CN106876502A - 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 PDF

Info

Publication number
CN106876502A
CN106876502A CN201710167092.6A CN201710167092A CN106876502A CN 106876502 A CN106876502 A CN 106876502A CN 201710167092 A CN201710167092 A CN 201710167092A CN 106876502 A CN106876502 A CN 106876502A
Authority
CN
China
Prior art keywords
nano
inkjet
printing
conductive ink
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710167092.6A
Other languages
Chinese (zh)
Other versions
CN106876502B (en
Inventor
熊胜虎
张继平
黄俊皓
袁晓
柳翠
叶晓军
李红波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN201710167092.6A priority Critical patent/CN106876502B/en
Publication of CN106876502A publication Critical patent/CN106876502A/en
Application granted granted Critical
Publication of CN106876502B publication Critical patent/CN106876502B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022408Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41JTYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005Typewriters 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
    • B41J2/01Ink jet
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Abstract

The present invention relates to a kind of method that 3D inkjet printings prepare HIT electrodes, using 3D inkjet technologies, is carried out by inkjet printing twice and acquisition front electrode is dried for the front on the HIT solar cells for forming TCO films using two kinds of different formula of size first, then inkjet printing is carried out to the back side in the same way and obtains backplate, finally solidified.The present invention reduces the use of silver, battery cost is saved, and spraying printing twice reduces contact resistance and line resistance respectively, improves photoelectric transformation efficiency.Additionally, HIT electrode fabrications only need low-temperature sintering, heating energy consumption is reduced, the energy is saved, obtained ink good dispersion, stability is high, the phenomenon that agglomerated particle in ink blocks spray printing hole can be substantially reduced, the characteristics of with low production cost, simple process equipment, preparation process green high-efficient.

