CN104759634A - Preparation method for superfine silver nanowire - Google Patents
Preparation method for superfine silver nanowire Download PDFInfo
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- CN104759634A CN104759634A CN201510095360.9A CN201510095360A CN104759634A CN 104759634 A CN104759634 A CN 104759634A CN 201510095360 A CN201510095360 A CN 201510095360A CN 104759634 A CN104759634 A CN 104759634A
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Abstract
The invention relates to the technical field of one-dimensional nanomaterial preparation, and in particular relates to a preparation method for superfine silver nanowire applied to flexible transparent conducting film. The preparation method for superfine silver nanowire takes the ethylene glycol and silver nitrate as the raw materials, metal halide is added and material adding speed and reaction temperature are controlled to obtain the superfine silver nanowire which is good in dispersibility, the average diameter of the superfine silver nanowire which is 20-50nm and the length is 5-20mum. Seed crystal is not needed, the preparation method for superfine silver nanowire is simple in experiment process, moderate in condition, environment friendly and effective, the dispersibility of the prepared silver nanowire is good, the uniformity is high, the length-diameter ratio is big, and the silver nanowire has potential application prospect in the transparent conducting film.
Description
Technical field
The present invention relates to monodimension nanometer material preparing technical field, particularly relate to a kind of preparation method that can be used for the ultra-fine silver nano wire of flexible transparent conducting film.
Background technology
Along with the fast development of various display screen industry and the demand to flexible electrical equipment, people have higher requirement to flexible and transparent conductive material, therefore, find suitable conductive material, are one of hot research contents of current flexible transparent conducting film; Wherein, silver nano material is due to optics, electromagnetism, the mechanical property of its uniqueness, important role in numerous opto-electronic device, flexible electronic device, particularly nano silver wire is except possessing the excellent electric conductivity of silver, also there is the advantages such as pliability is good, energy homogeneous film formation, procedure for processing are simple, be considered to be the most possible material replacing conventional I TO transparency electrode, provide possibility for realizing flexibility, bent LED display, touch-screen etc., obtaining extensive concern.
Alcohothermal method is at present for the preparation of the main method of nano silver wire, application number be 201310491884.0 Chinese patent research report in polyalcohol, to add the method that silver compound and PVP obtain high length-diameter ratio nano silver wire, but need in reaction to add Ag as crystal seed, prepared nanowire diameter is about 100 nm; Application number is the Chinese patent report MnCl of 201010281639.3
2prepare the method for nano silver wire as controlling agent, but course of reaction needs to pass into inert gas shielding, this improves preparation cost undoubtedly, also makes complex technical process, and prepared nano silver wire diameter is difficult to reach 50 below nm; Chinese patent 201310302393.7 reports a kind of nano silver wire preparation method of high-aspect-ratio, adopt disposable hybrid reaction material, and add a certain amount of halide promotion reaction, obtain average length 52 μm, the nano silver wire that length, width and height ratio is greater than 400, but the average 130nm of its diameter, and the reaction needed heating process of 5 ~ 24 hours.
Physicochemical properties and the potential application of nano silver wire depend on its size, (the The optical and electrical properties of silver nanowire mesh films such as the G. Khanarian of Dow Chemical company, Appl. Phys. 2013,114,024302) by experiment and theory calculate, report the diameter <50 nm when nano silver wire, during length >5 μm, prepared conducting film has excellent performance, therefore, the preparation of ultra-fine silver nano wire, is significant.
Summary of the invention
The object of the invention is to in current nano silver wire preparation process, complex process, diameter is difficult to the shortcomings such as control, and provide one not need to add crystal seed, experimentation is simple, and mild condition, the method for environment-friendly high-efficiency prepares ultra-fine silver nano wire.
For achieving the above object, the invention provides a kind of preparation method of ultra-fine silver nano wire, adopt following technical scheme:
(1) get ethylene glycol, metal halide mixes, obtain mixed liquor A; Mixed liquor A is added hot reflux.
(2) certain density AgNO is prepared respectively
3two kinds of solution are slowly added in mixed liquor A, stirring reaction by solution and PVP solution simultaneously.
(3) solution after reacting completely, through sonic oscillation, filtration washing, namely obtains ultra-fine silver nano wire.
Reflux temperature described in step (1) is 140 ~ 180 DEG C, and return time is 0.5 ~ 2h.
In step (1), metal halide is KBr, and in mixed liquor A, the molal volume concentration of KBr is 0.00125 ~ 0.005 mol/L.
In step (2), solvent is ethylene glycol, PVP and AgNO
3mol ratio be 1.5 ~ 4:1, AgNO
3molal volume concentration be the molal volume concentration of 0.05 ~ 0.20 mol/L, PVP be 0.15 ~ 0.6 mol/L, AgNO
3volume and the volume ratio of mixed liquor A be 1:2 ~ 8; Ag ion reduction becomes nano silver wire by concentration restriction, otherwise easily generation particle or draw ratio do not reach target call.
