CN106876502B - A kind of method that 3D inkjet printings prepare HIT electrodes - Google Patents
A kind of method that 3D inkjet printings prepare HIT electrodes Download PDFInfo
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- CN106876502B CN106876502B CN201710167092.6A CN201710167092A CN106876502B CN 106876502 B CN106876502 B CN 106876502B CN 201710167092 A CN201710167092 A CN 201710167092A CN 106876502 B CN106876502 B CN 106876502B
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- 238000007641 inkjet printing Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 42
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000007639 printing Methods 0.000 claims abstract description 31
- 239000007921 spray Substances 0.000 claims abstract description 16
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 49
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- 239000000463 material Substances 0.000 claims description 41
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- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention relates to a kind of methods that 3D inkjet printings prepare HIT electrodes, utilize 3D inkjet printing technologies, the front on HIT solar cells first using two different formula of size to forming TCO films carries out inkjet printing twice and dries acquisition front electrode, then inkjet printing is carried out to the back side in the same way and obtains backplate, finally cured.The present invention reduces the uses of silver, have saved battery cost, and spraying printing twice reduces contact resistance and line resistance respectively, improves photoelectric conversion efficiency.In addition, HIT electrode fabrications only need low-temperature sintering, heating energy consumption is reduced, the energy, ink good dispersion obtained, stability height are saved, the phenomenon that agglomerated particle blocks spray printing hole in ink can be substantially reduced, has the characteristics that production cost is low, process equipment is simple, preparation process green high-efficient.
Description
Technical field
The present invention relates to a kind of preparation methods of electrode of solar battery, are prepared more particularly, to a kind of 3D inkjet printings
The method of HIT electrodes.
Background technology
Inkjet printing technology is a kind of contactless, no pressure, the conventional printing techniques without printing plate, is conventionally used in paper substrates
Font, in pattern printing, pattern is generally Two-dimensional morphology, and spray printing material is carbon-based ink or organic and inorganic salt material
Color inks.With the combination of rapid shaping technique and printing technique, there is three-dimensional printing technology (3D printing), it can will be each
Kind organic and inorganic functional material forms the vertical of specific form structure without mask, non-contactly successively printing is piled up in substrate surface
Shape can be function element, part, model, even human organ or bone etc..Original can be saved using 3D printing technique
Material is realized from computer design pattern straight forming, shortens the R＆D cycle, can quickly, neatly change design.Printer sheet
The manufacture of body is relatively easy, and which kind of being selected, the material of printing is suitble to realize objective function, becomes the pass of 3D printing technique development
Key.
Since eighties of last century oil crisis, each state all carrys out alleviating energy crisis in a kind of new energy of discussion.Solar-electricity
Pond directly converts sunlight to electric power, is a kind of clean energy resource, thus this novel energy is increasingly concerned.With too
The promotion of positive energy cell photoelectric transfer efficiency, the cost of photovoltaic generation have been approached thermal power generation cost, state in sunny place
Border energy administration prediction solar power generation amount accounts for about the 16% of global generated energy in the year two thousand fifty, will be the main shape of future source of energy acquisition
One of formula.There are many types, wherein HIT solar cells to have high conversion efficiency for solar cell, and preparation process is simple, and temperature is low
The features such as, it is one of low price battery of large-scale application.Advantage of the HIT solar cells in preparation process and material, in addition its
High conversion efficiency, therefore there is preferable development prospect.
Similar with crystal silicon solar batteries, in industrialized production, the surface metalation of HIT solar cells also uses silver
Silk-screen printing technique is starched, therefore electrode fabrication is one of the critical process of HIT solar cells.The method for making electrode mainly has
Vacuum evaporation, plating, silk-screen printing etc., the wherein silk-screen printing of silver paste and low-temperature sintering are used in current HIT battery productions
Process.Silver electrode is distributed in battery surface in H-type finger-like, filament (thin grid) collected current, thick line (main grid) export electricity
Stream.To improve the performance of HIT batteries, need to consider the following aspects in electrode fabrication：1. silver electrode is shared by front
Area determines the size of light-receiving surface, is inversely proportional with photoelectric conversion efficiency of the solar battery, therefore, shading-area answer it is as small as possible,
Thin grid and main grid are as narrow as possible, to improve the J of batterysc；2. the internal resistance of silver electrode should be as low to improve delivery efficiency as possible, in body
Under resistivity same case, grid line is as high as possible, increases cross-sectional area to reduce electrode internal resistance, between electrode and battery surface
Contact resistance size should be as low as possible, generally directly proportional to electrode primary granule size 3. to use high quality, low-resistance grid line
Electrode material, to improve the FF of battery, grid line resistance and the electrode primary granule size of general battery are inversely proportional.
