use absolute ethanol washing again 2 times earlier; Then in vacuum drying chamber 60 ℃ dry 6 hours down, obtain the silver powder particles that ultra-fine fluoro containing polymers coats;
E, select for use dibutyl phthalate (DBP), carbitol, ethyl cellulose, epoxy resin to be mixed and made into organic binder bond with the weight ratio of 9:5:3:1; After silver powder particles that step D is made and organic binder bond mix with the weight ratio of 4:1; Using three-roll grinder to be ground to granularity with the rotating speed of 10 rpm is below the 8 μ m; Viscosity is 550 ± 10Pas, promptly gets solid content and is 83% silicon solar cell and use silver paste.
The silver paste of gained is done the front electrode printing respectively with 325 order silk screens seal on 156 polysilicon chips and 125 monocrystalline silicon pieces, get into tunnel kiln sintering, actual measurement sintering curre peak temperature is 812 ℃.Appearance qualities such as the empty seal of positive nothing, the disconnected grid of nothing behind the sintering.Recording its average photoelectric conversion efficient is 15.88% and 17.66%, with similar imported product correction data such as table 1.
Embodiment 4
A, with AgNO
3586.31g add in the 2L deionized water, process liquor argenti nitratis ophthalmicus, again KOH 241.97g is added in the 2L deionized water; Process potassium hydroxide solution; Then liquor argenti nitratis ophthalmicus is slowly added in the potassium hydroxide solution, stirring reaction 1 hour made Ag in 4 ~ 8 hours 95 ~ 110 ℃ of oven dry
2The O powder;
B, with perfluoroethylene-propylene (FEP) emulsion, 1.3wt%; Tetrafluoroethene and perfluor n-propyl vinyl ether copolymer (PFA) emulsion, 3wt%; Ag
2The O powder, 84wt%; NH
4VO
3, 2.9wt%; H
3PO
4(80%), 4.5wt%; Zr (NO
3)
45H
2O, 2.7wt%; Zn (NO
3)
26H
2O, the planetary ball mill of packing into after 1.6wt% mixes adds 800ml deionized water and 1000g zirconia ball simultaneously, and at rotation 260rpm, under the revolution 240rpm, planetary ball mill got mixed emulsion in 4 hours;
C, be the autoclave of 2L, add again the capacity of packing into of the mixed emulsion behind the ball milling
Diisopropylamine180g, glycerine 90ml, diethanol amine 120ml are warmed up to 150 ℃ with autoclave with the programming rate of 1 ℃/min then, are incubated 8 hours, and controlling pressure simultaneously is 4MPa;
D, will go out still through the mixed emulsion after the step C temperature reaction after; Filter with vacuum filter, at every turn with the deionized water wash of 3 times of volumes 4 times, use absolute ethanol washing again 2 times earlier; Then in vacuum drying chamber 60 ℃ dry 6 hours down, obtain the silver powder particles that ultra-fine fluoro containing polymers coats;
E, select for use dibutyl phthalate (DBP), terpinol, carbitol, ethyl cellulose, epoxy resin to be mixed and made into organic binder bond with the weight ratio of 8:3:3:4:1; After silver powder particles that step D is made and organic binder bond mix with the weight ratio of 9:1; Using three-roll grinder to be ground to granularity with the rotating speed of 10rpm is below the 10 μ m; Viscosity is 600 ± 10Pas, promptly gets solid content and is 89% silicon solar cell and use silver paste.
The silver paste of gained is done the front electrode printing respectively with 325 order silk screens seal on 156 polysilicon chips and 125 monocrystalline silicon pieces, get into tunnel kiln sintering, actual measurement sintering curre peak temperature is 820 ℃.Appearance qualities such as the empty seal of positive nothing, the disconnected grid of nothing behind the sintering.Recording its average photoelectric conversion efficient is 16.08% and 17.83%, with similar imported product correction data such as table 1.
Table 1 embodiment products obtained therefrom and similar imported product performance comparison