CN103192092B - The manufacture method of nano silver wire - Google Patents

The manufacture method of nano silver wire Download PDF

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CN103192092B
CN103192092B CN201310152157.1A CN201310152157A CN103192092B CN 103192092 B CN103192092 B CN 103192092B CN 201310152157 A CN201310152157 A CN 201310152157A CN 103192092 B CN103192092 B CN 103192092B
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silver
acid
manufacture method
nano silver
nano
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CN103192092A (en
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潘克菲
冀月田
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SUZHOU NUOVO FILM Inc
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SUZHOU NUOVO FILM Inc
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Abstract

A kind of manufacture method of nano silver wire, it comprises the steps: that (a) provides mixed solution, at least containing a kind of protective agent and a kind of additive in this mixed solution, described additive is halide and/or can forms the compound of indissoluble salt with silver ion; B () provides the silver-colored precursor solution containing patina thing, and divide at least twice to join in described mixed solution this silver-colored precursor solution; C () is separated and obtains described nano silver wire.The invention has the beneficial effects as follows: adopt first with protective agent, reinject silver-colored presoma, and point at least twice injection (not being disposable injection), therefore not only can obtain the nano silver wire of high line diameter ratio but also be applicable to preparation in enormous quantities.

Description

The manufacture method of nano silver wire
Technical field
The present invention relates to a kind of manufacture method of nano silver wire, belong to Metallic Functional Materials, technical field of nano material.
Background technology
Nano silver wire has optical clear and high conductivity in visible-range, can be used for preparing transparent conductive film, for industries such as touch-screen, Organic Light Emitting Diode (OLED) and solar cells.Also can be used as electrocondution slurry, for printed circuit etc. simultaneously.
Nano silver wire due to its high conductivity and potential application widely, in the last few years more and more pay close attention to by people.The preparation method of nano silver wire is also varied, such as hydro-thermal method, polyol process or template etc.But the operability of Considering experimental, cost and productive rate etc., polyol process because it is simple to operate, productive rate is high and with low cost, and is paid close attention to by increasing people and is developed.But silver salt and protective agent are injected the polyalcohol of high temperature by the many employings of existing polyol process simultaneously, gained nano silver wire wire diameter is thick, line length is short, it is wide in range to distribute, and is difficult to mass production, can not meet reality need.
Therefore, be necessary to improve the manufacture method of existing nano silver wire, to overcome above technical problem.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method with the nano silver wire of high line diameter ratio.
Realize above-mentioned purpose for solving, the present invention adopts following technical scheme: a kind of manufacture method of nano silver wire, it comprises the steps:
(a). provide mixed solution, at least containing a kind of protective agent and a kind of additive in this mixed solution, described additive is halide and/or can forms the compound of indissoluble salt with silver ion;
(b). the silver-colored precursor solution containing patina thing is provided, and divides at least twice to join in described mixed solution this silver-colored precursor solution; When silver-colored presoma reacts to canescence after injecting for the first time, then second time injects silver-colored presoma, and the injection rate of silver-colored precursor solution is greater than the injection rate of the silver-colored precursor solution of second time for the first time;
(c). be separated and obtain described nano silver wire.
As further improved technical scheme of the present invention: in step (a), described protective agent is selected from:
Polyvinylpyrrolidone (the PVP, (C of various molecular weight 6h 9nO) n), the derivative of polyvinylpyrrolidone, polyvinyl alcohol (PVA, (C 2h 4o) n), PEO (PEO, (CH 2cH 2o) n), lauryl sodium sulfate (C 12h 25sO 4na), lauryl amine (C 12h 27n), octadecylamine (CH 3(CH 2) 16cH 2nH 2), hexadecyltrimethylammonium chloride (CTAC, C 16h 33(CH 3) 3nCl), softex kw (CTAB, C 16h 33(CH 3) 3nBr), gelatin, methylcellulose, the ninth of the ten Heavenly Stems two mercaptan, succinimide mercaptans; Or
Protective agent containing sulfydryl or amino; Or
The polymer formed by one or several monomers following, described monomer is selected from
Acrylic acid (C 3h 4o 2), butenoic acid (C 4h 6o 2), maleic acid (C 4h 4o 4), methyl-maleic acid, fumaric acid and its esters;
Containing aforesaid propylene acid (C 3h 4o 2), butenoic acid (C 4h 6o 2), maleic acid (C 4h 4o 4), the ester class of methyl-maleic acid, fumaric acid and salts substances thereof, amide-type, acid anhydrides, nitrile;
Acrylic sulfonic acid, vinyl sulfonic acid, methacrylic sulfonic acid, 3-sulfopropylmetliylacrylic and ester class, amide-type, nitrile containing phosphonate radical;
N-ethernamine class;
Any one in ethylene acetal, vinyl butyral, vinyl alcohol and ethers thereof, ester class.