HIT batteries determine that its sintering temperature can only be selected at 200 DEG C or so due to the characteristic of amorphous silicon membrane
Slurry must be low-temperature pulp, require that higher electric conductivity should be reached using low-temperature pulp, the contact resistance between TCO thin film
It is low again.Currently, can be applied to the low temperature silver pastes of HIT batteries, there are two types of types.One is thermoplasticity slurry, solvent content compared with
It is more, need control sintering temperature to prevent solvent hold-up in the contact area of electrode and silicon chip.The heating of this slurry is then started to gather
Solidification is closed, while being conducive to that long chain polymer molecules is made to move freely, and cooling then reduces this movement.Another kind is thermosetting property
Slurry, its performance are then entirely different.In heat curing process, thermosetting polymer formationization between adjacent polymer chain
Key is learned, three-dimensional net structure is resulted in, it is firmer than the two-dimensional structure that thermoplasticity slurry is formed.
In silk screen process technology, about 30-45 microns of the trepanning of web plate, after slurry single printing-sintering, width is micro- in 50-60
Rice is even broader, and height is generally at 12-20 micron, and the ratio of height and the width is 0.4 hereinafter, and since printing mesh blocks up
Plug has the possibility that electrode breaks.If using inkjet printing technology, accumulation molding is successively printed, it can be with formation width 30-50
The thin grid line of micron, 30-50 microns of height, depth-width ratio can accomplish 1, can reduce shading-area, reduce electrode internal resistance and carry
High conversion efficiency, while also reducing silver paste consumption.Its moulding mechanism is, inkjet print head is by ink jet printing to base material battery
On piece, at 150-200 DEG C, ink droplet is ejected into cell piece surface solvent and waves rapidly cell piece surface temperature due to being heated base station
Hair, remaining solid particle are accumulated on surface, and repeatedly in same local spray printing, grid line will gradually increase and line width is kept not
Become.
Traditional HIT electrode fabrications are typically based on screen printing technique, for example Chinese invention patent, application publication number
CN102738302A discloses a kind of forming method of HIT electrode of solar battery, its main feature is that forming the HIT of ito film too
On positive energy battery, the tow sides using secondary printing technology in battery print gate line electrode, wherein the second printing
Main grid silver paste it is lower than the silver content of the thin grid silver paste of the first printing.Though this method reduces cost, continue secondary
The advantages of printing technology, but still there are problems that silk-screen printing.For another example, Chinese invention patent, application publication number
CN103887348A discloses a kind of HIT solar cel electrodes and preparation method thereof, and feature is will according to certain spacing
Wire on the metal filament, is then pulled to above battery surface by wire-drawing frame and is covered by a certain amount of conducting resinl apposition, from
And constitute the thin gate line electrode of series of parallel arrangement.And its primary gate electrode still uses silk-screen printing technique, and its is heat treated
The temperature of Cheng Suoxu is higher than 200 DEG C, does not meet the low-temperature sintering requirement of HIT electrodes.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of 3D inkjet printing systems
The method of standby HIT electrodes, can save silver paste dosage, reduce production cost；Improve grid line depth-width ratio to reduce shielded area, from
And improve transfer efficiency；In addition, preparation process process equipment is simple, green high-efficient.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method that 3D inkjet printings prepare HIT electrodes is used two different first using 3D inkjet printing technologies
Front on HIT solar cells of the formula of size to forming TCO films carries out inkjet printing twice and dries acquisition front electrode,
Then inkjet printing is carried out to the back side in the same way and obtains backplate, finally cured.
Specifically, using inkjet print head by conductive ink spray printing to base material cell piece, base station heats simultaneously, battery
Piece surface temperature is at 100-200 DEG C, and ink droplet is ejected into cell piece surface solvent and volatilizees rapidly, and remaining solid particle is in surface heap
Product, repeatedly in same local spray printing, grid line will gradually increase and line width remains unchanged.
The conductive ink of first time inkjet printing is prepared using following components and parts by weight content：
Nano-Ag particles 1-55, organic solvent 40-99, dispersant 0.1-10, surfactant 0.1-5, thermosetting resin
0.1-10；
The conductive ink of second of inkjet printing is prepared using following components and parts by weight content：
Nano-Ag particles 1-55, organic solvent 40-99, dispersant 0.1-10, surfactant 0.1-5.