A kind of ultra-fine silver nanowire preparation method of the present invention, the stirring reaction temperature described in step (2) is 140 ~ 180 DEG C, and the reaction time is 1 ~ 4 h.
A kind of ultra-fine silver nanowire preparation method of the present invention, the solution described in step (2) adds speed and is 0.2-0.5 mLmin
-1.
A kind of ultra-fine silver nanowire preparation method of the present invention, its Mw ~ 1 of step (2) described PVP, 300,000.
A kind of ultra-fine silver nanowire preparation method of the present invention, step (3) described washing methods is that after ultrasonic vibration, core filters cleaning 3 times, and cleaning agent is followed successively by deionized water, acetone and ethanol or deionized water, acetone
With ethanol and acetone arbitrarily than mixed liquor.
The beneficial effect that the present invention compared with prior art has is:
1, do not need additionally to add crystal seed, cheaper starting materials is easy to get, simple to operate.
2, utilize KBr to Ag
+buffering release action, be mainly used to the speed of control Ag ion reduction Cheng Yin, be conducive to silver-colored linear growth, particle is few, and diameter, the length of nano wire is regulated by controlling the reaction conditions such as reaction temperature, time and reactant concentration, the diameter obtaining nano silver wire after washing is 20 ~ 50 nm, and length is 5 ~ 20 μm.
3, nano silver wire good dispersion, the uniformity is high, and draw ratio is large, possesses excellent light transmission, electric conductivity and resist to deflect performance, in flexible transparent conducting film, have potential application foreground.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of nano silver wire in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of nano silver wire in embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of nano silver wire in embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of nano silver wire in embodiment 2.
Fig. 5 is the scanning electron microscope (SEM) photograph of nano silver wire in embodiment 2.
Fig. 6 is the scanning electron microscope (SEM) photograph of nano silver wire in embodiment 3.
Fig. 7 is the scanning electron microscope (SEM) photograph of nano silver wire in comparative example.
Fig. 8 is the scanning electron microscope (SEM) photograph of nano silver wire in comparative example.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention and beneficial effect are further described.
Embodiment 1
(1) get 40 mL ethylene glycol, 0.1 mmolKBr mixes, obtain mixed liquor A; Mixed liquor A is poured in 250 mL there-necked flasks, 180 DEG C of oil bath magnetic agitation pots add hot reflux 0.5 h.
(2) AgNO that 10 mL molar concentrations are 0.15 M is prepared respectively
3solution and 10 mL molar concentrations are PVP(Mw ~ 1 of 0.6M, 300,000) and solution, by two kinds of solution with 0.2 mLmin
-1speed add in mixed liquor A, at 160 DEG C of stirring reaction 2 h simultaneously.
(3) solution after reacting completely cools naturally, filters cleaning 3 times successively, namely obtain ultra-fine silver nano wire with deionized water, acetone, ethanol with any of acetone than core after mixed liquor ultrasonic vibration.
Fig. 1 is the X-ray diffractogram of copper nano-wire prepared by embodiment 1, and as shown in Figure 1, prepared product is the metal silver nanowires of pure face-centred cubic structure.
Fig. 2, Fig. 3 are the scanning electron microscope (SEM) photographs of nano silver wire prepared by embodiment 1, and be 40 ~ 50 nm by the average diameter of the high-visible nano wire of Fig. 2, as shown in Figure 3, nano wire good dispersion, the uniformity is high, and its length is 15 ~ 20 μm.
Embodiment 2
(1) get 40 mL ethylene glycol, 0.1 mmolKBr mixes, obtain mixed liquor A; Mixed liquor A is poured in 250 mL there-necked flasks, 170 DEG C of oil bath magnetic agitation pots add hot reflux 1 h.
(2) AgNO that 10 mL molar concentrations are 0.15 M is prepared respectively
3solution and 10 mL molar concentrations are PVP(Mw ~ 1 of 0.45M, 300,000) and solution, by two kinds of solution with 0.3 mLmin
-1speed add in mixed liquor A, at 180 DEG C of stirring reaction 1 h simultaneously.
(3) solution after reacting completely cools naturally, filters cleaning 3 times successively, namely obtain ultra-fine silver nano wire with deionized water, acetone, ethanol with any of acetone than core after mixed liquor ultrasonic vibration.
Fig. 4, Fig. 5 are the scanning electron microscope (SEM) photographs of nano silver wire prepared by embodiment 2, and be 30 ~ 40 nm by the average diameter of the high-visible nano wire of Fig. 4, as seen from Figure 5, nano wire good dispersion, the uniformity is high, and length is 10 ~ 15 μm.