As further improved technical scheme of the present invention: in step (a), described halide is selected from sodium chloride (NaCl), potassium chloride (KCl), sodium bromide (NaBr), KBr (KBr), sodium iodide (NaI), KI (KI), softex kw (CTAB, C 16h 33(CH 3) 3or hexadecyltrimethylammonium chloride (CTAC, C NBr) 16h 33(CH 3) 3nCl) any one in.
As further improved technical scheme of the present invention: in step (a), the described compound that can form indissoluble salt with silver ion is selected from sodium sulphate (Na 2sO 4), potassium sulfate (K 2sO 4), sodium sulfite (Na 2sO 3), potassium sulfite (K 2sO 3), sodium carbonate (Na 2cO 3), potash (K 2cO 3), sodium phosphate (Na 3pO 4), potassium phosphate (K 3pO 4), vulcanized sodium (Na 2or potassium sulfide (K S) 2s) any one in.
As further improved technical scheme of the present invention: in step (b), described patina thing is selected from silver nitrate (AgNO 3), silver nitrite (AgNO 2), silver oxide (AgO), silver carbonate (AgCO 3), silver acetate (CH 3cOOAg), toillen's reagent ([Ag(NH 3) 2] OH), silver cyanide (AgCN), silver sulfate (Ag 2sO 4), silver sulfide (Ag 2s), trifluoroacetic acid silver (C 2f 3o 2ag), silver thiocyanate (AgSCN), silver chlorate (AgCl), silver bromide (AgBr), silver sulfite (Ag 2sO 3), silver iodide (AgI), silver orthophosphate (Ag 3pO 4), silver fluoride (AgF), silver tetrafluoroborate (AgBF 4), pelletization silver (Ag 3n), silver propionate (C 3h 5o 2ag), actol (C 3h 5agO 3), capric acid silver, carboxylic first silver, silver citrate (C 6h 5ag 3o 7), gluconic acid silver, silver cyanate (AgOCN), silver bromate (AgBrO 3), hyptafluorobutyric acid silver (CF 3cF 2cF 2cO 2ag), acetylacetone,2,4-pentanedione silver ([CH 3cOCH=C (O-) CH 3] Ag), five fluorine silver propionate (C 2f 5cO 2ag), inclined alum acid silver (AgVO 3), hexafluoroarsenate silver (AgAsF 6), hexafluorophosphoric acid silver (AgPF 6), p-methyl benzenesulfonic acid silver (CH 3c 6h 4sO 3ag), silver tetrafluoroborate (AgBF 4), complex compound Ag (I) and the part NH of silver 3-, CN-, Cl-, S 2o 3the complex compound that-the complex compound, Ag [II] and part Py (pyridine), an adjacent phenanthroline (0 one phen), the 8 monohydroxy quinolines (oxin) that generate generate or Ag [III] and part F-, IO 4-, TeO 66-generate complex compound in any one.