As preferred embodiment, the particle size range of nano-Ag particles in the conductive ink of first time inkjet printing<
50nm, it is preferred to use grain size is the nano-Ag particles of 40nm, and the parts by weight of addition are 35-45.Nano-Ag particles are smaller, unit plane
Nano-Ag particles are more in product, and contact points of the nano silver with battery surface are more, keep contact resistance smaller.Second of ink-jet is beaten
The particle size range of nano-Ag particles is 50-100nm in the conductive ink of print, it is preferred to use grain size is the nano-Ag particles of 60nm,
The parts by weight of addition are 35-45.Nano-Ag particles are big, and electric conductivity is good, and the nano particle volume that when sintering is discharged is few, and line is made to hinder
It reduces.The grain size of nano-Ag particles should be much smaller than the nozzle diameter of print head in spray printing device, ensure the solid in ink
Spray nozzle clogging will not be influenced the continuity of spray printing by particle, to greatly improve the quality and production efficiency of product.Nano silver
Compared with blocky silver, there is the specific surface area of bigger, the atomicity of unit area is more, and the population of unit volume is more, is burning
It during knot, is merged between particle and particle, surface disappears, if grain size is too small, can cause have a large amount of cavities, mistake in electrode body
Small nano silver is also easier to reunite and result in blockage, and the present invention distinguishes the nano silver of preferable particle size 40nm and 60nm in printing twice
Have the effect of excellent.For solid content, content is low to be unfavorable for improving silver layer deposition efficiency, unit volume in excessively high then ink
Interior silver granuel subnumber is excessive, is easy to be formed and reunite, currently preferred nano-Ag particles parts by weight are 35-45.
As preferred embodiment, organic solvent boiling point is 100-150 DEG C, surface tension 20-35dyn/cm, the ink
Solvent is different from normal ink, closely related with its technique.The spray printing of the ink accumulates temperature at 120-200 DEG C, using routine
Ink system, ink droplet can cannot be molded in substrate surface bumping；If selecting high boiling solvent, ink droplet can expand in substrate surface
It dissipates, causes lines wide, to influence the transfer efficiency of battery.Surface tension is too low, needs to turn down jet-printing head voltage, it is possible to
Ink droplet is set to be atomized in course of injection, nozzle surface and showerhead plate can build up ink and influence normal spray printing；Surface tension is excessively high,
Need the voltage of raising jet-printing head, it is possible to occur flying black phenomenon and cause nozzle service life reduction.
It is further preferred that organic solvent is selected from isobutanol, ethylene glycol-methyl ether, glycol-ether, isopropanol, propionic acid third
It is one or more in ester, acetic acid, butyl acetate, acetamide, pyridine, 3- ethylaminoethanols, butyl butyrate or epoxychloropropane.
The dispersant is selected from polyvinyl alcohol, polyethylene glycol, polyamide, polyurethane, polycarboxylic acids, polyvinylpyrrolidone
Or it is one or more in polymethylacrylic acid.Dispersant makes nano-powder particle be arranged mutually with certain same sex charge
Reprimand, to which stable suspersion is in dicyandiamide solution.
The surfactant be selected from polyvinylpyrrolidone, dodecyl sodium sulfate, polyacrylamide, stearic acid,
It is one or more in triethanolamine, lauric acid or polyoxyethylene ether.Surfactant is suitble to for adjusting ink surface tension
Inkjet printing requirement.
The particle diameter distribution of thermosetting resin is within 100nm, preferably 40-60nm, more preferably 50nm.
The ingredient of thermosetting resin is selected from phenolic resin, Lauxite, melamine formaldehyde resin, epoxy resin, insatiable hunger
With it is one or more in resin, polyurethane, polyimides.
