CN109809699A - A kind of p-doped glass powder and preparation method and the method for preparing positive silver paste used for solar batteries using it - Google Patents
A kind of p-doped glass powder and preparation method and the method for preparing positive silver paste used for solar batteries using it Download PDFInfo
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- CN109809699A CN109809699A CN201910043603.2A CN201910043603A CN109809699A CN 109809699 A CN109809699 A CN 109809699A CN 201910043603 A CN201910043603 A CN 201910043603A CN 109809699 A CN109809699 A CN 109809699A
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Abstract
A kind of p-doped glass powder and preparation method and the method for preparing positive silver paste used for solar batteries using it, it is related to a kind of glass powder and preparation method and the method for preparing positive silver paste using it.The doping efficiency of phosphorus is low when the invention aims to solve the problems, such as the p-doped glass of existing method preparation causes the incident photon-to-electron conversion efficiency of crystal silicon solar batteries low with when being printed on crystal silicon solar batteries piece using its positive silver paste used for solar batteries prepared.A kind of p-doped glass powder is by PbO, Bi2O3、SiO2、TeO2、ZnO、MgO、B2O3It is prepared with phosphorus source, method: one, mixing；Two, mixed-powder is prepared；Three, melting；Four, p-doped.It prepares positive silver paste used for solar batteries using a kind of p-doped glass powder to be prepared by p-doped glass powder, silver powder and organic carrier, method: one, weighing；Two, it grinds.The present invention can get a kind of p-doped glass powder.
Description
Technical field
The present invention relates to a kind of glass powder and preparation methods and the method for preparing positive silver paste using it.
Background technique
Solar-energy photo-voltaic cell is developed so far, many kinds of, in the solar battery of numerous kinds, crystal silicon solar
Earliest, technology of preparing is most mature for battery research and development.Therefore, improving crystal silicon battery photoelectric conversion efficiency, reducing cost is always
The developing goal of photovoltaic industry.The high efficiency for realizing crystal silicon solar batteries, will be dependent on the improve of two aspect technologies: one
It is from silicon semiconductor material；The other is such as passing through from existing crystal silicon battery preparation process and technology is improved
Application of selective emitter (Selective Emitter, SE) high-efficiency battery technology etc..
Known in the industry, last procedure of crystal silicon battery production is silk-screen printing positive electrode silver paste, and passes through high temperature
It is fast to burn the photoelectric conversion efficiency for realizing cell piece.Therefore, positive silver paste is the key that determine crystal silicon battery incident photon-to-electron conversion efficiency material
One of material.Positive silver paste is made of conductive phase silver powder (afflux effect), function phase glass and organic bond.Wherein, glass
Although powder proportion in conductive silver paste is few, corroding silicon nitride and silicon wafer are played, is bonded the effect of silverskin and silicon wafer.When
After the completion of organic carrier volatilization, glass powder softening is glass metal, infiltrates, can effectively drop to Argent grain and silicon chip surface
The surface tension of low metal solution, increases the surface contact of Argent grain and silicon wafer, to improve the compactness of sintering silverskin and attached
Put forth effort.
The application of crystal silicon solar batteries structure selectivity emitter (SE), for promoting transfer efficiency and reducing cost
It is significant.1., in gate electrode line lower zone formation heavy doping so-called SE emitter technology it is characterized in that tie good to be formed deeply
Good Ohmic contact and raising fill factor；2., non-grid region formation shallow junction is lightly doped, to obtain preferable surface passivation
Effect improves open-circuit voltage, short wave response and short circuit current etc. to improve cell conversion efficiency；3., between metal and N-shaped Si
With lower junction barrier (< 0.5eV) so as to have tunnel-effect between Si-Ag electrode；4., phosphorous glasses square region under the electrodes
Has the function of phosphorus diffusion to realize that SE selects emitter technology.When the prior art is to preparation phosphorous glasses, because phosphorus is at high temperature
Boiling characteristics are difficult to realize its highly doped efficiency.
Summary of the invention
The doping efficiency of phosphorus is low when the invention aims to solve the p-doped glass of existing method preparation and uses its system
Standby positive silver paste used for solar batteries leads to the photoelectric conversion of crystal silicon solar batteries when being printed on crystal silicon solar batteries piece
The problem of low efficiency, and a kind of p-doped glass powder and preparation method are provided and prepare positive silver paste used for solar batteries using it
Method.