As further improved technical scheme of the present invention: in step (b), in order to dissolve the mixture that the solvent of described silver-colored presoma is ester class, ethers or binary containing two or more hydroxyl or polyalcohol or is made up of described binary or polyalcohol or ester class; Described alcohols, ethers and ester class are selected from ethylene glycol (CH 2oHCH 2oH), propane diols (CH 2oHCH 2cH 2oH, CH 2oHCH 2oHCH 3), glycerine (CH 2oHCHOHCH 2oH), butanediol (C 4h 10o 2), pentanediol (C 5h 12o 2), hexylene glycol (C 6h 14o 2), cyclohexanediol (C 6h 10o 2), glycol dimethyl ether (C 4h 10o 2), ethylene glycol diethyl ether (C 6h 14o 2), diethylene glycol ether (C 6h 14o 3), 1,2-PD carbonic ester (C 4h 6o 3), propylene glycol methyl ether acetate (C 6h 12o 3), butyl glycol ether acetic acid esters (C 8h 16o 3) or ethylene glycol monomethyl ether acetate (C 5h 10o 3) in any one.
As further improved technical scheme of the present invention: the process forming described mixed solution in step (a) comprises and adds described protective agent and the step of heating for dissolving and add the step of described additive.
As further improved technical scheme of the present invention: be joined at twice in described mixed solution by described silver-colored precursor solution with the injection rate of 0.05mL/min ~ 10mL/min in step (b), and silver-colored precursor solution is respectively 60% and 40% with the addition of the silver-colored precursor solution of second time for the first time.
As further improved technical scheme of the present invention: the reaction temperature in step (b) is 60 DEG C ~ 250 DEG C.
As further improved technical scheme of the present invention: in step (a), described protective agent is polyvinylpyrrolidone (PVP, (C 6h 9nO) n), and by this protective agent heating for dissolving in glycerine; Described additive is hexadecyltrimethylammonium chloride (CTAC, C 16h 33(CH 3) 3and this additive is dissolved in glycerine NCl); In step (b), described silver-colored precursor solution is obtained liquor argenti nitratis ophthalmicus by being dissolved in glycerine by silver nitrate.
As further improved technical scheme of the present invention: in step (a), formed in the process of described additive, described hexadecyltrimethylammonium chloride (CTAC, C 16h 33(CH 3) 3nCl) after being dissolved in glycerine, the concentration ranges of gained solution is 0.1mM ~ 200mM;
In step (b), formed in the process of described liquor argenti nitratis ophthalmicus, after described silver nitrate is dissolved in glycerine, the concentration ranges of gained solution is 0.01M ~ 1M;
In step (a), formed in described protectant process, described polyvinylpyrrolidone (PVP, (C 6h 9nO) n) addition and described silver nitrate addition keep mass ratio interval to be 0.5 ~ 10.
As further improved technical scheme of the present invention: in step (c), solution step (b) obtained carries out centrifugal motion with certain speed, then adds ethanol and disperses, repeats this process that is centrifugal and dispersion.
As further improved technical scheme of the present invention: in step (c), after process that is centrifugal and dispersion terminates, gained nano silver wire to be scattered in water or ethanol thus to obtain described nano silver wire.
Compared with prior art, the present invention, by point at least twice injection silver presoma (not being disposable injection), therefore not only can obtain the nano silver wire of high line diameter ratio but also be applicable to preparation in enormous quantities.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the manufacture method of nano silver wire of the present invention.
Fig. 2 is the first microgram of the nano silver wire adopting the manufacture method of nano silver wire of the present invention to obtain.
Fig. 3 is the second microgram of the nano silver wire adopting the manufacture method of nano silver wire of the present invention to obtain.
Fig. 4 is the 3rd microgram of the nano silver wire adopting the manufacture method of nano silver wire of the present invention to obtain.
Fig. 5 is the line length distribution map of the nano silver wire adopting the manufacture method of nano silver wire of the present invention to obtain.
Fig. 6 is the footpath grain distribution map of the nano silver wire adopting the manufacture method of nano silver wire of the present invention to obtain.
Detailed description of the invention
Shown in please refer to the drawing 1, present invention is disclosed a kind of manufacture method of nano silver wire, it comprises the steps:
(a). provide mixed solution, at least containing a kind of protective agent and a kind of additive in this mixed solution, described additive is halide and/or can forms the compound of indissoluble salt with silver ion;
(b). the silver-colored precursor solution containing patina thing is provided, and divides at least twice to join in described mixed solution this silver-colored precursor solution;
(c). be separated and obtain described nano silver wire.
