CN106007389B - A kind of crystal silicon solar batteries front side silver paste glass powder and preparation method thereof - Google Patents
A kind of crystal silicon solar batteries front side silver paste glass powder and preparation method thereof Download PDFInfo
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- CN106007389B CN106007389B CN201610315603.XA CN201610315603A CN106007389B CN 106007389 B CN106007389 B CN 106007389B CN 201610315603 A CN201610315603 A CN 201610315603A CN 106007389 B CN106007389 B CN 106007389B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
Abstract
The present invention provides a kind of crystal silicon solar batteries front side silver paste glass powders, which is characterized in that calculates, includes at least as mass fraction: 5~70%TeO2, 5~65%PbO, 1~30%Bi2O3, 0.05~2%TiO2, 0.1~5%R2O, 0.5~31%R ' O, 0.5~28%R " O, 0.005~15% modifying oxides MO, wherein the R is IA race alkali metal；R ' is at least one of Al, Zn, Ca or a variety of；R " is at least one of Si, P, B, Ge or a variety of；M is at least one of V B race element, VI B race element or a variety of；Crystal silicon solar batteries front side silver paste glass powder of the present invention, its list that can adapt to high square resistance, polysilicon chip use, with lower contact and series resistance, higher open-circuit voltage and efficiency, higher value of thrust, welding, ageing properties are preferable, and preparation method is simple, cost is relatively low.
Description
Technical field
The invention belongs to a kind of crystal silicon solar batteries front side silver paste glass powders and preparation method thereof, more specifically, this
Invention is related to crystal silicon solar positive silver paste tellurate glass material and preparation method thereof.
Background technique
Currently, commercialized solar energy front side silver paste is with glass frit technology mainly by Du Pont, Samsung, he Li Shi, large standing grain institute
Grasp, crystal silicon solar batteries are mainly tellurate glass system with positive silver paste with glass powder, be adapted to more high square resistance list,
Polysilicon chip has lower contact resistance and series resistance, higher open-circuit voltage and short circuit current performance, while can mention
For higher pulling force characteristic.But Du Pont's positive silver paste glass powder is relatively low on pulling force characteristic, Samsung positive silver paste glass
Powder has that contact resistance and string resistance are slightly higher, and the glass powder, preparation method thereof higher cost of offshore company, ball mill grinding work
Skill process is complex.
In view of the above-mentioned problems, now needing a kind of crystal silicon solar batteries front side silver paste glass powder, Gao Fang can adapt to
List, the polysilicon chip of resistance use, and have lower contact and series resistance, higher open-circuit voltage and efficiency, higher pulling force
Value, welding, ageing properties are preferable, and preparation method is simple, cost is relatively low.
Summary of the invention
To solve the above-mentioned problems, one aspect of the present invention provides a kind of crystal silicon solar batteries front side silver paste glass
Powder is calculated as mass fraction, is included at least:
TeO25~70%
PbO 5~65%
Bi2O31~30%
TiO20.05~2%
R2O 0.1~5%
R ' O 0.5~31%
R " O 0.5~28%
Modifying oxides MO 0.005~15%
Wherein, the R is IA race alkali metal；R ' is at least one of Al, Zn, Ca or a variety of；R " at least Si, P,
B, one of Ge or a variety of；M is at least one of V B race element, VI B race element or a variety of.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, R are at least Li, Na, K
One of or it is a variety of.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, R ' O and R " O press quality
Score calculates, and includes at least:
Al2O30.01~3%
ZnO 0.5~20%
CaO 0.01~8%
SiO20.1~10%
P2O50.05~5%
B2O30.2~10%
GeO20.01~3%.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, M be at least V, Nb, Ta,
One of Cr, Mo, W or a variety of.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, modifying oxides MO
It calculates, includes at least as mass fraction:
V2O50.1~3.0%
Nb2O50.01~4.0%
Ta2O50~3.0%
Cr2O30~3.0%
MoO30.1~8.0%
WO30.1~8.0%.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, modifying oxides MO
It calculates, includes at least as mass fraction:
V2O50.2~2.0%
Nb2O50.1~3.0%
Ta2O50.1~2.0%
Cr2O30.1~2.5%
MoO30.5~7.0%
WO30.5~7.0%.