Description

A kind of method that 3D inkjet printings prepare HIT electrodes
Technical field
The present invention relates to a kind of preparation method of electrode of solar battery, prepared more particularly, to a kind of 3D inkjet printings The method of HIT electrodes.
Background technology
Inkjet technology is a kind of contactless, no pressure, the conventional printing techniques without printing plate, is conventionally used in paper substrates Font, pattern printing on, its 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, three-dimensional printing technology (3D printing) is occurred in that, can respectively The organic and inorganic functional material of kind is without mask, non-contactly successively printing is piled up in substrate surface, forms the vertical of specific form structure Shape, can be function element, part, model, even human organ or bone etc..Original can be saved using 3D printing technique Material, realizes from computer design pattern straight forming, shortens the R&D cycle, can quick, neatly change design.Printer sheet The manufacture of body is relatively easy, and the material which kind of is selected be adapted to printing realizes objective function, the pass as 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 Sunshine is directly converted into electric power by pond, is a kind of clean energy resource, thus this novel energy increasingly receives much concern.With too The lifting of positive energy cell photoelectric conversion efficiency, the cost of photovoltaic generation is sunny local close to thermal power generation cost, state Border energy administration prediction solar power generation amount accounts for the 16% of global generated energy in the year two thousand fifty, will be the main shape that future source of energy is obtained One of formula.Solar cell has numerous species, and wherein HIT solar cells have high conversion efficiency, and preparation process is simple, 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 technology and material, adds it High conversion efficiency, therefore with preferable development prospect.
Similar with crystal silicon solar batteries, in industrialized production, the surface metalation of HIT solar cells is also adopted by silver Slurry silk-screen printing technique, therefore electrode fabrication is one of critical process of HIT solar cells.The method for making electrode mainly has The silk-screen printing of vacuum evaporation, plating, silk-screen printing etc., wherein silver paste and low-temperature sintering are used in current HIT battery productions Process.Silver electrode is distributed in battery surface in H types finger-like, fine rule (thin grid) collected current, and thick line (main grid) derives 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 smooth surface, is inversely proportional with photoelectric conversion efficiency of the solar battery, therefore, shading-area should be 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, is typically directly proportional to electrode primary granule size and 3. uses 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 due to the characteristic of amorphous silicon membrane determine its sintering temperature can only at 200 DEG C or so, therefore select Slurry must be low-temperature pulp, should reach electric conductivity higher using low-temperature pulp requirement, the contact resistance between TCO thin film It is low again.At present, the low temperature silver paste that can be applied to HIT batteries has two types.One kind is thermoplasticity slurry, its solvent compared with It is many, it is necessary to control the sintering temperature to prevent solvent hold-up in electrode and the contact area of silicon chip.The heating of this slurry is then started to gather Solidification is closed, while be conducive to moving freely long chain polymer molecules, and cooling then reduces this movement.Another kind is thermosetting Slurry, its performance is 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 perforate of web plate, after slurry single printing-sintering, width is micro- in 50-60 Rice is even broader, and height is general at 12-20 microns, and the ratio of its height and the width is blocked up below 0.4 due to printing mesh Plug, there is the possibility that electrode breaks.If using inkjet technology, successively printing accumulation molding, width 30-50 can be formed Micron, height 30-50 microns of thin grid line, 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, ink jet-print head is by ink spray printing to base material battery On piece, because base station heats reason cell piece surface temperature at 150-200 DEG C, ink droplet is ejected into cell piece surface solvent and waves rapidly Hair, in surface sediment, repeatedly in same local spray printing, grid line will progressively increase remaining solid particle and line width keeps 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, is characterized in the HIT for forming ito film too On positive energy battery, the tow sides using secondary printing technology in battery print to 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 the method reduces cost, continue secondary The advantage of printing technology, but still there is a problem of 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 its feature is will according to certain spacing Wire is pulled to battery surface top and covered by a certain amount of conducting resinl apposition by wire-drawing frame on the metal filament, then, 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.
The content of the invention
The purpose of the present invention is exactly to provide a kind of 3D inkjet printing systems for the defect for overcoming above-mentioned prior art to exist The method of standby HIT electrodes, can save silver paste consumption, reduce production cost;Grid line depth-width ratio is improved to reduce shielded area, from And improve conversion efficiency;Additionally, 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 different using two kinds first using 3D inkjet technologies Formula of size carries out inkjet printing twice and dries acquisition front electrode to the front on the HIT solar cells for forming TCO films, Then inkjet printing is carried out to the back side in the same way and obtains backplate, finally solidified.
Specifically, using ink jet-print head by conductive ink spray printing to base material cell piece, base station is heated simultaneously, battery At 100-200 DEG C, ink droplet is ejected into cell piece surface solvent and volatilizees rapidly piece surface temperature, and remaining solid particle is in surface heap Product, repeatedly in same local spray printing, grid line will progressively increase and line width keeps constant.
