CN104084598A - Production method for solar cell high-density monodisperse silver powder - Google Patents
Production method for solar cell high-density monodisperse silver powder Download PDFInfo
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Abstract
The invention discloses a production method for solar cell high-density monodisperse silver powder. According to the production method, glyoxal serves as a reducing agent for reducing silver nitrate, and glycolic acid and oxalic acid generated by glyoxal reaction serve as components of silver powder dispersing protective agents. While flow concurrence is performed in a reactor, a glyoxal solution, a sodium hydroxide solution and a silver nitrate solution are added into the reactor, and the molar ratio of the silver nitrate, the glyoxal and sodium hydroxide is controlled to be 1:0.25-0.35:1-1.4, the pH value of a reaction solution is kept at 8-10, the reaction temperature is kept at 20 DEG C-40 DEG C, after feed intake is finished, stirring and reacting are continued for 0.5 hour-1 hour, and therefore reaction is complete, and silver crystal grain crystallization is complete. Silver powder particles are approximately spherical, the surfaces are smooth and glossy, the particle size distribution is narrow, the average particle size is 1.2 micrometers-1.8 micrometers, the apparent density is 2.0 g/cm<3>-2.5 g/cm<3>, the tap density is 4.5 g/cm<3>-5.0 g/cm<3>, and the molar yield is 97-99.5%. The consumption of the reducing agent is small in the process of producing the silver powder, production cost is low, safe and environmentally friendly effects are achieved, the reaction condition is easy to control, product quality is stable, and industrialized application is easy.
Description
Technical field
The present invention relates to a kind of production method of solar cell high density list dispersible silver powder; particularly a kind of silver nitrate that reduces using glyoxal as reducing agent; the production method of disperseing the high density list dispersible silver powder of protective agent component using glyoxal reaction product glycolic and oxalic acid as silver powder, belongs to new forms of energy and field of new.
Background technology
Silver powder is the important component part of solar cell anode sizing agent, and the electrocondution slurry that only meets the silver powder preparation of specified conditions just possesses good serigraphy performance, could form the positive silver electrode having compared with high square resistance and thin grid line after oversintering.Front electrode is divided into gate electrode line and main electrode line, and grid line mainly collects the carrier that opto-electronic conversion produces, and main electrode mainly makes cell piece be connected with outside line.Positive electrode gate line width 0.15 about mm, sintering temperature reaches 930 DEG C, high-temperature region sintering time only 5-8 second.If silver powder granularity is excessive, when printing in silver slurry, just can not be passed through silk screen completely, also cannot densified sintering product in the short time, and easily there is hole in sintered membrane, thereby affects electric conductivity.
Document is mainly concentrated research nano-silver powder at present, because nano-silver powder activity is high, easily occurs from sintering or agglomeration at normal temperatures, has caused nano-silver powder dispersiveness very poor, and tap density is low.Nano-silver powder modulation slurry is difficult for by organic carrier complete wetting, causes printing effect bad, after sintering large, the hole of silverskin shrinkage factor many be connected not fine and close.In addition, nano-silver powder is difficult to improve the silver content of conductive silver paste, and electric conductivity is poor.Silver powder used for solar batteries need to meet that particle diameter is moderate, degree of crystallinity is high, the condition such as tap density is high, good dispersion, spherical or class are spherical.
Application practice proof average grain diameter is the silver powder at 1-2 μ m at 0.2-3 μ m, particularly average grain diameter, can meet the condition of tap density height and narrow diameter distribution simultaneously, good with the silver paste of solar cells comprehensive comparison of its modulation.Prepare the high dispersive high density monodisperse spherical silver powder of particle diameter 1-2 μ m, significant for the raising of silver paste of solar cells printing performance and electric conductivity and the lifting of solar cell photoelectric conversion efficiency.
The preparation method of silver powder has high-energy ball milling method, spray heating decomposition (SP method), plasma evaporation condensation method, chemical liquid phase reducing process and microemulsion method etc., and wherein chemical liquid phase reducing process has obtained extensive attention because of advantages such as production equipment is simple, easily control of technique, low cost, low energy consumption.
Liquid phase reduction principle is exactly silver ion to be deposited with the form of silver powder from the solution of silver salt or silver complex with reducing agent.Normally silver nitrate [the AgNO of silver salt adopting
3] and silver potassium cyanide [KAg (CN)
2], or silver nitrate is converted into silver oxide [Ag
2o], silver carbonate [Ag
2cO
3] and silver ammino ion [Ag (NH
3)
2 +].