A kind of p-doped glass powder is in parts by weight by 1 part~10 parts PbO, 15 parts~30 parts Bi2O3, 15 parts~25 parts of SiO2、
10 parts~35 parts TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO, 5 parts~15 parts B2O3It is prepared with 1 part~10 parts phosphorus sources.
A kind of preparation method of p-doped glass powder, is completed by the following steps:
One, 1 part~10 parts PbO, 15 parts~30 parts Bi are weighed in parts by weight2O3, 15 parts~25 parts of SiO2, 10 parts~35
Part TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO, 5 parts~15 parts B2O3With 1 part~10 parts phosphorus sources；
Two, by weighed 1 part~10 parts PbO, 15 parts~30 parts Bi in step 12O3, 15 parts~25 parts of SiO2, 10 parts~
35 parts of TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO and 5 part~15 parts B2O3It is uniformly mixed, obtains mixed-powder；
Three, mixed-powder is placed in aluminium crucible, then aluminium crucible is placed in the high-temperature electric that temperature is 1200 DEG C~1400 DEG C
Melting 20min~60min in furnace, then aluminium crucible is quenched to room temperature in distilled water, obtain coarse glass frit；Coarse glass frit is led to
It crosses airslide disintegrating mill or mechanical crusher crushes, reuse distilled water and clean 5 times~8 times, then in the case where temperature is 60 DEG C~200 DEG C
Drying obtains the glass powder that partial size is 10 μm~15 μm；
Four, p-doped:
Partial size is uniformly mixed for 10 μm~15 μm of glass powder and 1 part~10 parts phosphorus sources, then passes through planetary ball mill
Or airslide disintegrating mill crushes, and reuses distilled water and cleans 5 times~8 times, then dries at being 300 DEG C~400 DEG C in temperature, partial size is
3 μm~5 μm of p-doped glass powder.
Using a kind of method that p-doped glass powder prepares positive silver paste used for solar batteries, it is completed by the following steps:
One, 1 part~4 parts p-doped glass powders are weighed in parts by weight, 80 parts~90 parts silver powder and 5 parts~10 parts have it is airborne
Body；
Two, weighed 1 part~4 parts p-doped glass powders, 80 parts~90 parts silver powder and 5 parts~10 parts in step 1 are had airborne
Body is uniformly mixed to be placed on three rolling pulp grinders and grind, and obtains positive silver paste used for solar batteries.
The principle of the present invention and advantage:
The present invention realizes the efficient doping of phosphorus, phosphorus holds very much at high temperature by the method for the rear doping phosphorus source of phosphorus diffusion
It is volatile fall, the rear method for adulterating phosphorus source can realize that phosphorus source is diffused into glass at low temperature；Use p-doped prepared by the present invention
When the positive silver paste used for solar batteries of glass powder (being named as rear p-doped glass powder) preparation is printed on crystal silicon solar batteries piece
Cause the incident photon-to-electron conversion efficiency of crystal silicon solar batteries high, being primarily due to phosphorus source can spread in glass, doping efficiency
Higher than the glass for first adulterating phosphorus.
The present invention can get a kind of p-doped glass powder.
Specific embodiment
Specific embodiment 1: a kind of p-doped glass powder of present embodiment is in parts by weight by 1 part~10 parts PbO, 15 parts
~30 parts of Bi2O3, 15 parts~25 parts of SiO2, 10 parts~35 parts of TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO, 5 parts~15 parts
B2O3It is prepared with 1 part~10 parts phosphorus sources.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: the phosphorus source is five oxidations
Two phosphorus, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium monohydrogen phosphate, calcium phosphate, calcium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, acid
Sodium acid pyrophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, sodium pyrophosphate, calcium dihydrogen phosphate, phosphoric acid, potassium dihydrogen phosphate,
Dipotassium hydrogen phosphate, sodium acid pyrophosphate, three defocusing phosphoric acid, potassium dihydrogen phosphate, potassium pyrophosphate, potassium tripolyphosphate, sodium metaphosphate, phosphorus
One of acid dihydride calcium, calcium dihydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate or in which several mixtures.Other steps
It is same as the specific embodiment one.
