CN101651155A - Composition and preparation method of silicon solar battery electrode slurry - Google Patents
Composition and preparation method of silicon solar battery electrode slurry Download PDFInfo
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Abstract
The invention relates to composition and a preparation method of silicon solar battery electrode slurry. The silicon solar battery electrode slurry comprises silicon solar battery sunny slope grid electrode silver slurry, back surface field silver-aluminium slurry and back surface field aluminium slurry which are used for preparing an ohm contact layer containing silicon alloy powder. In the invention, silver powder, aluminium powder, a simple substance element and the silicon alloy powder are used as raw materials, and an organic bond and an inorganic bond are used as accessories, and after the raw materials and the accessories are evenly mixed, a three-roller rolling mill is utilized to roll the mixture into the silicon solar battery electrode slurry of which the fineness is 20.0-25.0mum and the viscosity is 20000-40000mpa.s.
Description
One, technical field:
The present invention relates to a kind of composition and preparation method of electrode paste of silicon solar cell, is a kind ofly to prepare electronic information material with chemical method---the method for electrocondution slurry belongs to the chemical preparation technical field.
Two, background technology:
Silicon solar cell sunny slope grid silver slurry, back field aluminum paste, silver-colored aluminium paste belong to one of electronic information material, and solar energy is inexhaustible green energy resource.Silicon solar cell is one of them.In recent years silicon solar cell development both at home and abroad rapidly, only the output of China last year surpasses 2000MW.Sunny slope grid silver slurry is to form with electronation silver powder, interpolation ohmic contact simple substance element, glass dust, organic bond mixed rolling.A back of the body silver-colored aluminium paste is with electronation silver powder, aluminium powder, and other interpolation ohmic contact simple substance elements, glass dust, organic bond mixed rolling form.Back field aluminum paste is that the organic bond mixed rolling forms with aluminium powder, glass dust.The simple substance element that three kinds of slurries all require to add, aluminium powder generate alloy with matrix silicon in the high temperature and high speed sintering process, reduce the Schottky gesture Barrier of electrode and silicon interface, form potential well, electrode and silicon ohmic contact, thereby the electrical property of raising battery.But remove this and also require the silver-colored aluminium paste electrode soldering of the grid silver slurry back of the body, peeling force is qualified.Three kinds of slurries all require smooth surface, no bead, burr, gas blister, indeformable bending.
Known silver slurry has the PV149 product of du pont company and 33502 products of FERRO company, and silver-colored aluminium paste has 3398 products of U.S. FERRO company.Silver slurry, silver-colored aluminium paste that China has Kunming noble metal institute, Beijing Non-Fervoous Metal Inst., Shanghai East China University of Science to study are all unavailable.Aluminium paste has Chinese patent ZL200610011001.1 and ZL200610011050.5, the product that application number 200810047523.6 is produced, and they are silicon-containing alloy powder not.It is the price of every watt of power that silicon solar cell generating listing power supply network is popularized key, and the key of price is the cell photoelectric conversion efficiency., raise the efficiency except that purity of raw materials and preparation technology's improvement the manufacture of solar cells merchant, key is silver slurry, silver-colored aluminium paste and aluminium paste, and their main effect is to make the ohmic contact alloy layer, is only the output lead of battery then.People find that alloy-layer is thick more, and the efficient of battery is high more, and bending is just more little behind the battery sintering, and promptly alloy-layer has cushioned the bending that silicon, aluminium, silver-colored coefficient-of-linear-expansion difference cause.For this purpose, rely on the artificial simple substance functional element that adds in advance, under high temperature and high speed, can't realize.The conversion efficiency of battery is also relevant with the smooth degree of sunny slope grid, back of the body field plate in addition, the coverage rate of smooth electrodes and silicon is big more more, will improve the power of battery unit are, battery production merchant requires to eliminate bead, gas blister, burr and the shedding phenomenon of double-sided electrode, and not having arbitrary slurry production technology so far can solve.