In whole reduction reaction process, the selection of reducing agent is extremely important.The inorganic reducing agent of bibliographical information mainly contains hydrazine hydrate, hydrogen peroxide, inferior sodium phosphate, sodium dithionite, sodium borohydride, ferrous sulfate, sodium thiosulfate, potassium sulfite etc.; The organic reducing agent of bibliographical information mainly contains ascorbic acid, formaldehyde, formic acid, sodium potassium tartrate tetrahydrate, ethanol, glycerine, glucose, reduced sugar, triethanolamine, quinhydrones etc.If the reproducibility of reducing agent is too strong, the silver particles obtaining is difficult for shifting, the unordered growth in solution of the silver-colored crystal grain of generation, and the probability that collision generation is reunited is mutually very large, causes particle diameter easily to increase excessive, can not get all even monodispersed silver powder particles.Generally need to add and disperse protective agent to disperse protection to the silver-colored crystal grain generating, stop the reunion of silver-colored crystal grain.Disperse protective agent in reduction reaction, to mainly contain many-sided effect: (1) dispersant can with solution in Ag
+form ligand and change Ag
+activity, is convenient to reacting balance and carries out, and reaches the object of preliminary dispersion; (2) the silver-colored crystal grain that dispersant parcel generates hinders it to be continued to grow up: (3) dispersant space steric effect reduces silver-colored crystal grain and mutually collides reunion probability.
Normally macromolecular material, surfactant and ligand of the dispersion protective agent of bibliographical information; mainly contain polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), gelatin, carboxymethyl cellulose, Sodium Polyacrylate, alkanolamine, lauryl sodium sulfate (DBS), softex kw, polyethylene glycol, tween, LCFA, succinic acid, sulfuric acid etc., wherein being most widely used with PVP.
Patent about silver powder preparation method is a lot, for example, Chinese patent CN102921944(2013-02-13) a kind of silver powder for conductive silver paste of solar battery electrode and preparation method thereof is disclosed, adopting glucose, hydrazine hydrate, hydroquinones or ascorbic acid and composition thereof is reducing agent; Chinese patent CN102632248(2012-08-15) a kind of ball shape silver powder and preparation method thereof is disclosed, employing ascorbic acid is reducing agent, polyvinylpyrrolidone is protective agent; Chinese patent CN101941078(2011-01-12) a kind of solar battery electrode slurry silver powder and preparation method thereof is disclosed, adopting hydrazine hydrate, formaldehyde, sodium thiosulfate or sodium borohydride is reducing agent; Japan Patent JP2013189704(2013-09-26) it is open a kind of that to adopt formaldehyde be reducing agent, stearic acid is for disperseing protectant silver powder production method; US Patent No. 5000928(1991-03-19) silver powder production method that to adopt sodium formate be reducing agent; US Patent No. 4456473(1984-06-26) it is open a kind of that to adopt hydrazine hydrate be reducing agent production high-purity silver powder method; The open method of producing silver powder by inferior sodium phosphate of Korean Patent KR20100100210 (2010-09-15); JP2001107101(2001-0 4-17) a kind of high dispersive ball shape silver powder production method is disclosed, employing quinhydrones is reducing agent, makes to disperse protective agent with gelatin; JPH06122905(1994-05-06) disclose a kind of ball shape silver powder production method, adopting sodium borohydride, formaldehyde, quinhydrones and polyvinylpyrrolidone is reducing agent.
The deficiency that existing silver powder technology of preparing exists is mainly: (1) reducing agent hydrazine hydrate, formaldehyde and quinhydrones are poisonous, and excitant is very strong, and environmental protection and secure context problem are difficult to solve; (2) sodium borohydride, quinhydrones reducing agent high cost, affect silver powder productivity effect; (3) reducing agent ascorbic acid is to condition sensitives such as system acidity, concentration and temperature, and working condition is wayward; (4) reproducibility of reducing agent is excessively strong, conventionally need disperse protective agent to be used in conjunction with a large amount of macromolecules, causes follow-up silver powder separation difficulty; (5) product silver powder density is too low unstable with particle diameter, and particle size distribution is wide.