Conductive ink is prepared using following methods：
(1) by organic solvent and dispersant, it is warming up to 70-100 DEG C, stirring 1-5min to mixture is transparent molten
Liquid；
(2) when preparing the conductive ink of first time inkjet printing, the temperature of clear solution obtained by step (1) is down to 20-
25 DEG C, nano-Ag particles are added, after stirring 30min, open the long and narrow reaction tube that the outlet valve of bottom makes mixed liquor flow to lower part
It is interior, it opens ultrasonic stick and carries out ultrasound.Ultrasound wave vibrating bar is 3-5 times of ultrasonic stick diameter at a distance from reaction kettle tube wall, ultrasound
Wave vibrating head is more than 1.5 times of agitating paddle single page diameter at a distance from mixing component.When ultrasonic vibration stick is inserted directly into liquid, surpass
When sound wave directly acts on liquid internal, ultrasound cavitation effect is will produce, under its effect, will produce inside scattered substance
Powerful explosion, convection current, stirring, broken, mixing phenomena, it is evenly dispersed to achieve the purpose that.If ultrasonic vibration stick institute is in place
It sets with tube wall apart from too small, ultrasonic wave directly acts on tube wall, and the cavitation effect generated to dispersion liquid is limited；If away from
From excessive, since ultrasonic cavitation generates around vibrating head, and energy is highly uniform is distributed in around stick, then cavitation
Effect can be declined at away from ultrasonic stick farther out range, and whole dispersion effect is caused to decline.When opening ultrasound, open simultaneously anti-
Should the outlet valve of pipe lower end, circulating pump, reaction kettle inlet valve, respectively keep material slow into and out of the control valve at material mouth by control
It circulates, control material temperature is maintained at 20-45 DEG C, and material is after persistent loop, stirring, ultrasound 1-2 hours, into material
Thermosetting resin is heated, continues cycling through, stir, ultrasound 1-2 hours, obtaining the nano silver mixed liquor of first time inkjet printing；
(3) when preparing the conductive ink of second of inkjet printing, the temperature of clear solution obtained by step (1) is down to 20-
25 DEG C, nano-Ag particles are added, after stirring 30min, open the long and narrow reaction tube that the outlet valve of bottom makes mixed liquor flow to lower part
It is interior, it opens ultrasonic stick and carries out ultrasound.Ultrasound wave vibrating bar is 3-5 times of ultrasonic stick diameter at a distance from reaction kettle tube wall, ultrasound
Wave vibrating head is more than 1.5 times of agitating paddle single page diameter at a distance from mixing component.When ultrasonic vibration stick is inserted directly into liquid, surpass
When sound wave directly acts on liquid internal, ultrasound cavitation effect is will produce, under its effect, will produce inside scattered substance
Powerful explosion, convection current, stirring, broken, mixing phenomena, it is evenly dispersed to achieve the purpose that.If ultrasonic vibration stick institute is in place
It sets with tube wall apart from too small, ultrasonic wave directly acts on tube wall, and the cavitation effect generated to dispersion liquid is limited；If away from
From excessive, since ultrasonic cavitation generates around vibrating head, and energy is highly uniform is distributed in around stick, then cavitation
Effect can be declined at away from ultrasonic stick farther out range, and whole dispersion effect is caused to decline.When opening ultrasound, open simultaneously anti-
Should the outlet valve of pipe lower end, circulating pump, reaction kettle inlet valve, respectively keep material slow into and out of the control valve at material mouth by control
It circulates, control material temperature is maintained at 20-45 DEG C, and material obtains second after persistent loop, stirring, ultrasound 1-2 hours
The nano silver mixed liquor of secondary inkjet printing；
(4) obtained nano silver mixed liquor in step (2) and step (3) is mixed respectively with surfactant, is stirred
Uniformly, control mixed liquor surface tension is 20-40mN/m, viscosity 1-4cP, and it is 0.22 μm or 0.45 μm of micropore then to use aperture
Membrane filtration, removal obtain stable nano silver jet conductive ink after precipitating.
(5) two different nano silver jet conductive inks obtained by step (4) are subjected to ink-jet twice to front electrode
It prints, is dried after first time inkjet printing, second of inkjet printing is then carried out to electrode using the slurry different from first time
And it dries；Wherein, the slurry of second of inkjet printing is compared to unused thermosetting resin in the formula of size of first time；Then
Inkjet printing is carried out to backplate in the same way, is finally cured.
Compared with prior art, the HIT electrodes prepared using the present invention reduce the use of silver, have saved battery cost,
And spraying printing twice reduces contact resistance and line resistance respectively, improves photoelectric conversion efficiency.In addition, HIT electrode fabrications are only
Low-temperature sintering is needed, heating energy consumption is reduced, has saved the energy.Ink good dispersion obtained, stability is high, can substantially reduce ink
Agglomerated particle blocks the phenomenon that spray printing hole in water, with production cost is low, process equipment is simple, preparation process green high-efficient spy
Point.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
It takes 40.05g ethylene glycol-methyl ether to be added in reaction kettle, the dissolving of 1.20g polyvinyl alcohol is weighed wherein, using adding
Material in reactor temperature is heated to 100 DEG C by hot pin, is stirred transparent solution after 3min, after being cooled to room temperature, is slowly added to
The nano-Ag particles of 8.01g30nm after stirring 30min, open reaction kettle, reaction tube into and out of material mouth and circulating pump, material are made to follow
Circulation is dynamic, opens simultaneously stirring, Vltrasonic device, and cooling water is passed through to the temperature control outside reaction tube.Material persistently follows
Ring, stirring, ultrasound add phenolic resin into material after 1.5 hours, continue stirring, ultrasound 1.5 hours, are added into dispersion liquid
0.40g dodecyl sodium sulfates, be further continued for stirring, ultrasonic disperse 0.5 hour black mixed liquor, use 0.22 μm of filter membrane to carry out
Filtering removes precipitation, obtains the nano silver jet conductive ink for the stabilization of first time inkjet printing.After tested, get Qi Biao
Face tension is 32.255mN/m, viscosity 3.0cP, and room temperature is preserved and do not settled for 2 months.