Particularly, in step (a), described protective agent is selected from but is not limited to:
Polyvinylpyrrolidone (the PVP, (C of various molecular weight 6h 9nO) n), the derivative of polyvinylpyrrolidone, polyvinyl alcohol (PVA, (C 2h 4o) n), PEO (PEO, (CH 2cH 2o) n), lauryl sodium sulfate (C 12h 25sO 4na), lauryl amine (C 12h 27n), octadecylamine (CH 3(CH 2) 16cH 2nH 2), hexadecyltrimethylammonium chloride (CTAC, C 16h 33(CH 3) 3nCl), softex kw (CTAB, C 16h 33(CH 3) 3nBr), gelatin, methylcellulose, the ninth of the ten Heavenly Stems two mercaptan, succinimide mercaptans; Or
Protective agent etc. containing sulfydryl or amino; Or
The polymer formed by one or several monomers following, described monomer is selected from:
Acrylic acid (C 3h 4o 2), butenoic acid (C 4h 6o 2), maleic acid (C 4h 4o 4), methyl-maleic acid, fumaric acid and its esters etc.;
Containing aforesaid propylene acid (C 3h 4o 2), butenoic acid (C 4h 6o 2), maleic acid (C 4h 4o 4), the ester class, amide-type, acid anhydrides, nitrile etc. of methyl-maleic acid, fumaric acid and salts substances thereof, as methyl acrylate, ethyl acrylate, methyl methacrylate, EMA, dimethylaminoethyl acrylate, DMAA etc.;
Acrylic sulfonic acid, vinyl sulfonic acid, methacrylic sulfonic acid, 3-sulfopropylmetliylacrylic and ester class, amide-type, nitrile etc. containing phosphonate radical, as vinyl phosphonate, acrylic phosphonic acids etc.;
N-ethernamine classes etc., as N-ethernamine pyrrolidones, N-vinyl caprolactam etc.;
Any one in ethylene acetal, vinyl butyral, vinyl alcohol and ethers thereof, ester class etc.
In step (a), described halide is selected from sodium chloride (NaCl), potassium chloride (KCl), sodium bromide (NaBr), KBr (KBr), sodium iodide (NaI), KI (KI), softex kw (CTAB, C 16h 33(CH 3) 3nBr), hexadecyltrimethylammonium chloride (CTAC, C 16h 33(CH 3) 3etc. NCl) any one in.
In step (a), the described compound that can form indissoluble salt with silver ion is selected from sodium sulphate (Na 2sO 4), potassium sulfate (K 2sO 4), sodium sulfite (Na 2sO 3), potassium sulfite (K 2sO 3), sodium carbonate (Na 2cO 3), potash (K 2cO 3), sodium phosphate (Na 3pO 4), potassium phosphate (K 3pO 4), vulcanized sodium (Na 2s), potassium sulfide (K 2etc. S) any one in.
In step (b), described patina thing is selected from silver nitrate (AgNO 3), silver nitrite (AgNO 2), silver oxide (AgO), silver carbonate (AgCO 3), silver acetate (CH 3cOOAg), toillen's reagent ([Ag(NH 3) 2] OH), silver cyanide (AgCN), silver sulfate (Ag 2sO 4), silver sulfide (Ag 2s), trifluoroacetic acid silver (C 2f 3o 2ag), silver thiocyanate (AgSCN), silver chlorate (AgCl), silver bromide (AgBr), silver sulfite (Ag 2sO 3), silver iodide (AgI), silver orthophosphate (Ag 3pO 4), silver fluoride (AgF), silver tetrafluoroborate (AgBF 4), pelletization silver (Ag 3n), silver propionate (C 3h 5o 2ag), actol (C 3h 5agO 3), capric acid silver, carboxylic first silver, silver citrate (C 6h 5ag 3o 7), gluconic acid silver, silver cyanate (AgOCN), silver bromate (AgBrO 3), hyptafluorobutyric acid silver (CF 3cF 2cF 2cO 2ag), acetylacetone,2,4-pentanedione silver ([CH 3cOCH=C (O-) CH 3] Ag), five fluorine silver propionate (C 2f 5cO 2ag), inclined alum acid silver (AgVO 3), hexafluoroarsenate silver (AgAsF 6), hexafluorophosphoric acid silver (AgPF 6), p-methyl benzenesulfonic acid silver (CH 3c 6h 4sO 3ag), silver tetrafluoroborate (AgBF 4), complex compound Ag (I) and the part NH of silver 3-, CN-, Cl-, S 2o 3-wait the complex compound of generation, Ag [II] and part Py (pyridine), an adjacent phenanthroline (0 one phen), 8 monohydroxy quinolines (oxin) etc. to generate complex compound, Ag [III] and part F-, IO 4-, TeO 66-etc. any one in the complex compound etc. that generates of minority part.