The conductive ink of first time inkjet printing is prepared using following components and weight portion content:
Nano-Ag particles 1-55, organic solvent 40-99, dispersant 0.1-10, surfactant 0.1-5, thermosetting resin 0.1-10;
Second conductive ink of inkjet printing is prepared using following components and weight portion 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 particle diameter is the nano-Ag particles of 40nm, and the weight portion of addition is 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, make contact resistance smaller.Second 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 particle diameter is the nano-Ag particles of 60nm, The weight portion of addition is 35-45.Nano-Ag particles are big, and electric conductivity is good, and the nano particle volume discharged during sintering is few, hinders line Reduce.The grain size of nano-Ag particles should be much smaller than the nozzle diameter of printhead in spray printing device, it is ensured that the solid in ink Particle by spray nozzle clogging, will not influence the continuity of spray printing, so as to greatly improve the quality and production efficiency of product.Nano Silver Compared with block silver, there is bigger specific surface area, the atomicity of unit area is more, and the population of unit volume is more, burning During knot, merged between particle and particle, surface disappears, if particle diameter is too small, can cause have a large amount of cavities, mistake in electrode body Small Nano Silver is also easier to reunion and results in blockage, and the present invention distinguishes the Nano Silver of preferable particle size 40nm and 60nm in printing twice With excellent effect.For solids content, content is low to be unfavorable for improving silver layer deposition efficiency, unit volume in too high then ink Interior silver granuel subnumber is excessive, is easily formed and reunited, and currently preferred nano-Ag particles weight portion is 35-45.
Used 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 piles up temperature at 120-200 DEG C, using routine Ink system, ink droplet can be in substrate surface bumping, it is impossible to be molded;If from high boiling solvent, ink droplet can expand in substrate surface Dissipate, cause lines wide, so as to influence the conversion efficiency of battery.Surface tension is too low, it is necessary 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 too high, Need the voltage of raising jet-printing head, it is possible to occur flying ink phenomenon and cause shower 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 One or more in ester, acetic acid, butyl acetate, acetamide, pyridine, 3- ethylaminoethanols, butyl butyrate or epoxychloropropane.
Described dispersant is selected from polyvinyl alcohol, polyethylene glycol, polyamide, polyurethane, polycarboxylic acids, polyvinylpyrrolidone Or one or more in polymethylacrylic acid.Dispersant makes nano-powder particle be arranged mutually with certain same sex electric charge Reprimand, so that stable suspersion is in dicyandiamide solution.
Described surfactant be selected from polyvinylpyrrolidone, dodecyl sodium sulfate, polyacrylamide, stearic acid, One or more in triethanolamine, laurate or APEO.Surfactant is used to adjust ink surface tension, is adapted to Inkjet printing requirement.
The particle diameter distribution of thermosetting resin within 100nm, preferably 40-60nm, more preferably 50nm.
The composition of thermosetting resin is selected from phenolic resin, Lauxite, melamine formaldehyde resin, epoxy resin, insatiable hunger With one or more in resin, polyurethane, polyimides.
Conductive ink is prepared using following methods:
(1) by organic solvent and dispersant, 70-100 DEG C is warming up to, stirring 1-5min to mixture is transparent molten Liquid;
(2) when preparing the conductive ink of first time inkjet printing, the temperature of step (1) gained clear solution is down to 20- 25 DEG C, nano-Ag particles are added, after stirring 30min, the outlet valve for opening bottom makes mixed liquor flow to the long and narrow reaction tube of bottom Interior, opening ultrasonic rod carries out ultrasound.Ultrasound wave vibrating bar and 3-5 times that the distance of reactor tube wall is ultrasonic rod diameter, ultrasound Ripple vibrating head is more than 1.5 times of agitating paddle single page diameter with the distance of mixing component.When ultrasonic vibration rod is inserted directly into liquid, surpass When sound wave directly acts on liquid internal, ultrasound cavitation effect can be produced, under its effect, can be produced by scattered material inside Powerful explosion, convection current, stirring, broken, mixing phenomena, so as to reach dispersed purpose.If ultrasonic vibration rod institute is in place Put with tube wall apart from too small, ultrasonic wave is directly acted on tube wall, it has been limited the cavitation effect that dispersion liquid is produced;If away from From excessive, because ultrasonic cavitation is produced around vibrating head, and energy is highly uniform is distributed in around rod, then cavitation Effect can decline at ultrasonic rod farther out scope, cause overall dispersion effect to decline.When opening ultrasound, while opening anti- Should pipe lower end outlet valve, circulating pump, reactor inlet valve, make material slow into and out of the control valve at material mouth by the way that control is each Circulate, control material temperature is maintained at 20-45 DEG C, after material is through persistent loop, stirring, ultrasound 1-2 hours, in material Heating thermosetting resin, continues cycling through, stirs, ultrasound 1-2 hours, obtains the Nano Silver mixed liquor of first time inkjet printing;