Embodiment 3
(1) get 40 mL ethylene glycol, 0.2mmolKBr mixes, obtain mixed liquor A; Mixed liquor A is poured in 250 mL there-necked flasks, 140 DEG C of oil bath magnetic agitation pots add hot reflux 2 h.
(2) AgNO that 20 mL molar concentrations are 0.05 M is prepared respectively
3solution and 20 mL molar concentrations are PVP(Mw ~ 1 of 0.15M, 300,000) and solution, by two kinds of solution with 0.5 mLmin
-1speed add in mixed liquor A, at 170 DEG C of stirring reaction 2 h simultaneously.
(3) solution after reacting completely cools naturally, filters cleaning 3 times successively, namely obtain ultra-fine silver nano wire with core after deionized water, acetone, ethanolic solution ultrasonic vibration.
Fig. 6 is the scanning electron microscope (SEM) photograph of nano silver wire prepared by embodiment 3, and as seen from Figure 6, its average diameter is 20 ~ 30 nm, and length is 5 ~ 10 μm.
Embodiment 4
(1) get 40 mL ethylene glycol, 0.05 mmolKBr mixes, obtain mixed liquor A; Mixed liquor A is poured in 250 mL there-necked flasks, 160 DEG C of oil bath magnetic agitation pots add hot reflux 1 h.
(2) AgNO that 5 mL molar concentrations are 0.2 M is prepared respectively
3solution and 5 mL molar concentrations are PVP(Mw ~ 1 of 0.3 M, 300,000) and solution, by two kinds of solution with 0.2 mLmin
-1speed add in mixed liquor A, at 140 DEG C of stirring reaction 4 h simultaneously.
(3) solution after reacting completely cools naturally, and filter cleaning 3 times with core after deionized water, acetone, ethanolic solution ultrasonic vibration successively, namely obtain ultra-fine silver nano wire, its average diameter is 40 ~ 50 nm, length about 15 ~ 20 μm.
Comparative example:
In order to embody the effect of KBr as sustained release agent, this comparative example does not add KBr, and adopting uses the same method has prepared nano silver wire, specific as follows:
(1) getting 40 mL ethylene glycol pours in 250 mL there-necked flasks, and 180 DEG C of oil bath magnetic agitation pots add hot reflux 1 h.
(2) AgNO that 10 mL molar concentrations are 0.2 M is prepared respectively
3solution and 10 mL molar concentrations are PVP(Mw ~ 1 of 0.3 M, 300,000) and solution, by two kinds of solution with 0.2 mLmin
-1speed add in ethylene glycol solution, at 140 DEG C of stirring reaction 4 h simultaneously.
(3) solution after reacting completely cools naturally, filters cleaning 3 times successively, namely obtain nano silver wire with core after deionized water, acetone, ethanolic solution ultrasonic vibration.
Fig. 7, Fig. 8 are the scanning electron microscope (SEM) photographs of nano silver wire prepared by comparative example.From Fig. 7, Fig. 8, its average diameter is about 100 nm, and length is 15 ~ 20 μm.
Claims (8)
1. a preparation method for ultra-fine silver nano wire, is characterized in that step is as follows:
(1) get ethylene glycol, metal halide mixes, obtain mixed liquor A; Mixed liquor A is added hot reflux;
(2) certain density AgNO is prepared respectively
3two kinds of solution are slowly added in mixed liquor A, stirring reaction by solution and PVP solution simultaneously;
(3) solution after reacting completely, through sonic oscillation, filtration washing, namely obtains ultra-fine silver nano wire.
2. the preparation method of a kind of ultra-fine silver nano wire as claimed in claim 1, it is characterized in that: the reflux temperature described in step (1) is 140 ~ 180 DEG C, return time is 0.5 ~ 2h.
3. the preparation method of a kind of ultra-fine silver nano wire as claimed in claim 1, it is characterized in that in step (1), metal halide is KBr, in mixed liquor A, the molal volume concentration of KBr is 0.00125 ~ 0.005 mol/L.
4. the preparation method of a kind of ultra-fine silver nano wire as claimed in claim 1, is characterized in that: in step (2), solvent is ethylene glycol, PVP and AgNO
3mol ratio be 1.5 ~ 4:1, AgNO
3molal volume concentration be the molal volume concentration of 0.05 ~ 0.20 mol/L, PVP be 0.15 ~ 0.6 mol/L, AgNO
3volume and the volume ratio of mixed liquor A be 1:2 ~ 8; Ag ion reduction becomes nano silver wire by concentration restriction, otherwise easily generation particle or draw ratio do not reach target call.
5. the preparation method of a kind of ultra-fine silver nano wire as claimed in claim 1, it is characterized in that: the stirring reaction temperature described in step (2) is 140 ~ 180 DEG C, the reaction time is 1 ~ 4 h.