In step (b), the mixture that solvent in order to dissolve described silver-colored presoma is selected from ester class containing two or more hydroxyl, ethers or binary or polyalcohol etc. or is made up of described binary or polyalcohol or ester class, then or by the mixture of above-mentioned solvent and other solvent composition; Described alcohols, ethers and ester class are selected from ethylene glycol (CH 2oHCH 2oH), propane diols (CH 2oHCH 2cH 2oH, CH 2oHCH 2oHCH 3), glycerine (CH 2oHCHOHCH 2oH), butanediol (C 4h 10o 2), pentanediol (C 5h 12o 2), hexylene glycol (C 6h 14o 2), cyclohexanediol (C 6h 10o 2), glycol dimethyl ether (C 4h 10o 2), ethylene glycol diethyl ether (C 6h 14o 2), diethylene glycol ether (C 6h 14o 3), 1,2-PD carbonic ester (C 4h 6o 3), propylene glycol methyl ether acetate (C 6h 12o 3), butyl glycol ether acetic acid esters (C 8h 16o 3), ethylene glycol monomethyl ether acetate (C 5h 10o 3) etc. in any one.
The process forming described mixed solution in step (a) comprises and adds described protective agent and the step of heating for dissolving and add the step of described additive.
Be divide at least twice to join in described mixed solution described silver-colored precursor solution with the injection rate of 0.05mL/min ~ 10mL/min in step (b), and the injection rate (such as 2mL/min) of silver-colored precursor solution is greater than the injection rate (such as 0.4mL/min) of the silver-colored precursor solution of second time for the first time.
Reaction temperature in step (b) is 60 DEG C ~ 250 DEG C.
Preferably, in step (a), described protective agent is polyvinylpyrrolidone ((C 6h 9nO) n, hereinafter referred to as " PVP "), and by this protective agent heating for dissolving in glycerine; Described additive is hexadecyltrimethylammonium chloride (C 16h 33(CH 3) 3nCl, hereinafter referred to as " CTAC "), and this additive is dissolved in glycerine; In step (b), described silver-colored precursor solution is obtained liquor argenti nitratis ophthalmicus by being dissolved in glycerine by silver nitrate.
In step (a), formed in the process of described additive, after described CTAC is dissolved in glycerine, the concentration ranges of gained solution is 0.1mM ~ 200mM; The implication of M is molar concentration, i.e. mol/L, lower same.Such as can by 0.32mg ~ 0.64g CTAC powder dissolution in 10ml glycerine.
In step (b), formed in the process of described liquor argenti nitratis ophthalmicus, after described silver nitrate is dissolved in glycerine, the concentration ranges of gained solution is 0.01M ~ 1M.Such as 0.06115g ~ 6.115g silver nitrate powder can be dissolved in 36ml glycerine.
In step (a), formed in described protectant process, described PVP addition and described silver nitrate addition keep mass ratio interval to be 0.5 ~ 10.
In step (c), solution step (b) obtained carries out centrifugal motion with certain speed, then adds ethanol and disperses, repeats this process that is centrifugal and dispersion.