(3) during the conductive ink of second inkjet printing of preparation, the temperature of step (1) gained clear solution is down to 20- 25 DEG C, nano-Ag particles are added, after stirring 30min, the outlet valve for opening bottom makes mixed liquor flow to the long and narrow reaction tube of bottom Interior, opening ultrasonic rod carries out ultrasound.Ultrasound wave vibrating bar and 3-5 times that the distance of reactor tube wall is ultrasonic rod diameter, ultrasound Ripple vibrating head is more than 1.5 times of agitating paddle single page diameter with the distance of mixing component.When ultrasonic vibration rod is inserted directly into liquid, surpass When sound wave directly acts on liquid internal, ultrasound cavitation effect can be produced, under its effect, can be produced by scattered material inside Powerful explosion, convection current, stirring, broken, mixing phenomena, so as to reach dispersed purpose.If ultrasonic vibration rod institute is in place Put with tube wall apart from too small, ultrasonic wave is directly acted on tube wall, it has been limited the cavitation effect that dispersion liquid is produced;If away from From excessive, because ultrasonic cavitation is produced around vibrating head, and energy is highly uniform is distributed in around rod, then cavitation Effect can decline at ultrasonic rod farther out scope, cause overall dispersion effect to decline.When opening ultrasound, while opening anti- Should pipe lower end outlet valve, circulating pump, reactor inlet valve, make material slow into and out of the control valve at material mouth by the way that control is each Circulate, control material temperature is maintained at 20-45 DEG C, after material is through persistent loop, stirring, ultrasound 1-2 hours, obtain second The Nano Silver mixed liquor of secondary inkjet printing;
(4) Nano Silver mixed liquor resulting in step (2) and step (3) is mixed with surfactant respectively, is stirred Uniformly, control mixed liquor surface tension for 20-40mN/m, viscosity is 1-4cP, be then 0.22 μm or 0.45 μm of micropore with aperture Membrane filtration, the Nano Silver jet conductive ink stablized after removal precipitation.
(5) the different Nano Silver jet conductive ink of two kinds obtained by step (4) is carried out into ink-jet twice to front electrode Printing, dries after first time inkjet printing, then carries out second inkjet printing to electrode using the slurry different from first time And dry;Wherein, second slurry 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 solidified.
Compared with prior art, the HIT electrodes for being 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 transformation efficiency.Additionally, HIT electrode fabrications are only Low-temperature sintering is needed, heating energy consumption is reduced, the energy has been saved.Obtained ink good dispersion, stability is high, can substantially reduce ink Agglomerated particle blocks the phenomenon in spray printing hole in water, with low production cost, process equipment be simple, preparation process green high-efficient spy Point.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area 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
40.05g ethylene glycol-methyl ether is taken to be added in reactor, weigh 1.20g polyvinyl alcohol dissolving wherein, using plus Material in reactor temperature is heated to 100 DEG C by hot pin, and transparent solution after stirring 3min after being cooled to room temperature, is slowly added to The nano-Ag particles of 8.01g30nm, after stirring 30min, open reactor, reaction tube into and out of material mouth and circulating pump, follow material Circulation is moved, while opening stirring, Vltrasonic device, and cooling water is passed through the temperature control outside reaction tube.Material is persistently followed Ring, stirring, ultrasound, to phenolic resin is added in material, continue stirring, ultrasound 1.5 hours after 1.5 hours, are added in dispersion liquid 0.40g dodecyl sodium sulfates, are further continued for stirring, ultrasonic disperse and obtain black mixed liquor in 0.5 hour, are carried out using 0.22 μm of filter membrane 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 force is 32.255mN/m, and viscosity is 3.0cP, and normal 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 front electricity Pole carries out first time inkjet printing and dries.
40.05g ethylene glycol-methyl ether is taken to be added in reactor, weigh 1.20g polyvinyl alcohol dissolving wherein, using plus Material in reactor temperature is heated to 100 DEG C by hot pin, and transparent solution after stirring 3min after being cooled to room temperature, is slowly added to The nano-Ag particles of 8.01g30nm, after stirring 30min, open reactor, reaction tube into and out of material mouth and circulating pump, follow material Circulation is moved, while opening stirring, Vltrasonic device, and cooling water is passed through the temperature control outside reaction tube.Material is persistently followed Ring, stirring, ultrasound, to 0.40g dodecyl sodium sulfates are added in dispersion liquid, are further continued for stirring, ultrasonic disperse after 1.5 hours 0.5 hour black mixed liquor, filtered using 0.22 μm of filter membrane, remove precipitation, obtain for second inkjet printing The Nano Silver jet conductive ink of stabilization.After tested, its surface tension is obtained for 32.255mN/m, viscosity is 3.0cP, normal temperature is preserved Do not settle within 2 months.
On the electrode for having carried out first time inkjet printing 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 solidified.
Embodiment 2
Take 38.54g glycol-ethers to be added in reactor, weigh the dissolving of 1.16g polyethylene glycol wherein, at room temperature After stirring 3min, in homogeneous transparent solution, the nano-Ag particles of 7.71g50nm are slowly added to, after stirring 30min, open reaction Kettle, reaction tube flow Matter Transfer into and out of material mouth and circulating pump, while opening stirring, Vltrasonic device, and cooling water are led to Enter the temperature control outside reaction tube.Material persistent loop, stirring, ultrasound be after 1 hour, in material plus Lauxite, after Continue stirring, ultrasound 1.5 hours, to 0.19g polyacrylamides are added in dispersion liquid, continue stirring, ultrasonic disperse 0.5 hour, mix It is in brownish black to close liquid, and the mixed liquor is filtered with 0.45 μm of filter membrane, that is, obtain the stabilization for first time inkjet printing Nano Silver jet conductive ink.After tested, its surface tension is obtained for 30.980mN/m, viscosity is 2.8cP, normal temperature preserves 2 The moon is not settled.
On the HIT solar cells for forming TCO films, using Nano Silver jet conductive ink produced above to front electricity Pole carries out first time inkjet printing and dries.