On the HIT solar cells for forming TCO films, using nano silver jet conductive ink produced above to positive electricity
Pole carries out first time inkjet printing and dries.
It takes 40.05g ethylene glycol-methyl ether to be added in reaction kettle, the dissolving of 1.20g polyvinyl alcohol is weighed wherein, using adding
Material in reactor temperature is heated to 100 DEG C by hot pin, is stirred transparent solution after 3min, after being cooled to room temperature, is slowly added to
The nano-Ag particles of 8.01g30nm after stirring 30min, open reaction kettle, reaction tube into and out of material mouth and circulating pump, material are made to follow
Circulation is dynamic, opens simultaneously stirring, Vltrasonic device, and cooling water is passed through to the temperature control outside reaction tube.Material persistently follows
0.40g dodecyl sodium sulfates are added into dispersion liquid after 1.5 hours for ring, stirring, ultrasound, are further continued for stirring, ultrasonic disperse
0.5 hour black mixed liquor, be filtered using 0.22 μm of filter membrane, remove precipitation, obtained for second inkjet printing
Stable nano silver jet conductive ink.After tested, it is 32.255mN/m, viscosity 3.0cP, room temperature preservation to obtain its surface tension
It does not settle within 2 months.
On the electrode for having carried out first time inkjet printing the is carried out using nano silver jet conductive ink produced above
Secondary inkjet printing is simultaneously dried.
Then inkjet printing is carried out to backplate in the same way, is finally cured.
Embodiment 2
It takes 38.54g glycol-ethers to be added in reaction kettle, weighs the dissolving of 1.16g polyethylene glycol wherein, at room temperature
It is in homogeneous transparent solution after stirring 3min, is slowly added to the nano-Ag particles of 7.71g50nm, after stirring 30min, opens reaction
Kettle, reaction tube make Matter Transfer flow into and out of material mouth and circulating pump, open simultaneously stirring, Vltrasonic device, and cooling water is led to
Enter the temperature control outside reaction tube.Material persistent loop, stirring, ultrasound add Lauxite into material after 1 hour, after
Continuous stirring, ultrasound 1.5 hours, 0.19g polyacrylamides are added into dispersion liquid, continue stirring, ultrasonic disperse 0.5 hour, mix
It is in brownish black to close liquid, which is filtered with 0.45 μm of filter membrane to get to the stabilization for first time inkjet printing
Nano silver jet conductive ink.After tested, it is 30.980mN/m, viscosity 2.8cP, room temperature preservation 2 to obtain its surface tension
The moon does not settle.
On the HIT solar cells for forming TCO films, using nano silver jet conductive ink produced above to positive electricity
Pole carries out first time inkjet printing and dries.
It takes 38.54g glycol-ethers to be added in reaction kettle, weighs the dissolving of 1.16g polyethylene glycol wherein, at room temperature
It is in homogeneous transparent solution after stirring 3min, is slowly added to the nano-Ag particles of 7.71g50nm, after stirring 30min, opens reaction
Kettle, reaction tube make Matter Transfer flow into and out of material mouth and circulating pump, open simultaneously stirring, Vltrasonic device, and cooling water is led to
Enter the temperature control outside reaction tube.It is poly- that 0.19g is added into dispersion liquid after 1 hour for material persistent loop, stirring, ultrasound
Acrylamide, continues stirring, ultrasonic disperse 0.5 hour, and mixed liquor is in brownish black, which is carried out with 0.45 μm of filter membrane
Filtering is to get to obtaining the nano silver jet conductive ink for second of inkjet printing.After tested, obtaining its surface tension is
30.980mN/m, viscosity 2.8cP, room temperature are preserved 2 months and are not settled.
On the electrode for having carried out first time inkjet printing the is carried out using nano silver jet conductive ink produced above
Secondary inkjet printing is simultaneously dried.