China is maximum in the world crystal silicon solar battery component producing country, needs 64 kilograms of silver powder meters according to 1MW photovoltaic module, domestic silver powder demand is reached to 750 tons of left and right.Along with the continuous expansion in photovoltaic market, silver powder market will constantly expand, and the silver powder of the low and good conductivity of development environment close friend, cost, will promote solar cell industry development.
Summary of the invention
The object of this invention is to provide a kind of silver nitrate that reduces taking glyoxal as reducing agent; disperse protective agent component using glyoxal reaction product glycolic and oxalic acid as silver powder; the production method of the high density list dispersible silver powder of easy control of process conditions, the technical scheme of taking and production stage are:
(1) preparing respectively concentration is the glyoxal solution of 0.5-1.0mol/L and the NaOH of 0.5-1.0mol/L or potassium hydroxide solution;
(2) silver nitrate is dissolved in to deionized water, adds the macromolecule dispersing agent of silver nitrate quality 0.2%-1.0%, after dissolving, being diluted to concentration is the liquor argenti nitratis ophthalmicus containing dispersant of 0.5-1.0mol/L;
(3) in the glass reactor stirring to band, also stream adds glyoxal solution, sodium hydroxide solution and liquor argenti nitratis ophthalmicus simultaneously, control material molar ratio is: silver nitrate: glyoxal: NaOH=1:0.25-0.35:1-1.4, charging rate is controlled at the grey that is precipitated as generating in maintenance reactant liquor, maintains reactant liquor pH8-10 and reaction temperature 20-40 DEG C;
(4) the rear continuation stirring reaction that fed intake makes to react completely and silver-colored crystal grain perfect crystalline for 0.5-1 hour;
(5) to the BTA corrosion inhibiter that adds silver nitrate quality 0.02-0.1% in reaction residual liquor, stir 15 minutes, make the silver powder surface passivation generating;
(6) isolated by filtration silver powder, successively with deionized water and ethanol washing, the dry silver powder product that obtains at 80 DEG C.
It is closely spherical that silver powder particles is, smooth surface and glossy, narrow diameter distribution, average grain diameter 1.2-1.8 μ m, apparent density 2.0-2.5g/cm
3, tap density 4.5-5.0g/cm
3, molar yield 97%-99.5%.
Raw glyoxal of the present invention is commercially available 40% industrial glyoxal, and industrial glyoxal contains 0.5%-3% ethylene glycol, and the invention process is not affected.
Glyoxal is important fine chemical material and intermediate, is produced by ethylene glycol air oxidation process, of many uses in industries such as papermaking, weaving, oil, medicine and printing and dyeing.200,000 tons of China's 40% industrial glyoxal annual productions, its cheap market price, glyoxal is nonpoisonous and tasteless, can be used as the substitute of formaldehyde in many applications.
Raw silver nitrate of the present invention is reagent silver nitrate or industrial silver is dissolved in to the liquor argenti nitratis ophthalmicus that excessive nitric acid makes, and a small amount of nitric acid adulterating in industrial nitric acid silver material is implemented not impact to invention.
The dispersion protective agent adopting is the glycolic of glyoxal disproportionation decomposition reaction generation and oxalic acid and polyacrylamide, polyvinylpyrrolidone (PVP), polyethylene glycol (PEO), polyvinyl alcohol (PVA), gelatin, carboxymethyl cellulose or its mixture that oxidation reaction generates.Glycolic and oxalic acid are adsorbed on silver-colored grain surface and block it and grow up, and have reacted rear easy washing and have removed, and have greatly reduced macromolecule dispersing agent consumption, can be easily by silver-colored grain size limits in micron or sub-micrometer range.