Specific embodiment 3: present embodiment is: a kind of preparation method of p-doped glass powder is to complete according to the following steps
:
One, 1 part~10 parts PbO, 15 parts~30 parts Bi are weighed in parts by weight2O3, 15 parts~25 parts of SiO2, 10 parts~35
Part TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO, 5 parts~15 parts B2O3With 1 part~10 parts phosphorus sources；
Two, by weighed 1 part~10 parts PbO, 15 parts~30 parts Bi in step 12O3, 15 parts~25 parts of SiO2, 10 parts~
35 parts of TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO and 5 part~15 parts B2O3It is uniformly mixed, obtains mixed-powder；
Three, mixed-powder is placed in aluminium crucible, then aluminium crucible is placed in the high-temperature electric that temperature is 1200 DEG C~1400 DEG C
Melting 20min~60min in furnace, then aluminium crucible is quenched to room temperature in distilled water, obtain coarse glass frit；Coarse glass frit is led to
It crosses airslide disintegrating mill or mechanical crusher crushes, reuse distilled water and clean 5 times~8 times, then in the case where temperature is 60 DEG C~200 DEG C
Drying obtains the glass powder that partial size is 10 μm~15 μm；
Four, p-doped:
Partial size is uniformly mixed for 10 μm~15 μm of glass powder and 1 part~10 parts phosphorus sources, then passes through planetary ball mill
Or airslide disintegrating mill crushes, and reuses distilled water and cleans 5 times~8 times, then dries at being 300 DEG C~400 DEG C in temperature, partial size is
3 μm~5 μm of p-doped glass powder.
Specific embodiment 4: present embodiment prepares positive silver paste used for solar batteries using a kind of p-doped glass powder
Method is completed by the following steps:
One, 1 part~4 parts p-doped glass powders are weighed in parts by weight, 80 parts~90 parts silver powder and 5 parts~10 parts have it is airborne
Body；
Two, weighed 1 part~4 parts p-doped glass powders, 80 parts~90 parts silver powder and 5 parts~10 parts in step 1 are had airborne
Body is uniformly mixed to be placed on three rolling pulp grinders and grind, and obtains positive silver paste used for solar batteries.
Specific embodiment 5: the difference of present embodiment and specific embodiment four is: silver described in step 1
Powder is high tap density silver powder, and the partial size of high tap density silver powder is 1 μm~2 μm, and tap density is > 5.0g/mL.Other steps
Suddenly identical with specific embodiment four.
The principle and advantage of present embodiment:
Present embodiment realizes the efficient doping of phosphorus, phosphorus is at high temperature by the method for the rear doping phosphorus source of phosphorus diffusion
It is easy to vapor away, the rear method for adulterating phosphorus source can realize that phosphorus source is diffused into glass at low temperature；Use present embodiment system
The positive silver paste used for solar batteries of standby p-doped glass powder (being named as rear p-doped glass powder) preparation is printed on crystal silicon solar
Cause the incident photon-to-electron conversion efficiency of crystal silicon solar batteries high when cell piece, being primarily due to phosphorus source can spread in glass,
Doping efficiency is higher than the glass for first adulterating phosphorus.
Present embodiment can get a kind of p-doped glass powder.
Specific embodiment 6: one of present embodiment and specific embodiment four to five difference are: institute in step 1
The organic carrier stated is prepared according to the following steps:
One, weighing:
Weigh in parts by weight 40 parts~70 parts organic solvents, 1 part~8 parts thixotropic agent, 1 part~7 parts thickeners, 1 part~
10 parts of coupling agents, 1 part~10 parts surfactants and 1 part~5 parts lubricants；
Two, by weighed 40 parts~70 parts organic solvents, 1 part~8 parts thixotropic agent, 1 part~7 parts thickeners, 1 in step 1
Part~10 parts of coupling agents, 1 part~10 parts surfactants and 1 part~5 parts mix lubricants are uniform, then temperature be 100 DEG C~
60min~200min is reacted at 150 DEG C, is cooled to room temperature, is obtained organic carrier.Other steps and specific embodiment four to
Five is identical.
Specific embodiment 7: one of present embodiment and specific embodiment four to six difference are: institute in step 1
The organic solvent stated be alcohol ester 12, terpinol, tributyl citrate, triethanolamine, butyl carbitol, dimethyl glutarate,
One of dimethyl adipate, repefral and oleic acid or in which several mixed liquors.Other steps and specific
Embodiment four to six is identical.
Specific embodiment 8: one of present embodiment and specific embodiment four to seven difference are: institute in step 1
The thixotropic agent stated is fumed silica, organobentonite, rilanit special, polyamide wax or polyethylene wax；The poly- second
Alkene wax is Anjeka 4360.Other steps are identical as specific embodiment four to seven.