In step (c), after process that is centrifugal and dispersion terminates, gained nano silver wire to be scattered in water or ethanol or other solvent thus to obtain described nano silver wire.
Just the manufacture method of nano silver wire of the present invention illustrates below, and the concentration of wherein used liquor argenti nitratis ophthalmicus is the concentration of 1M, CTAC solution is 50mM.
Particularly, step (a) comprises to the container containing 50ml glycerine (such as, three mouthfuls of round-bottomed flasks) in add 5.1g PVP, be heated to 150 DEG C of stirring and dissolving, then 0.5ml CTAC solution is added, finally obtain described mixed solution (that is, polyhydric alcohol solutions), and implementation step (b) after waiting for 2 minutes.
Step (b) comprises with injection speed (such as 2mL/min) slowly, 18ml liquor argenti nitratis ophthalmicus is injected above-mentioned three mouthfuls of round-bottomed flasks, when question response becomes canescence, again 12ml liquor argenti nitratis ophthalmicus is injected above-mentioned three mouthfuls of round-bottomed flasks with injection speed (such as 0.4mL/min) slowly, after 3 hours, terminate reaction.
In above step when the actual production of nano silver wire is greater than or less than the output of the present embodiment, the consumption of each solution and addition etc. should be done the expansion of corresponding proportion and reduce; First time, silver-colored precursor solution was respectively 60% and 40% with the addition of the silver-colored precursor solution of second time.
Step (c) comprises the solution that obtains in step (b) with the centrifugation 20 minutes of 2000 revs/min, then add ethanol to disperse again, repeating this centrifugal process with disperseing three times, then gained nano silver wire being scattered in the liquid such as water or ethanol.Preferably, in above-mentioned steps (a) ~ (c), the equipment such as magnetic agitation heating jacket, peristaltic pump can be adopted as required.
Shown in please refer to the drawing 2 to Fig. 6, the nano silver wire obtained by the manufacture method of nano silver wire of the present invention, statistics line length is 35.4 microns, and particle diameter is 39.8 nanometers, and the line diameter ratio of most nano silver wire is greater than 1000.By the nano silver wire that the manufacture method of nano silver wire of the present invention obtains, the wire diameter of most nano silver wire is less than 50 nanometers, and line length is greater than 15 microns, and productive rate is not less than 50%, is applicable to batch preparation.
Utilize the conductive film prepared by nano silver wire that manufacture method of the present invention obtains, there is transmitance high, the features such as sheet resistance is little, and compared to tin indium oxide (ITO) film, with low cost, pliability is good, can be used for replacing ito thin film.
Compared to prior art, the present invention adopts first with protective agent, and reinject silver-colored presoma, and point at least twice injection (not being disposable injection), therefore not only can obtain the nano silver wire of high line diameter ratio but also be applicable to preparation in enormous quantities.
It should be noted that: above embodiment is only for illustration of the present invention and unrestricted technical scheme described in the invention, although this description reference the above embodiments are to present invention has been detailed description, but, those of ordinary skill in the art is to be understood that, person of ordinary skill in the field still can modify to the present invention or equivalent replacement, and all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, all should be encompassed in right of the present invention.

Claims (13)

1. a manufacture method for nano silver wire, is characterized in that: this manufacture method comprises the steps:
(a). provide mixed solution, at least containing a kind of protective agent and a kind of additive in this mixed solution, described additive is halide and/or can forms the compound of indissoluble salt with silver ion;
(b). the silver-colored precursor solution containing patina thing is provided, and divides at least twice to join in described mixed solution this silver-colored precursor solution; When silver-colored presoma reacts to canescence after injecting for the first time, then second time injects silver-colored presoma, and the injection rate of silver-colored precursor solution is greater than the injection rate of the silver-colored precursor solution of second time for the first time;
(c). be separated and obtain described nano silver wire.