6. the preparation method of a kind of ultra-fine silver nano wire as claimed in claim 1, is characterized in that: the solution described in step (2) adds speed and is 0.2-0.5 mLmin
-1.
7. the preparation method of a kind of ultra-fine silver nano wire as claimed in claim 1, is characterized in that: its Mw ~ 1 of step (2) described PVP, 300,000.
8. the preparation method of a kind of ultra-fine silver nano wire as claimed in claim 1, it is characterized in that: step (3) described washing methods is that after ultrasonic vibration, core filters cleaning 3 times, cleaning agent be followed successively by deionized water, acetone and ethanol or deionized water, acetone and ethanol and acetone arbitrarily than mixed liquor.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104999089A (en) * | 2015-07-15 | 2015-10-28 | 济宁利特纳米技术有限责任公司 | Method for preparing silver nanowire in hydrophobic phase |
| CN105537622A (en) * | 2016-01-07 | 2016-05-04 | 嘉兴禾浦光电科技有限公司 | Method for preparing silver nanowires |
| CN105537615A (en) * | 2015-12-24 | 2016-05-04 | 河南大学 | Method of preparing silver nanowires in different diameters with one-pot process |
| CN105750559A (en) * | 2016-01-13 | 2016-07-13 | 深圳市东方亮化学材料有限公司 | Method of preparing silver nanowire and transparent conductive film of silver nanowire |
| CN106513698A (en) * | 2016-11-01 | 2017-03-22 | 复旦大学 | Successive addition preparation technology of high-concentration nano silver thread |
| CN107030294A (en) * | 2015-07-23 | 2017-08-11 | 北京华纳高科科技有限公司 | A kind of ultra-fine silver nano wire and its fluid-tight preparation method |
| CN109604633A (en) * | 2018-12-28 | 2019-04-12 | 广东银研高新材料股份有限公司 | A kind of preparation method of nano-silver thread |
| CN110640163A (en) * | 2019-10-18 | 2020-01-03 | 上海交通大学 | Method for preparing superfine silver nanowires with ultrahigh length-diameter ratio |
| CN115870510A (en) * | 2022-11-29 | 2023-03-31 | 德清县浙工大莫干山研究院 | Method for preparing superfine silver nanowires with assistance of moisture |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104999089A (en) * | 2015-07-15 | 2015-10-28 | 济宁利特纳米技术有限责任公司 | Method for preparing silver nanowire in hydrophobic phase |
| CN104999089B (en) * | 2015-07-15 | 2017-07-25 | 济宁利特纳米技术有限责任公司 | The preparation method of nano silver wire in a kind of hydrophobic phase |
| CN107030294B (en) * | 2015-07-23 | 2019-02-19 | 北京华纳高科科技有限公司 | A kind of ultra-fine silver nano wire and its fluid-tight preparation method |
| CN107030294A (en) * | 2015-07-23 | 2017-08-11 | 北京华纳高科科技有限公司 | A kind of ultra-fine silver nano wire and its fluid-tight preparation method |
| CN105537615B (en) * | 2015-12-24 | 2018-10-30 | 河南大学 | The method that one kettle way prepares different-diameter nano silver wire |
| CN105537615A (en) * | 2015-12-24 | 2016-05-04 | 河南大学 | Method of preparing silver nanowires in different diameters with one-pot process |
| CN105537622A (en) * | 2016-01-07 | 2016-05-04 | 嘉兴禾浦光电科技有限公司 | Method for preparing silver nanowires |
| CN105750559A (en) * | 2016-01-13 | 2016-07-13 | 深圳市东方亮化学材料有限公司 | Method of preparing silver nanowire and transparent conductive film of silver nanowire |
| CN106513698A (en) * | 2016-11-01 | 2017-03-22 | 复旦大学 | Successive addition preparation technology of high-concentration nano silver thread |
| CN106513698B (en) * | 2016-11-01 | 2019-02-26 | 复旦大学 | A kind of gradually addition preparation process of highly concentrated nano silver wire |
| CN109604633A (en) * | 2018-12-28 | 2019-04-12 | 广东银研高新材料股份有限公司 | A kind of preparation method of nano-silver thread |
| CN110640163A (en) * | 2019-10-18 | 2020-01-03 | 上海交通大学 | Method for preparing superfine silver nanowires with ultrahigh length-diameter ratio |
| CN110640163B (en) * | 2019-10-18 | 2021-11-30 | 上海交通大学 | Method for preparing superfine silver nanowires with ultrahigh length-diameter ratio |
| CN115870510A (en) * | 2022-11-29 | 2023-03-31 | 德清县浙工大莫干山研究院 | Method for preparing superfine silver nanowires with assistance of moisture |
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