Take 38.54g glycol-ethers to be added in reactor, weigh the dissolving of 1.16g polyethylene glycol wherein, at room temperature After stirring 3min, in homogeneous transparent solution, the nano-Ag particles of 7.71g50nm are slowly added to, after stirring 30min, open reaction Kettle, reaction tube flow Matter Transfer into and out of material mouth and circulating pump, while opening stirring, Vltrasonic device, and cooling water are led to Enter the temperature control outside reaction tube.Material persistent loop, stirring, ultrasound are gathered after 1 hour to 0.19g is added in dispersion liquid Acrylamide, continues stirring, ultrasonic disperse 0.5 hour, and mixed liquor is in brownish black, and the mixed liquor is carried out with 0.45 μm of filter membrane Filtering, that is, obtain for second Nano Silver jet conductive ink of inkjet printing.After tested, obtaining its surface tension is 30.980mN/m, viscosity is 2.8cP, and normal temperature is preserved and do not settled for 2 months.
On the electrode for having carried out first time inkjet printing 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 solidified.
Embodiment 3
By following components and content dispensing:
Afterwards, following steps are 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 into 20 DEG C, nano-Ag particles is added and 30min is stirred, then entered with ultrasonic rod Row ultrasound, at 20 DEG C, ultrasound adds thermosetting resin to temperature control after 1 hour, then ultrasonic 1 hour, obtains Nano Silver mixed liquor;
(3) Nano Silver mixed liquor is mixed with surfactant, is stirred, it is 20mN/ to control mixed liquor surface tension M, viscosity is 1cP, then with the filtering with microporous membrane that aperture is 0.22um, obtains being beaten for first time ink-jet after removal precipitation 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 front electricity Pole carries out first time inkjet printing and dries.
By following components and content dispensing:
Afterwards, following steps are taken to prepare for second Nano Silver jet conductive ink 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 into 20 DEG C, nano-Ag particles is added and 30min is stirred, then entered with ultrasonic rod Row ultrasound, at 20 DEG C, ultrasound obtains Nano Silver mixed liquor to temperature control after 1 hour;
(3) Nano Silver mixed liquor is mixed with surfactant, is stirred, it is 20mN/ to control mixed liquor surface tension M, viscosity is 1cP, then with the filtering with microporous membrane that aperture is 0.22um, obtains being beaten for second ink-jet after removal precipitation The Nano Silver jet conductive ink of print.
On the electrode for having carried out first time inkjet printing 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 solidified.
Embodiment 4
By following components and content dispensing:
Afterwards, following steps are 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 into 25 DEG C, nano-Ag particles is added and 30min is stirred, then entered with ultrasonic rod Row ultrasound, at 45 DEG C, ultrasound adds thermosetting resin to temperature control after 2 hours, then ultrasonic 2 hours, obtains Nano Silver mixed liquor;
(3) Nano Silver mixed liquor is mixed with surfactant, is stirred, it is 40mN/ to control mixed liquor surface tension M, viscosity is 4cP, then with the filtering with microporous membrane that aperture is 0.45um, obtains being beaten for first time ink-jet after removal precipitation 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 front electricity Pole carries out first time inkjet printing and dries.
By following components and content dispensing:
Afterwards, following steps are taken to prepare for second Nano Silver jet conductive ink 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 into 25 DEG C, nano-Ag particles is added and 30min is stirred, then entered with ultrasonic rod Row ultrasound, at 45 DEG C, ultrasound obtains Nano Silver mixed liquor to temperature control after 2 hours;
(3) Nano Silver mixed liquor is mixed with surfactant, is stirred, it is 40mN/ to control mixed liquor surface tension M, viscosity is 4cP, then with the filtering with microporous membrane that aperture is 0.45um, obtains being beaten for second ink-jet after removal precipitation The Nano Silver jet conductive ink of print.
On the electrode for having carried out first time inkjet printing 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 solidified.
Embodiment 5
By following components and content dispensing:
Afterwards, following steps are 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 into 23 DEG C, nano-Ag particles is added and 30min is stirred, then entered with ultrasonic rod Row ultrasound, temperature control is at 35 DEG C, and ultrasound adds oxide component after 1.5 hours, then ultrasonic 1.5 hours, obtains Nano Silver and mixes Close liquid;
(3) Nano Silver mixed liquor is mixed with surfactant, is stirred, it is 30mN/ to control mixed liquor surface tension M, viscosity is 3cP, then with the filtering with microporous membrane that aperture is 0.45um, obtains being beaten for first time ink-jet after removal precipitation 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 front electricity Pole carries out first time inkjet printing and dries.
By following components and content dispensing:
Afterwards, following steps are taken to prepare for second Nano Silver jet conductive ink 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 into 23 DEG C, nano-Ag particles is added and 30min is stirred, then entered with ultrasonic rod Row ultrasound, at 35 DEG C, ultrasound obtains Nano Silver mixed liquor to temperature control after 1.5 hours;
(3) Nano Silver mixed liquor is mixed with surfactant, is stirred, it is 30mN/ to control mixed liquor surface tension M, viscosity is 3cP, then with the filtering with microporous membrane that aperture is 0.45um, obtains being beaten for second ink-jet after removal precipitation The Nano Silver jet conductive ink of print.
On the electrode for having carried out first time inkjet printing 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 solidified.
Electrode to being prepared by the above method is tested.Wherein, 35.6 μm of front electrode height, width is 45 μm, Depth-width ratio is 0.79, the μ Ω cm of resistivity 4.2;46 μm of backplate height, width is 35 μm, and depth-width ratio is 0.76, resistivity 4μΩ·cm.HIT batteries to being made are tested, and are opened pressure ratio conventional screen printed battery and are improved 2mv, and short circuit current increases 0.13A, photoelectric transformation efficiency increase by 0.4%.Silver paste consumption reduces 30% simultaneously.
Specific embodiment of the invention is described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can within the scope of the claims make various deformations or amendments, this not shadow Sound substance of the invention.