Specific embodiment 9: one of present embodiment and specific embodiment four to eight difference are: institute in step 1
The thickener stated be curdlan, methylcellulose, hydroxypropyl methyl cellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose,
Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, modified paraffin resin, carbomer, polyacrylic acid,
One of Polyacrylate Emulsion, butadiene rubber, butadiene-styrene rubber, polyurethane, modified polyurea and low-molecular polyethylene wax
Or in which several mixture.Other steps are identical as specific embodiment four to eight.
Specific embodiment 10: one of present embodiment and specific embodiment four to nine difference are: institute in step 1
The coupling agent stated is butyl titanate, titanate esters crosslinking agent TA-9-2,3- (aminopropyl) triethoxysilane, 3- (trimethoxy
Base silicyl) -1- propylamine, 3- aminopropyltriethoxy diethoxy silane, diethylenetriamine base propyl trimethoxy silicane, tertiary fourth
One of base the third amino trimethoxy silane and 4- amino -3,3- dimethylbutyl trimethoxy silane or in which several mixed
Close object；The surfactant is one of alkyl glycosides, fatty glyceride, sapn, tween and oleic acid or in which several
The mixture of kind；The lubricant be one of fatty diglycollic amide, oleic acid and polyethylene terephthalate or
Wherein several mixture.Other steps are identical as specific embodiment four to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of p-doped glass powder is in parts by weight by 8 parts of PbO, 21 parts of Bi2O3, 22 parts of SiO2, 15 parts of TeO2、
6 parts of ZnO, 4 parts of MgO, 6 parts of B2O3It is prepared with 7 parts of phosphorus sources, the preparation method is as follows:
One, 8 parts of PbO, 21 parts of Bi are weighed in parts by weight2O3, 22 parts of SiO2, 15 parts of TeO2, 6 parts of ZnO, 4 parts of MgO, 6 parts
B2O3With 7 parts of phosphorus sources；
Phosphorus source described in step 1 is phosphorus pentoxide；
Two, by 8 parts of PbO weighed in step 1,21 parts of Bi2O3, 22 parts of SiO2, 15 parts of TeO2, 6 parts of ZnO, 4 parts of MgO and 6
Part B2O3It is uniformly mixed, obtains mixed-powder；
Three, mixed-powder is placed in aluminium crucible, then aluminium crucible is placed in melting in the high-temperature electric resistance furnace that temperature is 1200 DEG C
60min, then aluminium crucible is quenched to room temperature in distilled water, obtain coarse glass frit；Coarse glass frit is passed through into airslide disintegrating mill powder
It is broken, it reuses distilled water and cleans 6 times, then dried at being 80 DEG C in temperature, obtain the glass powder that partial size is 10 μm~15 μm；
Four, p-doped:
Partial size is uniformly mixed for 10 μm~15 μm of glass powder and 7 parts of phosphorus sources, then is crushed by planetary ball mill, then
Make 6 times wash with distilled water, then is dried at being 380 DEG C in temperature, the p-doped glass powder that partial size is 3 μm~5 μm.
First comparative example one: without phosphorus glass powder is in parts by weight by 8 parts of PbO, 21 parts of Bi2O3, 22 parts of SiO2, 15 parts
TeO2, 6 parts of ZnO, 4 parts of MgO and 6 part of B2O3It is prepared, the preparation method is as follows:
One, 8 parts of PbO, 21 parts of Bi are weighed in parts by weight2O3, 22 parts of SiO2, 15 parts of TeO2, 6 parts of ZnO, 4 parts MgO and 6 part
B2O3；
Two, by 8 parts of PbO weighed in step 1,21 parts of Bi2O3, 22 parts of SiO2, 15 parts of TeO2, 6 parts of ZnO, 4 parts of MgO and 6
Part B2O3It is uniformly mixed, obtains mixed-powder；
Three, mixed-powder is placed in aluminium crucible, then aluminium crucible is placed in melting in the high-temperature electric resistance furnace that temperature is 1200 DEG C
60min, then aluminium crucible is quenched to room temperature in distilled water, obtain coarse glass frit；Coarse glass frit is passed through into airslide disintegrating mill powder
It is broken, it reuses distilled water and cleans 6 times, then dried at being 380 DEG C in temperature, obtaining partial size is 10 μm~15 μm without phosphorus glass
Powder.