2. the manufacture method of nano silver wire as claimed in claim 1, it is characterized in that: in step (a), described protective agent is selected from:
Polyvinylpyrrolidone (the PVP, (C of various molecular weight 6h 9nO) n), the derivative of polyvinylpyrrolidone, polyvinyl alcohol (PVA, (C 2h 4o) n), PEO (PEO, (CH 2cH 2o) n), lauryl sodium sulfate (C 12h 25sO 4na), lauryl amine (C 12h 27n), octadecylamine (CH 3(CH 2) 16cH 2nH 2), hexadecyltrimethylammonium chloride (CTAC, C 16h 33(CH 3) 3nCl), softex kw (CTAB, C 16h 33(CH 3) 3nBr), gelatin, methylcellulose, the ninth of the ten Heavenly Stems two mercaptan, succinimide mercaptans; Or
Protective agent containing sulfydryl or amino; Or
The polymer formed by one or several monomers following, described monomer is selected from:
Acrylic acid (C 3h 4o 2), butenoic acid (C 4h 6o 2), maleic acid (C 4h 4o 4), methyl-maleic acid, fumaric acid and its esters;
Containing aforesaid propylene acid (C 3h 4o 2), butenoic acid (C 4h 6o 2), maleic acid (C 4h 4o 4), the ester class of methyl-maleic acid, fumaric acid and salts substances thereof, amide-type, acid anhydrides, nitrile;
Acrylic sulfonic acid, vinyl sulfonic acid, methacrylic sulfonic acid, 3-sulfopropylmetliylacrylic and ester class, amide-type, nitrile containing phosphonate radical;
N-ethernamine class;
Any one in ethylene acetal, vinyl butyral, vinyl alcohol and ethers thereof, ester class.
3. the manufacture method of nano silver wire as claimed in claim 1, it is characterized in that: in step (a), described halide is selected from sodium chloride (NaCl), potassium chloride (KCl), sodium bromide (NaBr), KBr (KBr), sodium iodide (NaI), KI (KI), softex kw (CTAB, C 16h 33(CH 3) 3or hexadecyltrimethylammonium chloride (CTAC, C NBr) 16h 33(CH 3) 3nCl) any one in.
4. the manufacture method of nano silver wire as claimed in claim 1, is characterized in that: in step (a), and the described compound that can form indissoluble salt with silver ion is selected from sodium sulphate (Na 2sO4), potassium sulfate (K 2sO4), sodium sulfite (Na 2sO 3), potassium sulfite (K 2sO 3), sodium carbonate (Na 2cO 3), potash (K 2cO 3), sodium phosphate (Na 3pO 4), potassium phosphate (K 3pO 4), vulcanized sodium (Na 2or potassium sulfide (K S) 2s) any one in.
5. the manufacture method of nano silver wire as claimed in claim 1, it is characterized in that: in step (b), described patina thing is selected from silver nitrate (AgNO 3), silver nitrite (AgNO 2), silver oxide (AgO), silver carbonate (AgCO 3), silver acetate (CH 3cOOAg), toillen's reagent ([Ag(NH 3) 2] OH), silver cyanide (AgCN), silver sulfate (Ag 2sO 4), silver sulfide (Ag 2s), trifluoroacetic acid silver (C 2f 3o 2ag), silver thiocyanate (AgSCN), silver chlorate (AgCl), silver bromide (AgBr), silver sulfite (Ag 2sO 3), silver iodide (AgI), silver orthophosphate (Ag 3pO 4), silver fluoride (AgF), silver tetrafluoroborate (AgBF 4), pelletization silver (Ag 3n), silver propionate (C 3h 5o 2ag), actol (C 3h 5agO 3), capric acid silver, carboxylic first silver, silver citrate (C 6h 5ag 3o 7), gluconic acid silver, silver cyanate (AgOCN), silver bromate (AgBrO 3), hyptafluorobutyric acid silver (CF 3cF 2cF 2cO 2ag), acetylacetone,2,4-pentanedione silver ([CH 3cOCH=C (O-) CH 3] Ag), five fluorine silver propionate (C 2f 5cO 2ag), inclined alum acid silver (AgVO 3), hexafluoroarsenate silver (AgAsF 6), hexafluorophosphoric acid silver (AgPF 6), p-methyl benzenesulfonic acid silver (CH 3c 6h 4sO 3ag), silver tetrafluoroborate (AgBF 4), complex compound Ag (I) and the part NH of silver 3-, CN-, Cl-, S 2o 3the complex compound that-the complex compound, Ag [II] and part Py (pyridine), an adjacent phenanthroline (0 one phen), the 8 monohydroxy quinolines (oxin) that generate generate or Ag [III] and part F-, IO 4-, TeO 66-generate complex compound in any one.