Glyoxal reduction silver nitrate of the present invention is prepared silver powder and is carried out under alkali condition, and reaction equation is as follows:
4AgNO
3 + CHOCHO+ 4NaOH + 2H
2O = 4Ag + (COOH )
2+ 2H
2 + 4NaNO
3
In reaction, need constantly to add NaOH or potassium hydroxide solution control reactant liquor pH8-10, when reacting liquid basicity is too high, the aggravation that reduces side reaction of the disproportionation of glyoxal, has increased raw material glyoxal consumption, the actual rate of charge of glyoxal should be greater than theoretical amount, and the disproportionated reaction formula of glyoxal is as follows:
CHOCHO + NaOH = CH
2OHCOONa
In the incipient stage of the present invention reaction, the raw material liquor argenti nitratis ophthalmicus adding directly forms the silver-colored nucleus of black and oxalic acid with glyoxal reaction; In the subsequent reactions stage, first raw material liquor argenti nitratis ophthalmicus reacts oxalic silvery white precipitation with the oxalic acid containing in reactant liquor, silver oxalate generates silver atoms, releasing hydrogen gas and oxalic with glyoxal reaction again, the silver atoms that reduction generates is evenly grown to the silver-colored crystal grain of several microns on the silver-colored nucleus previously forming, the formation of silver oxalate precipitation and the reaction cycle that is further reduced into silver atoms are carried out, and reaction equation is as follows:
2AgNO
3 + (COOH)
2 + 2NaOH = (COOAg )
2 + 2NaNO
3
CHOCHO+ 2(COOAg )
2 + 2H
2O = 4Ag +2H
2+ 3(COOH )
2
Actual not necessarily silver oxalate precipitation itself of participating in reduction reaction in the present invention's reaction, it can be a small amount of silver ion that its dissociation forms, concentration of silver ions is mainly determined by silver oxalate solubility product constant, be subject to silver nitrate add speed and reaction temperatures affect less, because concentration of silver ions is more stable, reduction reaction conditions is easily controlled.
The oxalic acid that the glycolic that in the present invention, the decomposition of glyoxal disproportionation generates and oxidation generate adsorbs at silver-colored grain surface as dispersant, can effectively suppress the too fast of silver-colored nucleus grows up, the dispersant adsorption layer of each silver-colored nucleating surface is in occupation of certain space simultaneously, make the silver-colored crystal grain having formed cannot be coalescent, in the state of abundant dispersion, silver powder particle diameter is controlled.
In the present invention, reaction temperature is 20-40 DEG C, improves temperature by fast reaction speed, excessive temperature will make silver powder density reduce and particle diameter inhomogeneous, the while has also increased glyoxal disproportionation decomposition rate.
Advantage and the beneficial effect of invention are embodied in:
(1) the present invention reduces silver nitrate using glyoxal as reducing agent, and product density is high, narrow diameter distribution, is suitable as solar cell conductive silver slurry raw material;
(2) the present invention, using glyoxal reaction product glycolic and oxalic acid as disperseing protective agent component, can wash and remove, and greatly reduces polyelectrolyte protectant consumption, and product aftertreatment technology is simple, and product purity is high;
(3) oxalic acid that glyoxal of the present invention oxidation produces can with silver nitrate reaction precipitation, in reactant liquor, concentration of silver ions is stable, easy control of process conditions, constant product quality;
(4) silver powder production method reducing agent consumption of the present invention is few, and technique is simple, and production cost is low, safety and environmental protection, easily commercial application.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
Industrial 5.1g 40% glyoxal (0.035mol) is diluted to the glyoxal solution that concentration is 1.0mol/L by 30mL deionized water; 5.9 g chemical pure NaOH (0.14mol) are used to 134mL deionized water dissolving, obtain the sodium hydroxide solution of 1.0mol/L; 17.0g is analyzed to pure silver nitrate (0.1mol) and is dissolved in 80mL deionized water, add 0.17g polyacrylamide (PAM) dispersant, after dissolving completely, be diluted to 100mL, obtain 1.0mol/L containing PAM liquor argenti nitratis ophthalmicus.
In the 500mL glass reactor stirring to band, also stream drips glyoxal solution, sodium hydroxide solution and liquor argenti nitratis ophthalmicus simultaneously, there is at once black silver nucleus to produce, stop reinforced 10 minutes, in the time that precipitation changes grey into gradually, continue to add material liquid, rate of addition is controlled at the grey that is precipitated as generating in maintenance reactant liquor, maintains reactant liquor pH8-10 and reaction temperature 20-25 DEG C.Reinforced completing for approximately 30 minutes, continues stirring reaction 1 hour, until solution is colourless, generates linen silver-colored crystal grain.
In reaction residual liquor, add 0.017g BTA corrosion inhibiter, stir 15 minutes, make the silver powder surface passivation generating.Isolated by filtration silver powder successively, with deionized water 100mL and ethanol 20mL washing, is dried and obtains silver powder 10.75g at 80 DEG C, and it is closely spherical that silver powder particles is, smooth surface and glossy, and better dispersed, average grain diameter is 1.5 μ m, apparent density 2.5g/cm
3, tap density is 5.0g/cm
3, molar yield 99.5%.
Embodiment 2
Industrial 4.0g 40% glyoxal (0.0276mol) is diluted to the glyoxylic acid solution that concentration is 0.5mol/L by 50mL deionized water; 4.6g chemical pure NaOH (0.11mol) is used to 205mL deionized water dissolving, obtain the sodium hydroxide solution of 0.5mol/L; 10.80g industry silver strip (0.1mol) is dissolved in dilute nitric acid solution, make the acid liquor argenti nitratis ophthalmicus of 97.0g, add 0.10g polyvinyl alcohol (PVA) dispersant, after dissolving completely, be diluted to 200mL, obtain 0.5mol/L containing PVA liquor argenti nitratis ophthalmicus.
In the 1000mL glass reactor stirring to band, also stream drips glyoxylic acid solution, sodium hydroxide solution and liquor argenti nitratis ophthalmicus simultaneously, there is at once black silver nucleus to produce, stop reinforced 10 minutes, in the time that precipitation changes grey into gradually, continue to add material liquid, rate of addition is controlled at the grey that is precipitated as generating in maintenance reactant liquor, maintains reactant liquor pH9-10 and reaction temperature 30-35 DEG C.Feed in raw material and fed intake after approximately 50 minutes, continue stirring reaction 0.5 hour, until solution is colourless, generate linen silver-colored crystal grain.
In reaction residual liquor, add 0.017g BTA corrosion inhibiter, stir 15 minutes, make the silver powder surface passivation generating.Isolated by filtration silver powder successively, with deionized water 100mL and ethanol 20mL washing, is dried and obtains silver powder 10.55g at 80 DEG C, and it is closely spherical that silver powder particles is, smooth surface and glossy, and better dispersed, average grain diameter is 1.3 μ m, apparent density 2.3g/cm
3, tap density is 4.6g/cm
3, molar yield is 97.7%.
Claims (4)
1. the production method of a solar cell high density list dispersible silver powder; it is characterized in that reducing using glyoxal as reducing agent silver nitrate; disperse protective agent component using glyoxal reaction product glycolic and oxalic acid as silver powder, easy control of process conditions, comprises following production stage:
(1) preparing respectively concentration is the glyoxal solution of 0.5-1.0mol/L and the NaOH of 0.5-1.0mol/L or potassium hydroxide solution;
(2) silver nitrate is dissolved in to deionized water, adds the macromolecule dispersing agent of silver nitrate quality 0.2%-1.0%, after dissolving, being diluted to concentration is the liquor argenti nitratis ophthalmicus containing dispersant of 0.5-1.0mol/L;
(3) in the glass reactor stirring to band, also stream adds glyoxal solution, sodium hydroxide solution and liquor argenti nitratis ophthalmicus simultaneously, control material molar ratio is: silver nitrate: glyoxal: NaOH=1:0.25-0.35:1-1.4, charging rate is controlled at the grey that is precipitated as generating in maintenance reactant liquor, maintains reactant liquor pH8-10 and reaction temperature 20-40 DEG C;
(4) the rear continuation stirring reaction 0.5-1 hour that fed intake, makes to react completely and silver-colored crystal grain perfect crystalline;
(5) to the BTA corrosion inhibiter that adds silver nitrate quality 0.02-0.1% in reaction residual liquor, stir 15 minutes, make the silver powder surface passivation generating;
(6) isolated by filtration silver powder, successively with deionized water and ethanol washing, the dry silver powder product that obtains at 80 DEG C.
2. a kind of production method of solar cell high density list dispersible silver powder according to claim 1, is characterized in that raw material glyoxal is commercially available 40% industrial glyoxal.
3. a kind of production method of solar cell high density list dispersible silver powder according to claim 1, is characterized in that raw material silver nitrate is reagent silver nitrate or industrial silver is dissolved in to the liquor argenti nitratis ophthalmicus that excessive nitric acid makes.
4. a kind of production method of solar cell high density list dispersible silver powder according to claim 1, is characterized in that the dispersion protective agent adopting is the glycolic that generates of glyoxal reaction and oxalic acid and polyacrylamide (PAM), polyvinylpyrrolidone (PVP), polyethylene glycol (PEO), polyvinyl alcohol (PVA), gelatin, carboxymethyl cellulose.
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Application publication date: 20141008 |