Second comparative example one: it is a kind of elder generation p-doped glass powder in parts by weight by 8 parts of PbO, 21 parts of Bi2O3, 22 parts
SiO2, 15 parts of TeO2, 6 parts of ZnO, 4 parts of MgO, 6 parts of B2O3It is prepared with 7 parts of phosphorus sources, the preparation method is as follows:
One, 8 parts of PbO, 21 parts of Bi are weighed in parts by weight2O3, 22 parts of SiO2, 15 parts of TeO2, 6 parts of ZnO, 4 parts of MgO, 6 parts
B2O3With 7 parts of phosphorus sources；
Phosphorus source described in step 1 is phosphorus pentoxide；
Two, by 8 parts of PbO weighed in step 1,21 parts of Bi2O3, 22 parts of SiO2, 15 parts of TeO2, 6 parts of ZnO, 4 parts of MgO, 6
Part B2O3It is uniformly mixed with 7 parts of phosphorus sources, obtains mixed-powder；
Three, mixed-powder is placed in aluminium crucible, then aluminium crucible is placed in melting in the high-temperature electric resistance furnace that temperature is 1200 DEG C
60min, then aluminium crucible is quenched to room temperature in distilled water, obtain coarse glass frit；Coarse glass frit is passed through into airslide disintegrating mill powder
It is broken, it reuses distilled water and cleans 6 times, then dried at being 380 DEG C in temperature, obtain the first p-doped glass that partial size is 10 μm~15 μm
Powder.
Embodiment two: the method for preparing positive silver paste used for solar batteries using p-doped glass powder prepared by embodiment one,
It is completed by the following steps:
One, p-doped glass powder, 90 parts of silver powder and the 5 parts of organic carriers of the preparation of 5 parts of embodiments one are weighed in parts by weight；
Silver powder described in step 1 is high tap density silver powder, and the partial size of high tap density silver powder is 1 μm~2 μm, vibration
Real density is > 5.0g/mL；
Organic carrier described in step 1 is prepared according to the following steps:
1., weighing:
70 parts of organic solvents, 8 parts of thixotropic agent, 7 parts of thickeners, 5 parts of coupling agents, 5 parts of surface-actives are weighed in parts by weight
Agent and 5 parts of lubricants；
Step 1 1. described in organic solvent be tributyl citrate；
Step 1 1. described in thixotropic agent be rilanit special；
Step 1 1. described in thickener be hydroxyethyl cellulose；
Step 1 1. described in coupling agent be butyl titanate；
Step 1 1. described in surfactant be fatty glyceride；
Step 1 1. described in lubricant be fatty diglycollic amide；
2., by step 1 1. in weighed 70 parts of organic solvents, 8 parts of thixotropic agent, 7 parts of thickeners, 5 parts of coupling agents, 5 parts of tables
Face activating agent and 5 parts of mix lubricants are uniform, then react 60min at being 120 DEG C in temperature, are cooled to room temperature, obtain organic
Carrier；
Two, p-doped glass powder, 90 parts of silver powder and the 5 parts of organic carriers for preparing 5 parts of embodiments one weighed in step 1
It is uniformly mixed to be placed on three rolling pulp grinders and grind, be utilized the positive silver paste used for solar batteries of p-doped glass powder preparation.
Silver powder in embodiment two is according to application No. is 200810150800.6, and application publication number is
CN101347841A, denomination of invention are as follows: prepared by the preparation method of high tap density silver powder with controllable graininess.
First comparative example two: it is prepared using without phosphorus glass powder prepared by the first comparative example one used for solar batteries
The method of positive silver paste, is completed by the following steps:
One, the without phosphorus glass powder of 5 part of first comparative example one preparation is weighed in parts by weight, 90 parts of silver powder and 5 parts have
Airborne body；
Silver powder described in step 1 is high tap density silver powder, and the partial size of high tap density silver powder is 1 μm~2 μm, vibration
Real density is > 5.0g/mL；
Organic carrier described in step 1 is prepared according to the following steps:
1., weighing:
70 parts of organic solvents, 8 parts of thixotropic agent, 7 parts of thickeners, 5 parts of coupling agents, 5 parts of surface-actives are weighed in parts by weight
Agent and 5 parts of lubricants；
Step 1 1. described in organic solvent be tributyl citrate；
Step 1 1. described in thixotropic agent be rilanit special；
Step 1 1. described in thickener be hydroxyethyl cellulose；
Step 1 1. described in coupling agent be butyl titanate；
Step 1 1. described in surfactant be fatty glyceride；
Step 1 1. described in lubricant be fatty diglycollic amide；
2., by step 1 1. in weighed 70 parts of organic solvents, 8 parts of thixotropic agent, 7 parts of thickeners, 5 parts of coupling agents, 5 parts of tables
Face activating agent and 5 parts of mix lubricants are uniform, then react 60min at being 120 DEG C in temperature, are cooled to room temperature, obtain organic
Carrier；
Two, the without phosphorus glass powder for preparing 5 part of first comparative example one weighed in step 1,90 parts of silver powder and 5 parts
Organic carrier is uniformly mixed and is placed on three rolling pulp grinders and grinds, be utilized without phosphorus glass powder preparation it is used for solar batteries just
Silver paste.