Claims (10)

1. a kind of method that 3D inkjet printings prepare HIT electrodes, it is characterised in that the method utilizes 3D inkjet technologies, first First carry out twice that inkjet printing is simultaneously to the front on the HIT solar cells for forming TCO films using two kinds of different formula of size Drying obtains front electrode, and then carrying out inkjet printing to the back side in the same way obtains backplate, is finally solidified .
2. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, it is characterised in that utilize ink-jet By on conductive ink spray printing to base material cell piece, base station is heated printhead simultaneously, and cell piece surface temperature is black at 100-200 DEG C Drop is ejected into cell piece surface solvent and volatilizees rapidly, remaining solid particle in surface sediment, repeatedly in same local spray printing, grid Line will progressively increase and line width keeps constant.
3. the method that a kind of 3D inkjet printings according to claim 1 prepare HIT electrodes, it is characterised in that spray for the first time The conductive ink of ink printing is prepared using following components and weight portion content:
Nano-Ag particles 1-55, organic solvent 40-99, dispersant 0.1-10, surfactant 0.1-5, thermosetting resin 0.1- 10;
Second conductive ink of inkjet printing is prepared using following components and weight portion content:
Nano-Ag particles 1-55, organic solvent 40-99, dispersant 0.1-10, surfactant 0.1-5.
4. the method that a kind of 3D inkjet printings according to claim 4 prepare HIT electrodes, it is characterised in that spray for the first time The particle size range of nano-Ag particles in the conductive ink of ink printing<50nm, it is preferred to use particle diameter is the nano-Ag particles of 40nm, plus The weight portion for entering preferably 35-45;
The particle diameter of nano-Ag particles is 50-100nm in second conductive ink of inkjet printing, it is preferred to use particle diameter is 60nm's Nano-Ag particles, the weight portion of addition is preferably 35-45.
5. the method that a kind of 3D inkjet printings according to claim 4 prepare HIT electrodes, it is characterised in that described has The boiling point of machine solvent be 100-150 DEG C, surface tension is 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 One or more in alkane.
6. the method that a kind of 3D inkjet printings according to claim 4 prepare HIT electrodes, it is characterised in that described divides Powder is selected from polyvinyl alcohol, polyethylene glycol, polyamide, polyurethane, polycarboxylic acids, polyvinylpyrrolidone or polymethylacrylic acid One or more.
7. the method that a kind of 3D inkjet printings according to claim 4 prepare HIT electrodes, it is characterised in that described table Face activating agent be selected from polyvinylpyrrolidone, dodecyl sodium sulfate, polyacrylamide, stearic acid, triethanolamine, laurate or One or more in APEO.
8. the method that a kind of 3D inkjet printings according to claim 4 prepare HIT electrodes, it is characterised in that described heat The particle diameter distribution of thermosetting resin within 100nm, preferably 50nm, using phenolic resin, Lauxite, carbamide One or more in resin, epoxy resin, unsaturated-resin, polyurethane or polyimides.
9. the method that a kind of 3D inkjet printings according to claim 4 prepare HIT electrodes, it is characterised in that spray for the first time The conductive ink of ink 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 into 20-25 DEG C, nano-Ag particles is added and 30min is stirred, then carried out with ultrasonic rod Ultrasound, ultrasonic rod and 3-5 times that the distance of reaction tube wall is ultrasonic rod diameter, temperature control is at 20-45 DEG C, and ultrasonic 1-2 is small When after add thermosetting resin, then ultrasound 1-2 hours obtains Nano Silver mixed liquor;
(3) Nano Silver mixed liquor is mixed with surfactant, is stirred, control mixed liquor surface tension for 20-40mN/m, Viscosity is 1-4cP, and then with the filtering with microporous membrane that aperture is 0.22 μm or 0.45 μm, that is stablized after removal precipitation receives The silver-colored jet conductive ink of rice;
The conductive ink of second 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 It is clear solution;
(2) after above-mentioned clear solution being cooled into 20-25 DEG C, nano-Ag particles is added and 30min is stirred, then carried out with ultrasonic rod Ultrasound, ultrasonic rod and 3-5 times that the distance of reaction tube wall is ultrasonic rod diameter, temperature control is at 20-45 DEG C, and ultrasonic 1-2 is small Shi Hou, obtains Nano Silver mixed liquor;
(3) Nano Silver mixed liquor is mixed with surfactant, is stirred, control mixed liquor surface tension for 20-40mN/m, Viscosity is 1-4cP, and then with the filtering with microporous membrane that aperture is 0.22 μm or 0.45 μm, that is stablized after removal precipitation receives The silver-colored jet conductive ink of rice.
10. the method that a kind of 3D inkjet printings according to claim 10 prepare HIT electrodes, it is characterised in that for the first time The step of conductive ink of inkjet printing (2), specifically uses following methods:
The temperature of step (1) gained clear solution is down to 20-25 DEG C, nano-Ag particles are added, after stirring 30min, bottom is opened The outlet valve in portion makes mixed liquor flow in the long and narrow reaction tube of bottom, and opening ultrasonic rod carries out ultrasound, while outside to reaction tube Logical cooling water in temperature control, and outlet valve, circulating pump, the reactor inlet valve of reaction tube lower end are opened, it is each by control 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 be after 1-2 hours, to thermosetting resin is heated in material, continues cycling through, stirs, ultrasound 1-2 hours, obtains nanometer Silver-colored mixed liquor;
The step of conductive ink of second inkjet printing (2), specifically uses following methods:
The temperature of step (1) gained clear solution is down to 20-25 DEG C, nano-Ag particles are added, after stirring 30min, bottom is opened The outlet valve in portion makes mixed liquor flow in the long and narrow reaction tube of bottom, and opening ultrasonic rod carries out ultrasound, while outside to reaction tube Logical cooling water in temperature control, and outlet valve, circulating pump, the reactor inlet valve of reaction tube lower end are opened, it is each by control 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.
CN201710167092.6A 2017-03-20 2017-03-20 A kind of method that 3D inkjet printings prepare HIT electrodes Active CN106876502B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710167092.6A CN106876502B (en) 2017-03-20 2017-03-20 A kind of method that 3D inkjet printings prepare HIT electrodes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710167092.6A CN106876502B (en) 2017-03-20 2017-03-20 A kind of method that 3D inkjet printings prepare HIT electrodes