Another aspect of the present invention provides a kind of preparation method of just silver-colored silver paste tellurate glass powder of crystal silicon solar, institute
The method of stating includes the following steps:
(1) each raw material is weighed respectively by mass fraction, is sufficiently mixed uniformly；
(2) raw material is fitted into crucible, and is put into high temperature box furnace and heats up, melted；
(3) again by the glass metal melted quenching in deionized water, cooling, filters pressing, drying；
(4) add water for ball milling, filters pressing, drying to get solar cell front side silver paste tellurate glass powder into glass.
In one embodiment, the preparation method of the crystal silicon solar positive silver paste tellurate glass powder, institute
Stating fusion temperature is 900-1300 DEG C.
In one embodiment, the preparation method of the crystal silicon solar positive silver paste tellurate glass powder, institute
The partial size D50 for stating solar cell front side silver paste tellurate glass powder is 0.1-1.5 μm.
In one embodiment, the preparation method of the crystal silicon solar positive silver paste tellurate glass powder, institute
The partial size D50 for stating solar cell front side silver paste tellurate glass powder is 0.1-1.0 μm.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand
Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.
One aspect of the present invention provides a kind of crystal silicon solar batteries front side silver paste glass powder, as mass fraction
It calculates, includes at least:
TeO25~70%
PbO 5~65%
Bi2O31~30%
TiO20.05~2%
R2O 0.1~5%
R ' O 0.5~31%
R " O 0.5~28%
Modifying oxides MO 0.005~15%
Wherein, the R is IA race alkali metal；R ' is at least one of Al, Zn, Ca or a variety of；R " at least Si, P,
B, one of Ge or a variety of；M is at least one of V B race element, VI B race element or a variety of.
Preferably, the crystal silicon solar batteries front side silver paste glass powder, calculates as mass fraction, includes at least:
TeO235~70%
PbO 30~50%
Bi2O34~30%
TiO20.5~2%
R2O 0.1~5%
R ' O 3~31%
R " O 0.5~28%
Modifying oxides MO 0.05~15%.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, R are at least Li, Na, K
One of or it is a variety of.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, R ' O and R " O press quality
Score calculates, and includes at least:
Al2O30.01~3%
ZnO 0.5~20%
CaO 0.01~8%
SiO20.1~10%
P2O50.05~5%
B2O30.2~10%
GeO20.01~3%；
Preferably, the crystal silicon solar batteries front side silver paste glass powder, O is calculated as mass fraction by R ' O and R ", until
Include: less
Al2O30.08~3%
ZnO 1.0~20%
CaO 0.5~8%
SiO20.5~10%
P2O50.08~5%
B2O30.6~10%
GeO20.05~3%.
Tellurate glass is mainly to aoxidize hoof (TeO2) glass as glass network former.TeO2It is primarily present α-
TeO2With β-TeO2Two kinds of crystal forms；Both crystal forms are can mutual phase transition at a temperature of certain.In both crystal forms, tellurium from
The ligancy of son is 4, and tellurium ion and oxonium ion constitute [TeO4] double triangular pyramids.An apex angle on the cone equatorial plane is by tellurium
The lone pair electrons of ion occupy；Two oxonium ions occupy the another two apex angle on the equatorial plane, form Te-Oeq key；Another two oxygen
Ion is located on axial position, forms Te-Oax key.