Silver powder in first comparative example two is according to application No. is 200810150800.6, and application publication number is
CN101347841A, denomination of invention are as follows: prepared by the preparation method of high tap density silver powder with controllable graininess.
Second comparative example two: solar battery is prepared using first p-doped glass powder prepared by the second comparative example one
With the method for positive silver paste, it is completed by the following steps:
One, first p-doped glass powder, 90 parts of silver powder and 5 parts of the preparation of 5 part of second comparative example one are weighed in parts by weight
Organic carrier；
Silver powder described in step 1 is high tap density silver powder, and the partial size of high tap density silver powder is 1 μm~2 μm, vibration
Real density is > 5.0g/mL；
Organic carrier described in step 1 is prepared according to the following steps:
1., weighing:
70 parts of organic solvents, 8 parts of thixotropic agent, 7 parts of thickeners, 5 parts of coupling agents, 5 parts of surface-actives are weighed in parts by weight
Agent and 5 parts of lubricants；
Step 1 1. described in organic solvent be tributyl citrate；
Step 1 1. described in thixotropic agent be rilanit special；
Step 1 1. described in thickener be hydroxyethyl cellulose；
Step 1 1. described in coupling agent be butyl titanate；
Step 1 1. described in surfactant be fatty glyceride；
Step 1 1. described in lubricant be fatty diglycollic amide；
2., by step 1 1. in weighed 70 parts of organic solvents, 8 parts of thixotropic agent, 7 parts of thickeners, 5 parts of coupling agents, 5 parts of tables
Face activating agent and 5 parts of mix lubricants are uniform, then react 60min at being 120 DEG C in temperature, are cooled to room temperature, obtain organic
Carrier；
Two, first p-doped glass powder, the 90 parts of silver powder and 5 for preparing 5 part of second comparative example one weighed in step 1
Part organic carrier, which is uniformly mixed to be placed on three rolling pulp grinders, to be ground, and the solar battery of first p-doped glass powder preparation is utilized
Use positive silver paste.
Silver powder in second comparative example two is according to application No. is 200810150800.6, and application publication number is
CN101347841A, denomination of invention are as follows: prepared by the preparation method of high tap density silver powder with controllable graininess.
(1), the application for the positive silver paste used for solar batteries using the preparation of p-doped glass powder that embodiment two obtains:
The positive silver paste used for solar batteries using the preparation of p-doped glass powder that embodiment two obtains passes through silk screen print method
It prints electrode on polysilicon solar battery slice front；The specification of polysilicon solar battery slice are as follows: side length 156*156mm,
190 ± 10 μm of thickness, 60~100 Ω of sheet resistance.Silk screen print method prints electrode halftone on polysilicon solar battery slice front
Parameter are as follows: aluminium outer frame diameter 320mm*320mm, 400 mesh of screen cloth mesh number, 20 μm of linear diameter, 20 μm of film thickness, tension 22N；Printed
Thin grid width is generally 80 μm, 23 μm of height.
(2), the positive silver paste used for solar batteries using the preparation of without phosphorus glass powder that first comparative example two obtains
Using:
The positive silver paste used for solar batteries using the preparation of without phosphorus glass powder that first comparative example two obtains passes through silk
Net print process prints electrode on polysilicon solar battery slice front；The specification of polysilicon solar battery slice are as follows: side length
156*156mm, 190 ± 10 μm of thickness, 60~100 Ω of sheet resistance.Silk screen print method prints on polysilicon solar battery slice front
Brush electrode halftone parameter are as follows: aluminium outer frame diameter 320mm*320mm, 400 mesh of screen cloth mesh number, 20 μm of linear diameter, 20 μm of film thickness, tension
22N；Printed thin grid width is generally 80 μm, 23 μm of height.