Three, summary of the invention
The composition and the preparation method that the purpose of this invention is to provide a kind of electrode paste of silicon solar cell are a kind of silicon solar cell sunny slope grid silver pastes of ohmic contact layer of silicon-containing alloy powder formation, a back of the body silver-colored aluminum slurry, back field aluminum paste material.It is to be raw material with silver powder, aluminium powder, simple substance element and silicon alloy powder, after being aided with organic bond and inorganic binder and mixing, is rolled to fineness 20.0-25.0 μ m, viscosity 20000-40000mpas with three-high mill.Get product.
Described silver powder is that silver powder is commercially available purity 〉=99.95%, class sphere, average grain diameter 0.1-0.5 μ m.
The commercially available purity of described silicon alloy powder 〉=99.95%, the alloyed powder of average grain diameter 5 μ m.
Described elemental metals element powders is commercially available purity 〉=99.95%, average grain diameter 3-5 μ m, the simple substance element is that one of institute's column element is planted in the table 1, described silicon alloy powder is the alloyed powder (MSi) of listed simple substance element (M) and matrix element silicon in the table 1, this silicon alloy powder contains Si0.01-40 quality %, and surplus is the simple substance element.
Table 1:
| The simple substance element M | ??B、Al、Ga、In、Sb、Ni、Ge、P、Sn、Li、Cu、Mg、Ca、Sr、 ??Ba、Au、Mn、Zn、Ti、Pd、Pt |
| Matrix element | ??Si |
| The silicon alloy powder is formed M Si | Si=0.01-40% (mass percent) is surplus to be M |
Described inorganic binder is a glass dust, and its prescription is diboron trioxide (B
2O
3) 15-30 quality %, lead oxide (PbO) 40-70 quality %, vanadium pentoxide (V
2O
5) 1-5 quality %, silicon dioxide (SiO
2) 15-28 quality %, alundum (Al (A
2O
3) 3-6 quality %, total amount 100%.Its preparation technology is:
The glass powder for preparing is mixed, and the porcelain crucible of packing into after 500 ℃ of preheatings, is put into 1100-1250 ℃ of stove heating, is incubated shrend after 1.5 hours, oven dry, and broken back ball milling is to the glass powder of 5-8 μ m.
The prescription of described organic bond is ethyl cellulose 1.0-12.0 quality %, phenolic resins or novolac epoxy resin 0.5-10.0 quality %, rosin 0.1-2.0 quality %, calcium stearate or zinc stearate 1.0-10.0 quality %, terpinol 30-60 quality %, additive 25-50 quality %, total amount 100%.Described additive comprises one or more in ethylene glycol phenyl ether, diethyl phthalate, butyl carbitol, butyl carbitol acetate and the phenmethylol.Its preparation technology is: by above-mentioned prescription, 100-150 ℃ of heating for dissolving, get transparent organic bond.
The present invention implements by following technical scheme
1, sunny slope grid silver paste prescription and preparation method
(1) prescription: silver powder 70.～90 quality %, antimony powder 0.01～1.0 quality %, silicon alloy powder 1.0～5.0 quality %, modification organic bond 10～20 quality %, inorganic binder 1～10 quality %, total amount 100%.
(2) preparation method: by above-mentioned prescription weighing and mix, be rolling to granularity 2.0-5.0 μ m through three-high mill, viscosity 9.0-11.0 ten thousand mpas, sunny slope grid silver slurry product.
2, the prescription and the preparation method of a back of the body silver-colored aluminum slurry:
(1) prescription: silver powder 70.～90 quality .%, aluminium powder 1.0～5.0 quality %, silicon alloy powder 0.1～5.0 quality %, organic bond 10～20 quality %, inorganic binder 1～10 quality %, total amount 100%.
(2) preparation method: by above-mentioned prescription weighing and mix, compound is rolled to granularity≤10.0 μ m through three-high mill, and viscosity 9.0-11.0 ten thousand mpas must carry on the back a silver-colored aluminium paste product.
3, the prescription of back field aluminum paste material and preparation method
(1) prescription: aluminium powder 40-70 quality %, indium powder 0.01～5 quality %, organic bond 20～30 quality %, inorganic binder 0.1～15 quality %, silicon alloy powder 0.1～40 quality %, total amount 100%
(2) preparation method: by above-mentioned prescription weighing and mix, be rolled to granularity 20.0-25.0 μ m, viscosity 20000-40000mpas with three-high mill.Get back field aluminum paste material product.