6. the manufacture method of nano silver wire as claimed in claim 5, it is characterized in that: in step (b), in order to dissolve the mixture that the solvent of described silver-colored presoma is ester class, ethers or binary containing two or more hydroxyl or polyalcohol or is made up of described binary or polyalcohol or ester class; Described alcohols, ethers and ester class are selected from ethylene glycol (CH 2oHCH 2oH), propane diols (CH 2oHCH 2cH 2oH, CH 2oHCH 2oHCH 3), glycerine (CH 2oHCHOHCH 2oH), butanediol (C 4h 10o 2), pentanediol (C 5h 12o 2), hexylene glycol (C 6h 14o 2), cyclohexanediol (C 6h 10o 2), glycol dimethyl ether (C 4h 10o 2), ethylene glycol diethyl ether (C 6h 14o 2), diethylene glycol ether (C 6h 14o 3), 1,2-PD carbonic ester (C 4h 6o 3), propylene glycol methyl ether acetate (C 6h 12o 3), butyl glycol ether acetic acid esters (C 8h 16o 3) or ethylene glycol monomethyl ether acetate (C 5h 10o 3) in any one.
7. the manufacture method of the nano silver wire as described in any one in claim 1 to 6, is characterized in that: the process forming described mixed solution in step (a) comprises and adds described protective agent and the step of heating for dissolving and add the step of described additive.
8. the manufacture method of the nano silver wire as described in any one in claim 1 to 6, is characterized in that: be the injection rate with 0.05mL/min ~ 10mL/min in step (b) willdescribed silver-colored precursor solution joins in described mixed solution at twice, and silver-colored precursor solution is respectively 60% and 40% with the addition of the silver-colored precursor solution of second time for the first time.
9. the manufacture method of the nano silver wire as described in any one in claim 1 to 6, is characterized in that: the reaction temperature in step (b) is 60 DEG C ~ 250 DEG C.
10. the manufacture method of the nano silver wire as described in any one in claim 1 to 6, it is characterized in that: in step (a), described protective agent is polyvinylpyrrolidone (PVP, (C 6h 9nO) n), and by this protective agent heating for dissolving in glycerine; Described additive is hexadecyltrimethylammonium chloride (CTAC, C 16h 33(CH 3) 3and this additive is dissolved in glycerine NCl); In step (b), described silver-colored precursor solution is obtained liquor argenti nitratis ophthalmicus by being dissolved in glycerine by silver nitrate.
The manufacture method of 11. nano silver wires as claimed in claim 10, is characterized in that: in step (a), is formed in the process of described additive, described hexadecyltrimethylammonium chloride (CTAC, C 16h 33(CH 3) 3nCl) after being dissolved in glycerine, the concentration ranges of gained solution is 0.1mM ~ 200mM;
In step (b), formed in the process of described liquor argenti nitratis ophthalmicus, after described silver nitrate is dissolved in glycerine, the concentration ranges of gained solution is 0.01M ~ 1M;
In step (a), formed in described protectant process, described polyvinylpyrrolidone (PVP, (C 6h 9nO) n) addition and described silver nitrate addition keep mass ratio interval to be 0.5 ~ 10.
The manufacture method of 12. nano silver wires as described in any one in claim 1 to 6, it is characterized in that: in step (c), solution step (b) obtained carries out centrifugal motion with certain speed, then add ethanol to disperse again, repeat this process that is centrifugal and dispersion.
The manufacture method of 13. nano silver wires as claimed in claim 12, is characterized in that: in step (c), after process that is centrifugal and dispersion terminates, to be scattered in by gained nano silver wire in water or ethanol thus to obtain described nano silver wire.
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