Then inkjet printing is carried out to backplate in the same way, is finally cured.
Embodiment 3
By following components and content dispensing：
Later, following steps is taken to prepare the nano silver jet conductive ink for first time inkjet printing：
(1) by organic solvent and dispersant, 70 DEG C are warming up to, stirring 1min to mixture is clear solution；
(2) after above-mentioned clear solution being cooled to 20 DEG C, nano-Ag particles are added and simultaneously stir 30min, then with ultrasound stick into
Row ultrasound, temperature are controlled at 20 DEG C, and thermosetting resin is added in ultrasound after 1 hour, then 1 hour ultrasonic, obtains nano silver mixed liquor；
(3) nano silver mixed liquor is mixed with surfactant, is stirred evenly, control mixed liquor surface tension is 20mN/
M, viscosity 1cP, the filtering with microporous membrane for being then 0.22um with aperture, removal obtain beating for first time ink-jet after precipitating
The nano silver jet conductive ink of print.
On the HIT solar cells for forming TCO films, using nano silver jet conductive ink produced above to positive electricity
Pole carries out first time inkjet printing and dries.
By following components and content dispensing：
Later, following steps is taken to prepare the nano silver jet conductive ink for second of inkjet printing：
(1) by organic solvent and dispersant, 70 DEG C are warming up to, stirring 1min to mixture is clear solution；
(2) after above-mentioned clear solution being cooled to 20 DEG C, nano-Ag particles are added and simultaneously stir 30min, then with ultrasound stick into
Row ultrasound, temperature are controlled at 20 DEG C, and ultrasound obtains nano silver mixed liquor after 1 hour；
(3) nano silver mixed liquor is mixed with surfactant, is stirred evenly, control mixed liquor surface tension is 20mN/
M, viscosity 1cP, the filtering with microporous membrane for being then 0.22um with aperture, removal obtain beating for second of ink-jet after precipitating
The nano silver jet conductive ink of print.
On the electrode for having carried out first time inkjet printing the is carried out using nano silver jet conductive ink produced above
Secondary inkjet printing is simultaneously dried.
Then inkjet printing is carried out to backplate in the same way, is finally cured.
Embodiment 4
By following components and content dispensing：
Later, following steps is taken to prepare the nano silver jet conductive ink for first time inkjet printing：
(1) by organic solvent and dispersant, 100 DEG C are warming up to, stirring 5min to mixture is clear solution；
(2) after above-mentioned clear solution being cooled to 25 DEG C, nano-Ag particles are added and simultaneously stir 30min, then with ultrasound stick into
Row ultrasound, temperature are controlled at 45 DEG C, and thermosetting resin is added in ultrasound after 2 hours, then 2 hours ultrasonic, obtains nano silver mixed liquor；
(3) nano silver mixed liquor is mixed with surfactant, is stirred evenly, control mixed liquor surface tension is 40mN/
M, viscosity 4cP, the filtering with microporous membrane for being then 0.45um with aperture, removal obtain beating for first time ink-jet after precipitating
The nano silver jet conductive ink of print.
On the HIT solar cells for forming TCO films, using nano silver jet conductive ink produced above to positive electricity
Pole carries out first time inkjet printing and dries.
By following components and content dispensing：
Later, following steps is taken to prepare the nano silver jet conductive ink for second of inkjet printing：
(1) by organic solvent and dispersant, 100 DEG C are warming up to, stirring 5min to mixture is clear solution；
(2) after above-mentioned clear solution being cooled to 25 DEG C, nano-Ag particles are added and simultaneously stir 30min, then with ultrasound stick into
Row ultrasound, temperature are controlled at 45 DEG C, and ultrasound obtains nano silver mixed liquor after 2 hours；
(3) nano silver mixed liquor is mixed with surfactant, is stirred evenly, control mixed liquor surface tension is 40mN/
M, viscosity 4cP, the filtering with microporous membrane for being then 0.45um with aperture, removal obtain beating for second of ink-jet after precipitating
The nano silver jet conductive ink of print.
On the electrode for having carried out first time inkjet printing the is carried out using nano silver jet conductive ink produced above
Secondary inkjet printing is simultaneously dried.
Then inkjet printing is carried out to backplate in the same way, is finally cured.