Compare advantage and the good effect that has with known technology
(1) thickened alloy layer thickness.The present invention also adds the thickness of alloy-layer between thick electrode and the silicon artificially in the sintering fusing with the alloyed powder of silicon except sintering generates alloy-layer.Eliminate the Schottky gesture Barrier at electrode and interface, formed potential well, improved ohmic contact, reduced the solar cell series resistance, improved the photoelectric conversion efficiency of battery.
(2) the silicon alloy powder fusing of the present invention's adding is an endothermic process, and heat absorption is offset each other with heat release, and it is smooth to obtain electrode surface like this, silvery white or greyish white, no gas blister, bead and burr.Increased the coverage rate of electrode like this, flawless electrode has improved the electrical property of battery naturally.
(3) because the coefficient of linear expansion of silicon and aluminium, silver differs very big, battery sheet bending is mainly caused by silicon, aluminium, silver-colored coefficient of linear expansion difference behind the sintering.After adding the silicon alloy powder, silicon and aluminium, the alloy layer thickness between silicon and silver increases, and has cushioned the difference of coefficient of linear expansion, and the bending of battery sheet has diminished, and has improved the rate of finished products of product like this.
(4) in slurry, add the silicon alloy powder, improve ohmic contact, reduce series resistance, battery efficiency improves, the refuse battery sheet reduces, every watt of battery unit price descends like this, solar cell power generation factory is incorporated into the power networks with the market electrical network powers possibility, and this day can treat in the universal use of solar power generation in the people's livelihood so.
Four, embodiment
Embodiment 1: the preparation ball shape silver powder 78.0% of sunny slope silver grid slurry, antimony powder 0.20%, silication antimony powder (SbSi) 1.0%, contain Sb 99.4 quality % in the silication antimony powder, Si 0.6 quality %, glass dust 6.0%, organic bond 14.8%, compound is rolling to granularity 2.5 μ m through three-high mill, viscosity 10.2 ten thousand mpas.The side's of recording resistance 2.7m Ω/, linear resolution 0.123mm.With homemade FP-3HD aluminium paste, FERRO3398 silver aluminium paste coupling, through the high temperature and high speed sintering, surface silvery white, smooth, monocrystalline silicon original thickness 0.18mm, specification 125 * 125mm, bending＜1.0mm.The scolding tin good weldability, lead-in wire band peeling force 320g.Battery average light photoelectric transformation efficiency 17.28%.
Embodiment 2: a back of the body preparation with silver-colored aluminum slurry: ball shape silver powder 77.0%.Ball aluminum powder 3.2%.Silication bronze (AuSi) 0.8% contains Au 96.8 quality % in the silication bronze, Si 3.2 quality %, glass dust 6.0 quality %, organic bond 13.0 quality %.Compound is rolled to granularity 10.0 μ m, viscosity 9.7 ten thousand mpas through three-high mill.The side's of recording resistance 3.2m Ω/.With homemade FP-3HD aluminium paste, the PV149 of Du Pont silver slurry coupling, printing monocrystalline silicon original thickness 0.18mm, specification 125 * 125mm, through the high temperature and high speed sintering, the surface silvery white is smooth, and is smooth with the aluminium paste overlap joint, bending＜1.1mm welds good with the wide lead-in wire band of 1.6mm, scolding tin, peeling force 312g.Battery average light photoelectric transformation efficiency 17.32%.
Embodiment 3: back of the body field prepares with aluminum slurry: aluminium powder 70 quality %, and indium powder 0.5 quality %, organic bond 16 quality %, inorganic binder 4 quality %, silication manganese powder 9.5 quality % contain Mn 95 quality % in the silication manganese powder, Si 5 quality % total amounts 100%.By above-mentioned prescription weighing and mix, be rolled to granularity 22～25 μ m, viscosity 30000-40000mpas with three-high mill.Get back field aluminum paste material product.Obtain being greyish white, smooth behind the aluminum slurry sintering, the EVA bonding is qualified, the photoelectric conversion efficiency height.