Tellurate glass can regard α-TeO as2A kind of structure for being disturbed of ordered structure exist in this configuration
Two kinds of tellurium oxygen keys, Te-Oeq indicate tellurium oxygen key on face under the line, and Te-Oax indicates the tellurium oxygen key in axial face；[TeO] double triangles
It is mutually connected with each other using top connection type altogether between cone, finally connects into three-dimensional network space structure.And in β-TeO2In,
[TeO4] four Te-O keys in suspension body bond distance it is each unequal, [TeO4] double triangular pyramids are using rib altogether or top connection altogether
Mode connects, and ultimately forms two-dimensional layered structure.
The calculation formula of each vertex freedom degree of glass network structure unit
f=d-Cav{δ-[δ(δ+1)/2V]} (1)
In formula (1), f represents the number of degrees of freedom, of coordination polyhedrom each point, and d represents space dimensionality, usually takes 3, Cav table
Show the coordination polyhedrom number on a public vertex, δ represents the dimension of coordination polyhedrom and V represents the vertex of coordination polyhedrom
Number.
Glass can be stabilized, and the mean freedom f for constituting each vertex of coordination polyhedrom of glass, which has to be larger than, to be equal to
0.Such as by taking silica glass as an example, constitute glass structural unit be [SiO4] tetrahedron, according to formula (1) obtain formula f=
3-2 [3-3* (3+1)/(2*4)]=0, the freedom degree on each vertex is 0 on the tetrahedron, meets mean freedom f and has to be larger than
Requirement equal to 0, therefore silica forms glass and can be stabilized.
It is if being entirely [TeO that the structural unit of glass is constituted in tellurium oxide glass4] double triangular pyramids.Due in this pair
There are lone pair electrons in triangular pyramids, therefore in [TeO4] double triangular pyramids in each vertex averagely have 9/5 coordination more
Face body is connected thereto, and the freedom degree on each vertex is brought into obtain formula and be obtained according to formula (1): f=3-9/5 [3-3* (3+1)/
(2*5)]=- 6/25, calculated result show the mean freedom on each vertex of double triangular pyramids less than 0, therefore, single dioxy
That changes tellurium can not form stable glass.In order to obtain stable tellurate glass, it is necessary to some other ions be added to oxidation
In tellurium.When so that the mean freedom of the coordination polyhedrom of the internal group in glass being met more than or equal to 0, it could prepare in this way
Stable glass out.
In TeO2Different oxides is added in glass and promotes TeO2Glass is formed, reason is not quite similar.
When to TeO2Li is added in glass2The alkaline earth oxides such as the basic anhydride such as O and calcium oxide are conducive to tellurium oxide
The generation of glass.This is mainly that the promotion of these alkali and alkaline earth metal ions provides a large amount of free oxonium ion, so that tellurium oxygen
Average coordination number can reduce.Te-O-Te chain is broken, so that [TeO4] double pyrometric cones are first changed into [TeO3+1] coordination multi-panel
Body intermediate state, is finally changed into [TeO3] triangular pyramids, while these alkali and alkaline earth metal ions cation dispersions are matched in tellurium oxygen
Play balancing charge in polyhedron gap in position.In addition, Li ion, Na ion and Ca ion have lesser ionic radius,
Multi-phonon relaxation effect can be effectively suppressed, strong IR fluorescence radiation is generated.
Body is formed when the traditional networks such as silica, diboron trioxide and phosphorus pentoxide are added into tellurate glass,
It can promote the formation of glass network, while also improve the chemical stability of glass, due to Si4+、B3+、P5+Ion itself is
Network former, therefore they can form coordination polyhedrom with oxonium ion in glass and participate in network, therefore cannot provide free
Oxonium ion makes [TeO4] double pyrometric cones are to [TeO3] triangular pyramids and [TeO3+1] coordination polyhedrom transformation.But since they itself are
Glass former just promotes the formation of glass, while also promoting the raising of mean freedom.Therefore, it is also beneficial to glass
It is formed.