(3), the positive silver paste used for solar batteries using first p-doped glass powder preparation that the second comparative example two obtains
Application:
The positive silver paste used for solar batteries using first p-doped glass powder preparation that second comparative example two obtains passes through
Silk screen print method prints electrode on polysilicon solar battery slice front；The specification of polysilicon solar battery slice are as follows: side length
156*156mm, 190 ± 10 μm of thickness, 60~100 Ω of sheet resistance.Silk screen print method prints on polysilicon solar battery slice front
Brush electrode halftone parameter are as follows: aluminium outer frame diameter 320mm*320mm, 400 mesh of screen cloth mesh number, 20 μm of linear diameter, 20 μm of film thickness, tension
22N；Printed thin grid width is generally 80 μm, 23 μm of height.
Table 1 is that the positive silver paste used for solar batteries using the preparation of p-doped glass powder that embodiment two obtains is printed on side length
156*156mm, is surveyed after the polysilicon solar battery slice front drying of 60~100 Ω of sheet resistance, sintering by 190 ± 10 μm of thickness
Determine the unit for electrical property parameters of solar battery.
Table 2 is that the positive silver paste used for solar batteries using the preparation of without phosphorus glass powder that the first comparative example two obtains prints
Brush is in side length 156*156mm, and 190 ± 10 μm of thickness, the polysilicon solar battery slice front drying of 60~100 Ω of sheet resistance,
The unit for electrical property parameters of solar battery is measured after sintering.
Table 3 is the positive silver paste used for solar batteries using first p-doped glass powder preparation that the second comparative example two obtains
It is printed on side length 156*156mm, 190 ± 10 μm of thickness, the polysilicon solar battery slice front of 60~100 Ω of sheet resistance is through drying
Dry, measurement solar battery after sintering unit for electrical property parameters.
Table 1
Table 2
Table 3
From table 1, table 2 and table 3 it is found that p-doped glass powder incident photon-to-electron conversion efficiency less p-doped glass powder is high, embodiment is utilized
The positive silver paste used for solar batteries of p-doped glass powder (the being named as rear p-doped glass powder) preparation of one preparation is printed on crystal silicon too
The sun of first p-doped glass powder preparation of the incident photon-to-electron conversion efficiency than utilizing the preparation of the second comparative example one when positive energy cell piece
Energy battery is printed on incident photon-to-electron conversion efficiency height when crystal silicon solar batteries piece with positive silver paste, illustrates that phosphorus doping can change light
Electrotransformation efficiency, but the doping efficiency of first p-doped glass powder is not high, p-doped glass powder prepared by embodiment one (is mixed after being named as
Phosphorus glass powder) pass through phosphorus diffusion, it can be achieved that higher doping efficiency.
Claims (10)
1. a kind of p-doped glass powder, it is characterised in that a kind of p-doped glass powder in parts by weight by 1 part~10 parts PbO, 15 parts~
30 parts of Bi2O3, 15 parts~25 parts of SiO2, 10 parts~35 parts of TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO, 5 parts~15 parts B2O3
It is prepared with 1 part~10 parts phosphorus sources.
2. a kind of p-doped glass powder according to claim 1, it is characterised in that the phosphorus source is phosphorus pentoxide, phosphoric acid
Hydrogen diammonium, ammonium dihydrogen phosphate, calcium monohydrogen phosphate, calcium phosphate, calcium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, acid pyrophosphoric acid
Sodium, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, sodium pyrophosphate, calcium dihydrogen phosphate, phosphoric acid, potassium dihydrogen phosphate, phosphoric acid hydrogen two
Potassium, sodium acid pyrophosphate, three defocusing phosphoric acid, potassium dihydrogen phosphate, potassium pyrophosphate, potassium tripolyphosphate, sodium metaphosphate, biphosphate
One of calcium, calcium dihydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate or in which several mixtures.
3. a kind of preparation method of p-doped glass powder as described in claim 1, it is characterised in that a kind of system of p-doped glass powder
Preparation Method is completed by the following steps:
One, 1 part~10 parts PbO, 15 parts~30 parts Bi are weighed in parts by weight2O3, 15 parts~25 parts of SiO2, 10 parts~35 parts
TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO, 5 parts~15 parts B2O3With 1 part~10 parts phosphorus sources；
Two, by weighed 1 part~10 parts PbO, 15 parts~30 parts Bi in step 12O3, 15 parts~25 parts of SiO2, 10 parts~35 parts
TeO2, 5 parts~15 parts of ZnO, 3 parts~5 parts MgO and 5 part~15 parts B2O3It is uniformly mixed, obtains mixed-powder；
Three, mixed-powder is placed in aluminium crucible, then aluminium crucible is placed in the high-temperature electric resistance furnace that temperature is 1200 DEG C~1400 DEG C
Melting 20min~60min, then aluminium crucible is quenched to room temperature in distilled water, obtain coarse glass frit；Coarse glass frit is passed through into gas
It flows pulverizer or mechanical crusher crushes, reuse distilled water and clean 5 times~8 times, then dried at being 60 DEG C~200 DEG C in temperature
It is dry, obtain the glass powder that partial size is 10 μm~15 μm；
Four, p-doped:
Partial size is uniformly mixed for 10 μm~15 μm of glass powder and 1 part~10 parts phosphorus sources, then passes through planetary ball mill or gas
It flows pulverizer to crush, reuses distilled water and clean 5 times~8 times, then dried at being 300 DEG C~400 DEG C in temperature, partial size is 3 μm
~5 μm of p-doped glass powder.