Embodiment 5
By following components and content dispensing：
Later, following steps is taken to prepare the nano silver jet conductive ink for first time inkjet printing：
(1) by organic solvent and dispersant, 80 DEG C are warming up to, stirring 3min to mixture is clear solution；
(2) after above-mentioned clear solution being cooled to 23 DEG C, nano-Ag particles are added and simultaneously stir 30min, then with ultrasound stick into
Row ultrasound, temperature are controlled at 35 DEG C, and oxide component is added in ultrasound after 1.5 hours, then 1.5 hours ultrasonic, and it is mixed to obtain nano silver
Close liquid；
(3) nano silver mixed liquor is mixed with surfactant, is stirred evenly, control mixed liquor surface tension is 30mN/
M, viscosity 3cP, the filtering with microporous membrane for being then 0.45um with aperture, removal obtain beating for first time ink-jet after precipitating
The nano silver jet conductive ink of print.
On the HIT solar cells for forming TCO films, using nano silver jet conductive ink produced above to positive electricity
Pole carries out first time inkjet printing and dries.
By following components and content dispensing：
Later, following steps is taken to prepare the nano silver jet conductive ink for second of inkjet printing：
(1) by organic solvent and dispersant, 80 DEG C are warming up to, stirring 3min to mixture is clear solution；
(2) after above-mentioned clear solution being cooled to 23 DEG C, nano-Ag particles are added and simultaneously stir 30min, then with ultrasound stick into
Row ultrasound, temperature are controlled at 35 DEG C, and ultrasound obtains nano silver mixed liquor after 1.5 hours；
(3) nano silver mixed liquor is mixed with surfactant, is stirred evenly, control mixed liquor surface tension is 30mN/
M, viscosity 3cP, the filtering with microporous membrane for being then 0.45um with aperture, removal obtain beating for second of ink-jet after precipitating
The nano silver jet conductive ink of print.
On the electrode for having carried out first time inkjet printing the is carried out using nano silver jet conductive ink produced above
Secondary inkjet printing is simultaneously dried.
Then inkjet printing is carried out to backplate in the same way, is finally cured.
The electrode prepared by the above method is tested.Wherein, 35.6 μm of front electrode height, width are 45 μm,
Depth-width ratio is 0.79,4.2 μ Ω cm of resistivity；46 μm of backplate height, width are 35 μm, depth-width ratio 0.76, resistivity
4μΩ·cm.Manufactured HIT batteries are tested, pressure ratio conventional screen printed battery is opened and improves 2mv, short circuit current increases
0.13A, photoelectric conversion efficiency increase by 0.4%.Silver paste consumption reduces 30% simultaneously.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of method that 3D inkjet printings prepare HIT electrodes, which is characterized in that this method utilizes 3D inkjet printing technologies, first
First the front on the HIT solar cells using two different formula of size to forming TCO films carries out twice that inkjet printing is simultaneously
Drying obtains front electrode, and then carrying out inkjet printing to the back side in the same way obtains backplate, is finally cured
；
The conductive ink of first time inkjet printing is prepared using following components and parts by weight content：
Nano-Ag particles 1-55, organic solvent 40-99, dispersant 0.1-10, surfactant 0.1-5, thermosetting resin 0.1-
10；
The conductive ink of second of inkjet printing is prepared using following components and parts by weight content：
Nano-Ag particles 1-55, organic solvent 40-99, dispersant 0.1-10, surfactant 0.1-5；
The conductive ink of first time inkjet printing is prepared using following methods：
(1) organic solvent is mixed with dispersant in reaction tube, is warming up to 70-100 DEG C, stirring 1-5min to mixture is
Bright solution；
(2) after above-mentioned clear solution being cooled to 20-25 DEG C, nano-Ag particles is added and stir 30min, then carried out with ultrasonic stick
Ultrasound, ultrasonic stick are 3-5 times of ultrasonic stick diameter at a distance from reaction tube wall, and temperature is controlled at 20-45 DEG C, and ultrasonic 1-2 is small
When after be added thermosetting resin, then ultrasound 1-2 hours obtains nano silver mixed liquor；
(3) nano silver mixed liquor being mixed with surfactant, is stirred evenly, control mixed liquor surface tension is 20-40mN/m,
Viscosity is 1-4cP, and it is 0.22 μm or 0.45 μm of filtering with microporous membrane then to use aperture, and stable receive is obtained after removal precipitation
The silver-colored jet conductive ink of rice；
The conductive ink of second of inkjet printing is prepared using following methods：
(1) organic solvent in reaction tube is mixed into mixing with dispersant, is warming up to 70-100 DEG C, stirring 1-5min to mixture
For clear solution；
(2) after above-mentioned clear solution being cooled to 20-25 DEG C, nano-Ag particles is added and stir 30min, then carried out with ultrasonic stick
Ultrasound, ultrasonic stick are 3-5 times of ultrasonic stick diameter at a distance from reaction tube wall, and temperature is controlled at 20-45 DEG C, and ultrasonic 1-2 is small
Shi Hou obtains nano silver mixed liquor；
(3) nano silver mixed liquor being mixed with surfactant, is stirred evenly, control mixed liquor surface tension is 20-40mN/m,
Viscosity is 1-4cP, and it is 0.22 μm or 0.45 μm of filtering with microporous membrane then to use aperture, and stable receive is obtained after removal precipitation
The silver-colored jet conductive ink of rice.
2. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that utilize ink-jet
By on conductive ink spray printing to base material cell piece, base station heats print head simultaneously, and cell piece surface temperature is at 100-200 DEG C, ink
Drop is ejected into cell piece surface solvent and volatilizees rapidly, and remaining solid particle is accumulated on surface, repeatedly in same local spray printing, grid
Line will gradually increase and line width remains unchanged.
3. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that spray for the first time
The particle size range of nano-Ag particles in the conductive ink of ink printing<The parts by weight of 50nm, addition are 35-45；Second of ink-jet is beaten
The grain size of nano-Ag particles is 50-100nm in the conductive ink of print, and the parts by weight of addition are 35-45.
4. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that spray for the first time
The grain size of nano-Ag particles is 40nm in the conductive ink of ink printing；Nano-Ag particles in the conductive ink of second of inkjet printing
Grain size be 60nm.
5. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that described has
The boiling point of solvent is 100-150 DEG C, surface tension 20-35dyn/cm, selected from isobutanol, ethylene glycol-methyl ether, ethylene glycol-
Ether, isopropanol, propyl propionate, acetic acid, butyl acetate, acetamide, pyridine, 3- ethylaminoethanols, butyl butyrate or epoxy chloropropionate
It is one or more in alkane.
6. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that point
Powder is in polyvinyl alcohol, polyethylene glycol, polyamide, polyurethane, polycarboxylic acids, polyvinylpyrrolidone or polymethylacrylic acid
It is one or more.
7. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that the table
Face activating agent be selected from polyvinylpyrrolidone, dodecyl sodium sulfate, polyacrylamide, stearic acid, triethanolamine, lauric acid or
It is one or more in polyoxyethylene ether.
8. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that the heat
The particle diameter distribution of thermosetting resin is within 100nm, using phenolic resin, Lauxite, melamine formaldehyde resin, asphalt mixtures modified by epoxy resin
It is one or more in fat, unsaturated-resin, polyurethane or polyimides.
9. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that the heat
The grain size of thermosetting resin is 50nm.
10. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, which is characterized in that spray for the first time
The step of conductive ink of ink printing (2), specifically uses following methods：
The temperature of clear solution obtained by step (1) is down to 20-25 DEG C, nano-Ag particles are added, after stirring 30min, opens bottom
The outlet valve in portion makes mixed liquor flow in the long and narrow reaction tube of lower part, opens ultrasonic stick and carries out ultrasound, while to outside reaction tube
Lead to cooling water in temperature control, and opens the outlet valve of reaction tube lower end, circulating pump, reaction kettle inlet valve, it is each by controlling
Material is set slowly to circulate into and out of the control valve at material mouth, control material temperature is maintained at 20-45 DEG C, and material is through persistently following
Ring, stirring, ultrasound heat thermosetting resin into material after 1-2 hours, continue cycling through, stir, ultrasound 1-2 hours, obtaining nanometer
Silver-colored mixed liquor；
The step of conductive ink of second of inkjet printing (2), specifically uses following methods：
The temperature of clear solution obtained by step (1) is down to 20-25 DEG C, nano-Ag particles are added, after stirring 30min, opens bottom
The outlet valve in portion makes mixed liquor flow in the long and narrow reaction tube of lower part, opens ultrasonic stick and carries out ultrasound, while to outside reaction tube
Lead to cooling water in temperature control, and opens the outlet valve of reaction tube lower end, circulating pump, reaction kettle inlet valve, it is each by controlling
Material is set slowly to circulate into and out of the control valve at material mouth, control material temperature is maintained at 20-45 DEG C, and material is through persistently following
Ring, stirring, ultrasound obtain nano silver mixed liquor after 1-2 hours.
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| CN108749327A (en) * | 2018-08-30 | 2018-11-06 | 广东工业大学 | A kind of method and apparatus making electrode using ink jet printing method |
| CN110828597B (en) * | 2019-10-30 | 2021-06-29 | 深圳市百柔新材料技术有限公司 | Solar cell string and preparation method thereof |
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