The common valence state of Bi ion has+3(such as Bi2O3) and+5 valence (such as NaBiO3), wherein more stable valence state is+3
Valence.In general, Bi3+[ BiO is generated in glass3, and Bi5+Then generate [ BiO6Coordination structure.[ BiO3Eigen vibration
Absorption peak is located at 841cm-1, [ BiO6Eigen vibration absorption peak be located at 420~480cm-1。
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, M be at least V, Nb, Ta,
One of Cr, Mo, W or a variety of.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, modifying oxides MO
It calculates, includes at least as mass fraction:
V2O50.1~3.0%
Nb2O50.01~4.0%
Ta2O50~3.0%
Cr2O30~3.0%
MoO30.1~8.0%
WO30.1~8.0%.
In one embodiment, the crystal silicon solar batteries front side silver paste glass powder, modifying oxides MO
It calculates, includes at least as mass fraction:
V2O50.2~2.0%
Nb2O50.1~3.0%
Ta2O50.1~2.0%
Cr2O30.1~2.5%
MoO30.5~7.0%
WO30.5~7.0%.
Introduce heavy metallic oxide WO3And Nb2O5, so that a variety of vibration levels in glass is fused into broader band structure, with
Phase obtains bigger Raman gain bandwidth, and the multicomponent tellurate glass being formed simultaneously also is expected to increase substantially the anti-analysis of glass
Brilliant thermal stability.
There are mainly two types of coordination structures, i.e. [WO in glass for tungsten oxide6] octahedra and [WO4] tetrahedral structural unit.
[WO6] octahedra as Network modifier, it can connect the tellurium oxygen chain in glass, reinforce the chain-shaped network knot of tellurate glass
Structure;[WO4] tetrahedron is then used as Network former, directly participate in the building of glass network, therefore 920cm-1The reinforcing of Raman peaks
Show W6+Ion is mainly with [WO4] form of tetrahedral structural unit enters in tellurate glass network structure, become glass web
Network forms body, makes tellurate glass close structure, improves the open-circuit voltage performance of crystal silicon solar batteries.
W6+Ion has biggish electronegativity, can obtain free oxygen and with [WO4] tetrahedral structural unit form into
Enter in glass network structure, the network connection of fracture is got up, therefore, with WO3Doping increases, and the oxo anion of tungsten gathers
Collection, enhances the compactness of glass network structure, increases the viscosity of glass, improve the anti-crystallization thermal stability of glass.
Nb2O5It is a kind of good glass formers, and there is very high refractive index, refractive index is up to 2.1.Therefore, in glass
A small amount of Nb is added in glass component2O5The refractive index of glass can effectively be adjusted.
Nb5+The electronegativity of ion is up to 1.6, strong to the attraction power of electronics, can be by multiple [TeO4] double triangular pyramids,
[TeO3+1] distortion triangular pyramids and [TeO3] triangular pyramids structural unit constrains in Nb5+Around ion, make glass network structure
More complete, fine and close, the anti-crystallization thermal stability of glass improves.
Rare earth Ta2O5With good chemical stability, thermal stability and electrical properties, and with integrated circuit processing work
Skill has excellent compatibility.Rare earth ion Ta5+It is melted in glass phase, but is difficult to enter network as glass generation ion,
It may be that the effect of structural network modified ion is in high ligancy (6 or 8 or 8 or more).It can according to the ratio between zwitterion radius
Judge Ta5+For Gao Peiwei, except structural network, and its ionic charge is high, field strength is big, has stronger accumulation to act on, is
Glass structure is close, to increase the viscosity of glass metal, improves sintering temperature.
Molybdenum and wolfram element radius due to lanthanide contract are very close, but the ionic radius of molybdenum ion is slightly less than tungsten
Ionic radius then increases WO3Lattice defect, lattice defect be in electronegativity, become the trap center in hole, improve electricity
Sub- hole reduces electron hole pair coincidence rate to separative efficiency.