4. special using a kind of method that p-doped glass powder prepares positive silver paste used for solar batteries as described in claim 1
Sign is to be completed by the following steps using a kind of method that p-doped glass powder prepares positive silver paste used for solar batteries:
One, 1 part~4 parts p-doped glass powders, 80 parts~90 parts silver powder and 5 parts~10 parts organic carriers are weighed in parts by weight；
Two, weighed 1 part~4 parts p-doped glass powders, 80 parts~90 parts silver powder and 5 parts~10 parts organic carriers in step 1 are mixed
It closes uniformly to be placed on three rolling pulp grinders and grind, obtain positive silver paste used for solar batteries.
5. the method that a kind of p-doped glass powder according to claim 4 prepares positive silver paste used for solar batteries, feature
It is that silver powder described in step 1 is high tap density silver powder, the partial size of high tap density silver powder is 1 μm~2 μm, vibration density
Degree is > 5.0g/mL.
6. the method that a kind of p-doped glass powder according to claim 4 prepares positive silver paste used for solar batteries, feature
It is that organic carrier described in step 1 is prepared according to the following steps:
One, weighing:
40 parts~70 parts organic solvents, 1 part~8 parts thixotropic agent, 1 part~7 parts thickeners, 1 part~10 parts are weighed in parts by weight
Coupling agent, 1 part~10 parts surfactants and 1 part~5 parts lubricants；
Two, by weighed 40 parts~70 parts organic solvents in step 1,1 part~8 parts thixotropic agent, 1 part~7 parts thickeners, 1 part~
10 parts of coupling agents, 1 part~10 parts surfactants and 1 part~5 parts mix lubricants are uniform, then temperature be 100 DEG C~150 DEG C
Lower reaction 60min~200min, is cooled to room temperature, obtains organic carrier.
7. the method that a kind of p-doped glass powder according to claim 6 prepares positive silver paste used for solar batteries, feature
Be organic solvent described in step 1 be alcohol ester 12, terpinol, tributyl citrate, triethanolamine, butyl carbitol,
One of dimethyl glutarate, dimethyl adipate, repefral and oleic acid or in which several mixed liquors.
8. the method that a kind of p-doped glass powder according to claim 6 prepares positive silver paste used for solar batteries, feature
It is that thixotropic agent described in step 1 is fumed silica, organobentonite, rilanit special, polyamide wax or polyethylene
Wax；The polyethylene wax is Anjeka 4360.
9. the method that a kind of p-doped glass powder according to claim 6 prepares positive silver paste used for solar batteries, feature
It is that thickener described in step 1 is curdlan, methylcellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose
Sodium, hydroxyethyl cellulose, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, modified paraffin resin, card
Wave resin, polyacrylic acid, Polyacrylate Emulsion, butadiene rubber, butadiene-styrene rubber, polyurethane, modified polyurea and low molecule
One of polyethylene wax or in which several mixtures.
10. the method that a kind of p-doped glass powder according to claim 6 prepares positive silver paste used for solar batteries, feature
It is that coupling agent described in step 1 is butyl titanate, titanate esters crosslinking agent TA-9-2,3- (aminopropyl) triethoxy
Silane, 3- (trimethoxysilyl) -1- propylamine, 3- aminopropyltriethoxy diethoxy silane, diethylenetriamine base propyl three
One in methoxy silane, tert-butyl the third amino trimethoxy silane and 4- amino -3,3- dimethylbutyl trimethoxy silane
Kind or in which several mixtures；The surfactant is alkyl glycosides, fatty glyceride, sapn, tween and oleic acid
One of or in which several mixtures；The lubricant is fatty diglycollic amide, oleic acid and poly terephthalic acid
One of second diester or in which several mixtures.
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