Claims (4)
1, a kind of electrode paste of silicon solar cell, it comprises sunny slope grid silver paste, a back of the body silver-colored aluminum slurry and back field aluminum paste material is characterized in that:
1), sunny slope grid silver paste prescription: silver powder 70.～90 quality %, simple substance element antimony powder 0.01～1.0 quality %, silicon alloy powder 1.0～5.0 quality %, modification organic bond 10～20 quality %, inorganic binder 1～10 quality %, total amount 100%,
2), the prescription of the back of the body silver-colored aluminum slurry: silver powder 70.～90 quality .%, simple substance element aluminium powder 1.0～5.0 quality %, silicon alloy powder 0.1～5.0 quality %, organic bond 10～20 quality %, inorganic binder 1～10 quality %, total amount 100%,
3), the prescription of back field aluminum paste material: aluminium powder 40-70 quality %, simple substance element indium powder 0.01～5 quality %, organic bond 20～30 quality %, inorganic binder 0.1～15 quality %, silicon alloy powder 0.1～40 quality %, total amount 100%,
Described silver powder is commercially available purity 〉=99.95%, average grain diameter 0.1-0.5 μ m,
The commercially available purity of described silicon alloy powder 〉=99.95%, the alloyed powder of average grain diameter 5 μ m,
Described simple substance element powder is commercially available purity 〉=99.95%, average grain diameter 3-5 μ m, the simple substance element is a kind of among B, Al, Ga, In, Sb, Ni, Ge, P, Sn, Li, Cu, Mg, Ca, Sr, Ba, Au, Mn, Zn, Ti, Pd and the Pt, described silicon alloy powder is the alloyed powder (MSi) of simple substance element (M) and matrix element silicon, this silicon alloy powder contains Si 0.01-40 quality %, and surplus is the simple substance element.
2, according to the preparation method of the described electrode paste of silicon solar cell of claim 1, it is characterized in that:
1), sunny slope grid silver slurry preparation method: by above-mentioned prescription weighing and mix, be rolling to granularity 2.0-5.0 μ m through three-high mill, viscosity 9.0-11.0 ten thousand mpas, sunny slope grid silver paste product,
2), a back of the body silver-colored aluminium paste preparation method: by above-mentioned prescription weighing and mix, compound is rolled to granularity≤10.0 μ m through three-high mill, and viscosity 9.0-11.0 ten thousand mpas must carry on the back a silver-colored aluminum slurry product,
3), the back field aluminum paste preparation method for material: by above-mentioned prescription weighing and mix, be rolled to granularity 20.0-25.0 μ m with three-high mill, viscosity 20000-40000mpas, back field aluminum paste material product.
3, electrode paste of silicon solar cell according to claim 1 is characterized in that:
Described inorganic binder is a glass dust, and its prescription is B
2O
315-30 quality %, PbO 40-70 quality %, V
2O
51-5 quality %, SiO
215-28 quality %, A
2O
33-6 quality %, total amount 100%, the prescription of described organic bond is ethyl cellulose 1.0-12.0 quality %, phenolic resins or novolac epoxy resin 0.5-10.0 quality %, rosin 0.1-2.0 quality %, calcium stearate or zinc stearate 1.0-10.0 quality %, terpinol 30-60 quality %, additive 25-50 quality %, total amount 100%, described additive comprises one or more in ethylene glycol phenyl ether, diethyl phthalate, butyl carbitol, butyl carbitol acetate and the phenmethylol.
4, the preparation method of electrode paste of silicon solar cell according to claim 2 is characterized in that:
The preparation method of described glass dust is for to mix the glass powder for preparing, the porcelain crucible of packing into, after 500 ℃ of preheatings, put into 1100-1250 ℃ of stove heating, be incubated shrend after 1.5 hours, oven dry, broken back ball milling is to 5-8 μ m, the preparation method of described organic bond is: batch mixes is even, 100-150 ℃ of heating for dissolving, get transparent organic bond.
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