Publications (2)

Publication Number Publication Date
CN106876502A true CN106876502A (en) 2017-06-20
CN106876502B CN106876502B (en) 2018-09-14

Family

ID=59171626

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710167092.6A Active CN106876502B (en) 2017-03-20 2017-03-20 A kind of method that 3D inkjet printings prepare HIT electrodes

Country Status (1)

Country Link
CN (1) CN106876502B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2019005947A1 (en) * 2017-06-27 2019-01-03 Sabic Global Technologies B.V. Additive manufacturing of multiple materials with nanoparticulate slurry printing
CN110828597A (en) * 2019-10-30 2020-02-21 深圳市百柔新材料技术有限公司 Solar cell string and preparation method thereof
CN113237580A (en) * 2021-05-19 2021-08-10 郑州大学 MXene high-sensitivity piezoresistive sensor and preparation method thereof
CN113394554A (en) * 2020-03-13 2021-09-14 昆山哈勃电波电子科技有限公司 Method for preparing antenna by adopting TDP printing process
CN114220588A (en) * 2021-11-23 2022-03-22 苏州思尔维纳米科技有限公司 Ink-jet printing HIT low-temperature silver paste and preparation method thereof
CN116072350A (en) * 2023-04-07 2023-05-05 江西理工大学南昌校区 Method for preparing conductive silver paste for solar cell electrode in situ