V in modifying oxides MO2O5、Nb2O5、Ta2O5、Cr2O3、WO3Between act synergistically, promote tellurate glass knot
Structure is close, to improve the open-circuit voltage performance of crystal silicon solar batteries.
Another aspect of the present invention provides a kind of preparation method of crystal silicon solar positive silver paste tellurate glass powder, institute
The method of stating includes the following steps:
(1) each raw material is weighed respectively by mass fraction, by being sufficiently mixed uniformly, obtains mixed original
Material；
(2) raw material mixed is fitted into high purity aluminium oxide crucible, crucible is put into high temperature box furnace again at room temperature
Middle heating is melted 0.5-1 hours in 900-1300 DEG C of at a temperature of heat preservation, obtains uniform clear glass melts；
(3) by the glass metal melted quenching in deionized water, glass particle is taken out after cooling, in 120 DEG C of baking ovens
It is dry；
(4) ball milling, addition deionized water use the big mill of diameter 10-30mm to the glass for obtaining drying in the ball mill
Ball, ball milling 2-6 hours；
(5) abrading-ball is taken out into the obtained glass powder solution sieving of step 4, reuses the small abrading-ball of diameter 1-5mm, is added
Appropriate amount of deionized water, ball milling 0.5-4 hours；
(6) glass powder and water mixed liquid obtained step 5 carries out sieving and takes out small abrading-ball, obtains glass powder and water mixing
Liquid；
(7) glass powder and water mixed liquid obtained step 6 is put into the convection oven that set temperature is 120 DEG C and carries out
It is sufficiently dry, obtain solar cell front side silver paste glass powder of the present invention.
In one embodiment, the preparation method of the crystal silicon solar positive silver paste tellurate glass powder, institute
Stating fusion temperature is 900-1300 DEG C;Preferably, the fusion temperature is 900-1100 DEG C.
In one embodiment, the preparation method of the crystal silicon solar positive silver paste tellurate glass powder, institute
The partial size D50 for stating solar cell front side silver paste tellurate glass powder is 0.1-1.5 μm.
In one embodiment, the preparation method of the crystal silicon solar positive silver paste tellurate glass powder, institute
The partial size D50 for stating solar cell front side silver paste tellurate glass powder is 0.1-1.0 μm；Preferably, the solar battery
The partial size D50 of front side silver paste tellurate glass powder is 0.2-0.8 μm.
In one embodiment, the solar cell front side silver paste is with the specific surface area of tellurate glass powder
1.0~5.0m2/g;Preferably, the specific surface area of the solar cell front side silver paste tellurate glass powder be 1.5 ~
4.0m2/g。
The high glass powder of vitrifying degree has the advantage that (1) glass compared to crystal, there is one between solid phase and liquid phase
A viscous state has very big adhesion strength, due to the presence of this pilot process, when using glass as high-temperature agglomerant
It is that film layer can be attached on substrate well；(2) glass platform is metastable state, so the identical substance of constituent, glass
The energy of state is higher than crystalline state, and the energy difference of the higher glassy state of energy is smaller, and glassy state at relatively low temperature can
To there is liquid phase, and under liquid phase environment, chemical activity and diffusion velocity are all much higher than solid phase reaction, be more advantageous to reaction into
Capable and substance migration, and liquid phase can infiltrate solid phase, can equally increase adhesive force.Therefore, solar battery front side is starched
Material has to height with glass powder vitrifying degree.
During the sintering process, glass powder starts to soften front side silver paste after reaching certain temperature, and glass powder penetrates antireflective coating,
There is competition of both the dissolution of Argent grain and sintering during this, the softening temperature of glass powder is higher, and the reaction time gets over
It is short, it is then bigger with the response area of Argent grain；Reaction time, which shortens, can reduce the sintering effect of Argent grain, and the increasing of response area
Be conducive to Argent grain greatly to be dissolved in liquid Pb, the former makes the glassy layer between Argent grain and Si matrix surface (be set as b1) become
Thin, the latter makes the glassy layer between Argent grain and Argent grain (be set as b2) thicken.
Rc=ρI/ d+ ρT/ a(2)
In formula: ρIIt is the intrinsic resistivity of silver powder；D is the diameter of contact point；ρTIt is tunnel resistor rate；A is contact area.
As can be seen that recrystallization Argent grain size is bigger from formula (2), resistivity is smaller.When softening temperature is higher, glassy layer b1Very
It is thin, quantum tunneling effect occurs, resistivity becomes smaller, however, glassy layer b2It is thicker, when hindering the transmission of electric current, and reacting
Between it is short, lead to recrystallize that silver-colored crystallite dimension is small, and resistivity becomes larger, so softening temperature cannot be too high.When softening temperature is lower, glass
Glass powder good fluidity, the reaction time is longer, and sintering effect is more preferable, and recrystallization Argent grain size is bigger, and glassy layer b2It is thinning,
Resistivity is small, and series resistance then becomes smaller.But softening temperature is too low, such as 200 DEG C or so or when being lower than 200 DEG C, glass powder is too early
Softening, it is long in the liquid duration, it is easy to cause emitter to puncture, and since mobility is excessively good, easily deposit under Argent grain,
Contact of the Argent grain with silicon chip is hindered, series resistance is increased.Series resistance has fill factor FF and photoelectric conversion efficiency
The series resistance of very big influence, solar battery is smaller, then fill factor is bigger；Series resistance is bigger, short circuit current decline
More, fill factor is smaller (open-circuit voltage does not influence).It can be seen from photoelectric conversion efficiency formula (formula (3)) with
Fill factor, short circuit current decline, photoelectric conversion efficiency decline.
η=ImVm/Pin=FFIscVoc/Pin (3)
In formula: η is photoelectric conversion efficiency, ImFor maximum power point electric current, VmFor maximum power point voltage, PinFor sunlight
Input power, FF are fill factor, IscFor short circuit current, VocFor open-circuit voltage.
Due to the scrupulously and respectfully point that glass powder is not fixed, therefore using glass transition temperature (Tg) Lai Hengliang of measurement glass powder
There is the temperature of liquid phase in glass powder.
Heat analysis is carried out to original glass powder by function compensation type Differential Scanning Calorimeter, surveys and draws DSC curve.Power-compensation
DSC is a kind of skill that the energy difference of unit time varies with temperature between measurement of species and reference substance under programed temperature
Art.Principle and differential thermal analysis are substantially similar, except that two group benefits of the device below sample and reference substance container are utilized
Repay sintering silk.When sample during the sintering process, when occurring temperature difference △ T due to thermal response, pass through differential thermal amplification and differential heat
Compensation makes the electric current for flowing into compensation silk change.When sample heat absorption, compensation increases the electric current on sample one side immediately.Instead
It, in sample heat release increases then the electric current on reference substance one side, until both sides heat balance, until temperature difference △ T disappears.
In order to enhance absorption of the solar battery sheet to sunlight, one layer of antireflective on the town Dou Hui of crystal silicon solar battery front
Film, chemical component SiNx other than requiring good adhesive force, must also when glass powder is used for solar cell front side silver paste
Antireflective coating must be penetrated and form good Ohmic contact.Require glass powder can be with antireflection layer during sintering in this way
Reaction, and take Argent grain to silicon face and form good Ohmic contact.
Glass powder mainly influences the series resistance (Rs) and open-circuit voltage (Voc) of solar battery sheet, and then influences too
Transfer efficiency (the E of positive energy batteryff), for solar battery sheet, the series resistance (Rs) of cell piece is the smaller the better, open circuit
The higher the better for voltage (Voc), transfer efficiency (Eff) the higher the better.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from Guangzhou Chemical Reagent Factory.
Embodiment 1
(1) each raw material is weighed respectively by mass fraction, by being sufficiently mixed uniformly, obtains mixed original
Material；
(2) raw material mixed is fitted into high purity aluminium oxide crucible, crucible is put into high temperature box furnace again at room temperature
Middle heating is melted 0.75 hour in 1000 DEG C of at a temperature of heat preservation, obtains uniform clear glass melts；
(3) by the glass metal melted in deionized water 200g quenching, take out glass particle after cooling, dried at 120 DEG C
It is 20 hours dry in case；
(4) by the obtained glass of drying ball milling in the ball mill, deionized water is added, using the big abrading-ball of diameter 15mm,
Abrading-ball revolving speed 425r/min, ball milling 4 hours；
(5) abrading-ball is taken out into the obtained glass powder solution sieving of step 4, reuses the small abrading-ball of diameter 2mm, is added suitable
Amount deionized water, abrading-ball revolving speed 425r/min, ball milling 3 hours；
(6) glass powder and water mixed liquid obtained step 5 carries out sieving and takes out small abrading-ball, obtains glass powder and water mixing
Liquid；
(7) glass powder and water mixed liquid obtained step 6 is put into the convection oven that set temperature is 120 DEG C and carries out
It is sufficiently 24 hours dry, then be sieved with 200-400 mesh, obtain solar cell front side silver paste glass of the present invention
Powder.
Embodiment 2~11
The preparation method is the same as that of Example 1, only the difference of inventory and the type that feeds intake, and specific difference is shown in Table 1.
Comparative example 1~5
The preparation method is the same as that of Example 1, only the difference of inventory and the type that feeds intake, and specific difference is shown in Table 1.
The setting of 1 embodiment of table
Performance test:
1, it is tested using NETZSCH STA 449C thermal analyzer, experiment condition is under nitrogen protection atmosphere in 0-
1000 DEG C of temperature ranges, with heating rate for l0 DEG C of min-1It is detected, determines glass powder glass transition temperature (Tg).
2, the electric performance test of solar battery sheet is carried out using 3i SYSTEM solar battery sorter.The mark of test
Quasi is the solar cell test standard on ground: spatial distribution when air quality is AM1.5, the incident sun
Linchpin illumination is 1000W/m2, temperature is 25 DEG C.Solar battery output power is just defined as the peak of solar battery under this condition
Wattage is indicated, the series resistance (Rs) of solar battery sheet, the transfer efficiency of solar battery with symbol WP (peakwatt)
(Eff)。
Photoelectric conversion efficiency formula:
η=ImVm/Pin=FFIscVoc/Pin (3)
In formula: η is photoelectric conversion efficiency, ImFor maximum power point electric current, VmFor maximum power point voltage, PinFor sunlight
Input power, FF are fill factor, IscFor short circuit current, VocFor open-circuit voltage.
3, glass powder particle diameter distribution uses Micro-Plus type laser particle size analyzer, and a small amount of glass powder is dispersed in water
After then dispersing using ultrasonic wave, the calibration and analysis of glass powder granularity are carried out with laser particle size analyzer.
4, the test of electrode sintered membrane adhesive force is to draw welding (width along 180 degree direction on cell piece primary gate electrode
(1.6 ± 0.1) mm), welding uses 30W electric iron, and coating tin-lead welding, (HLSn63PbA or HLSn63PbB, welding should meet
The regulation of GB/T3131), weld interval is no more than 3S, measures its pulling force with 0~50N of range, the puller system that precision is ± 5%
Value.
2 the performance test results of table
In conclusion it is found that crystal silicon solar batteries front slurry tellurate glass material of the invention is matched with difference
The TeO of ratio2、PbO、Bi2O3, alkali metal (Li, Na, K), MO(V2O5、Nb2O5、Ta2O5、Cr2O3、MoO3、WO3) and different grains
The glass powder of diameter is compared, and has lower contact and series resistance, higher open-circuit voltage and efficiency, higher pulling force
Value.
The above embodiments are merely illustrative, some features of feature for explaining the present invention.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the combined selection of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature, and the progress in science and technology will be formed language express it is inaccurate due to and
The possible equivalent that is not presently considered or son replacement, and these variations should also be interpreted in the conceived case it is appended
Claim covering.
Claims (2)
1. a kind of crystal silicon solar batteries front side silver paste glass powder, which is characterized in that calculate, include at least as mass fraction:
Wherein, the R is IA race alkali metal；The sum of described each component is 100%；
O is calculated as mass fraction by the R ' O and R ", is included at least:
The modifying oxides MO is calculated as mass fraction, is included at least:
2. crystal silicon solar batteries front side silver paste glass powder described in claim 1, which is characterized in that R is at least Li, Na, K
One of or it is a variety of.
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| CN106601335B (en) * | 2016-12-30 | 2018-08-31 | 无锡帝科电子材料科技有限公司 | It is used to prepare the paste composition, electrode of solar battery and solar cell of electrode of solar battery |
| CN107216041B (en) * | 2017-05-04 | 2020-09-25 | 无锡帝科电子材料股份有限公司 | Glass frit for preparing solar cell electrode, paste composition comprising same, solar cell electrode and solar cell |
| CN107117824A (en) * | 2017-05-18 | 2017-09-01 | 江苏东昇光伏科技有限公司 | A kind of lead-free glass powder used for solar batteries and preparation method thereof |
| CN107746184B (en) * | 2017-10-20 | 2020-11-24 | 苏州晶银新材料股份有限公司 | Glass powder composition, conductive silver paste containing glass powder composition and preparation method of conductive silver paste |
| CN111302636A (en) * | 2018-12-11 | 2020-06-19 | 苏州晶银新材料股份有限公司 | Glass powder composition, conductive silver paste containing glass powder composition and solar cell |
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| CN110590168A (en) * | 2019-10-28 | 2019-12-20 | 四川东树新材料有限公司 | Glass material for crystalline silicon solar cell, preparation method thereof and silver paste |
| CN112777938B (en) * | 2019-11-11 | 2023-03-17 | 江西佳银科技有限公司 | Glass powder for crystalline silicon solar front silver paste and preparation method and application thereof |
| CN112777935A (en) * | 2019-11-11 | 2021-05-11 | 江西佳银科技有限公司 | Glass powder containing nano silver and preparation method thereof |
| CN111732342B (en) * | 2020-08-07 | 2022-12-27 | 上海银浆科技有限公司 | Glass component and crystalline silicon solar cell conductive silver paste containing same |
| CN112592068B (en) * | 2020-12-15 | 2022-11-15 | 广州市儒兴科技股份有限公司 | Glass powder, preparation method thereof and application of glass powder in TOPCon battery |
| CN112723750A (en) * | 2021-01-22 | 2021-04-30 | 上海银浆科技有限公司 | Glass powder for high-adhesion high-contact front silver paste and preparation method thereof |
| CN112960908B (en) * | 2021-02-04 | 2023-03-28 | 江苏日御光伏新材料科技有限公司 | Glass powder and preparation method thereof |
| CN113045207B (en) * | 2021-03-10 | 2022-04-01 | 浙江奕成科技有限公司 | Glass powder for TOPCON crystalline silicon solar cell back silver paste and preparation method thereof |
| CN113345621A (en) * | 2021-04-23 | 2021-09-03 | 常州聚和新材料股份有限公司 | Glass material for solar cell conductive paste, conductive paste and solar cell |
| CN113698103B (en) * | 2021-08-26 | 2023-03-28 | 浙江光达电子科技有限公司 | Glass powder for front silver electrode of PERC crystalline silicon solar cell and preparation method thereof |
| CN114057393B (en) * | 2021-11-16 | 2022-11-18 | 海南大学 | Glass negative electrode material and preparation method and application thereof |
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