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010144487A2 (en) * 2009-06-09 2010-12-16 Sdsu Research Foundation Organic photovoltaic cell and light emitting diode with an array of 3-dimensionally fabricated electrodes
CN103107212A (en) * 2013-02-01 2013-05-15 中国科学院上海微系统与信息技术研究所 Heterojunction solar battery with electroplate electrodes and preparation method
US20140008746A1 (en) * 2010-12-09 2014-01-09 Faculdade de Ciências e Tecnolgia da Universidade Nova de Lisboa Mesoscopic optoelectronic devices comprising arrays of semiconductor pillars deposited from a suspension and production method thereof
CN105489666A (en) * 2016-01-12 2016-04-13 山东联星能源集团有限公司 System and method for preparing solar cell electrode by inkjet 3D printing
CN105694598A (en) * 2016-04-21 2016-06-22 华东理工大学 Nano silver 3D inkjet conductive ink and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010144487A2 (en) * 2009-06-09 2010-12-16 Sdsu Research Foundation Organic photovoltaic cell and light emitting diode with an array of 3-dimensionally fabricated electrodes
US20140008746A1 (en) * 2010-12-09 2014-01-09 Faculdade de Ciências e Tecnolgia da Universidade Nova de Lisboa Mesoscopic optoelectronic devices comprising arrays of semiconductor pillars deposited from a suspension and production method thereof
CN103107212A (en) * 2013-02-01 2013-05-15 中国科学院上海微系统与信息技术研究所 Heterojunction solar battery with electroplate electrodes and preparation method
CN105489666A (en) * 2016-01-12 2016-04-13 山东联星能源集团有限公司 System and method for preparing solar cell electrode by inkjet 3D printing
CN105694598A (en) * 2016-04-21 2016-06-22 华东理工大学 Nano silver 3D inkjet conductive ink and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王奡等: "喷墨打印太阳电池栅线的成型实验研究", 《太阳能学报》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019005947A1 (en) * 2017-06-27 2019-01-03 Sabic Global Technologies B.V. Additive manufacturing of multiple materials with nanoparticulate slurry printing
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
CN110828597A (en) * 2019-10-30 2020-02-21 深圳市百柔新材料技术有限公司 Solar cell string and preparation method thereof
CN113394554A (en) * 2020-03-13 2021-09-14 昆山哈勃电波电子科技有限公司 Method for preparing antenna by adopting TDP printing process
CN113237580A (en) * 2021-05-19 2021-08-10 郑州大学 MXene high-sensitivity piezoresistive sensor and preparation method thereof
CN113237580B (en) * 2021-05-19 2023-01-10 郑州大学 MXene high-sensitivity piezoresistive sensor and preparation method thereof
CN114220588A (en) * 2021-11-23 2022-03-22 苏州思尔维纳米科技有限公司 Ink-jet printing HIT low-temperature silver paste and preparation method thereof
CN114220588B (en) * 2021-11-23 2024-02-09 苏州思尔维纳米科技有限公司 HIT low-temperature silver paste for ink-jet printing and preparation method thereof
CN116072350A (en) * 2023-04-07 2023-05-05 江西理工大学南昌校区 Method for preparing conductive silver paste for solar cell electrode in situ
CN116072350B (en) * 2023-04-07 2023-08-15 江西理工大学南昌校区 Method for preparing conductive silver paste for solar cell electrode in situ

Also Published As

Publication number Publication date
CN106876502B (en) 2018-09-14

Similar Documents

Publication Publication Date Title
CN106876502B (en) A kind of method that 3D inkjet printings prepare HIT electrodes
CN101803037B (en) Composite membrane for super straight solar cell, process for producing the composite membrane for super straight solar cell, composite membrane for substraight solar cell, and process for producing the composite membrane for substraight solar cell
CN104263082B (en) Graphene organic silver conductive printing ink and preparation method thereof
CN106128555B (en) A kind of highly conductive crystal silicon solar batteries front electrode silver slurry and preparation method thereof
CN110355381B (en) Nano silver powder and preparation method and application thereof
CN106086979A (en) A kind of Graphene/metallic composite and preparation method thereof
CN105694598A (en) Nano silver 3D inkjet conductive ink and preparation method thereof
CN107513311B (en) Antioxidant copper-graphene composite conductive ink and preparation method thereof
CN101805538A (en) Lower-temperature sintered conductive ink
CN102585589A (en) Thermal sublimation ink as well as direct printing technology and equipment
CN106752381A (en) Without particle silver inks water and preparation method thereof and transparent silver-colored conductive film and preparation method thereof
CN108753044A (en) A kind of plating copper nano-particle Graphene conductive ink and preparation method thereof
CN107140676A (en) A kind of preparation method of metal doped zinc oxide even in liquid phase dispersion
CN105600828A (en) Preparation method of porous nano CuFe2O4
WO2020239143A1 (en) Graphene conductive ink and preparation method therefor
CN108711462A (en) A kind of conductive silver paste without glass powder and preparation method thereof and sintering method
CN102555521A (en) Printing head for solar battery front silver paste
CN110467178A (en) A method of preparing graphene
CN106433317A (en) Water-based ink-jet nano-silver conductive ink and preparation method thereof
CN108372310A (en) A kind of preparation method of small-size nano-silver for water-base conductive ink
CN112828300A (en) Nano silver, preparation method and application
CN102286226B (en) Colorless transparent conductive ink as well as preparation method and application thereof
CN104162682A (en) Preparation method of silver powder for positive silver electrode of silicon solar battery
CN104708930A (en) Nanometer metal particle-containing conductive ink-based printing method
CN102738254A (en) Composition of transparent conductive film for thin-film solar battery and transparent conductive film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant