CN103639422A - Preparation method for ultralong transparent silver nanowires - Google Patents
Preparation method for ultralong transparent silver nanowires Download PDFInfo
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- CN103639422A CN103639422A CN201310714543.5A CN201310714543A CN103639422A CN 103639422 A CN103639422 A CN 103639422A CN 201310714543 A CN201310714543 A CN 201310714543A CN 103639422 A CN103639422 A CN 103639422A
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- preparation
- silica flour
- agno
- nano silver
- silver wire
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Abstract
The invention provides a preparation method for ultralong transparent silver nanowires. The preparation method utilizes the redox reaction of silica powder and HF (hydrofluoric acid)/AgNO3 (silver nitrate) water solution under a high-pressure boiling condition: the silica powder is oxidized by the strong oxidization system formed by the HF/AgNO3 water solution, Ag (silver) ions near the surfaces of the silica powder are deacidized into Ag atoms, and the Ag atoms are deposited on the surfaces of the silica powders to form the ultralong transparent silver nanowires. The preparation method has the advantages of fewer preparation steps, simplicity of operation, environment friendliness and high yield, and can be applied for the scale production of silver nanowires; the prepared silver nanowires have a larger length, and can replace ITO (indium tin oxide) to serve as electrodes of a flexible display.
Description
Technical field
The invention belongs to technical field of nano material, relate to be a kind ofly produced on a large scale, the method for the transparent nano silver wire of overlength.
Background technology
At present, the screen surface material of flexible display screen---tin indium oxide (Indium Tin Oxides, ITO) occurred rare situation, the rare related industries that makes of this material has been absorbed in awkward situation, also makes people start to find the substitute of this material.Nano silver wire is because having good electric conductivity, the alternative ITO of transparent and flexible feature as the electrode of flexible display screen.The preparation method of nano silver wire is mainly divided into Physical and chemical method, and wherein chemical method is because its technique is simple, cost is low, easy large-scale production develops rapidly.The method of chemical preparation nano silver wire mainly contains wet chemistry method, template electrochemical method at present, yet these method complicated operations and contaminated environment can not generate transparent conductive silver nano wire.
Summary of the invention
The present invention is in order to solve the problems of the technologies described above, and a kind of method of transparent nano silver wire that can large-scale production overlength is provided.
A preparation method for nano silver wire, comprises the steps:
Silica flour is cleaned, and then silica flour is put into and is filled HF/AgNO
3in the reactor of the aqueous solution, form reaction solution, after sealing, be heated to reaction solution boiling, after naturally cooling 24 ~ 48 h, finish reaction; From reaction solution, filter out silica flour, and silica flour is joined to standing 12 ~ 48 h in deionized water, by its taking-up and immerse the AgNO of 0.5 ~ 10wt%
3in solution, soak 10 ~ 50 min, repeatedly clean three times afterwards by deionized water, under 100 ~ 210 ℃ of argon atmosphers, dry 10 ~ 72 h obtain nano silver wire.
The cleaning way of described silica flour comprises the steps: to use successively acetone, ethanol, washed with de-ionized water silica flour, then puts into H
2sO
4/ H
2o
2standing 10 ~ 50 min in solution (volume ratio is 3:1), after ultrasonic 12 ~ 48 h, clean up by deionized water.
Described silica flour, its fineness is 5 ~ 5000 μ m.
Described HF/AgNO
3the aqueous solution, accounts for 20 ~ 60% of reactor volume, and the content of HF is 5wt% ~ 20wt%, AgNO
3molar concentration be 10 ~ 45mM.
Described inert gas is nitrogen or argon gas.
In this experiment, the deposition of Ag is based on following chemical equation:
This equation can be decomposed into two half-reaction equation:
By aforesaid equation, we can find out, Ag is deposited on silicon powder surface, silicon powder surface Ag under HF solution system auxiliary
+minimizing with the cost that is oxidized to of silicon.
Fig. 1 has shown that to us silica flour is containing AgNO
3hF solution in there is etched process.In the time of incipient, the silicon powder surface that is deposited on of the etching of Si and Ag occurs simultaneously, and first the Ag atom of deposition forms equally distributed nucleus at silicon powder surface, then forms ag nano-cluster; The ag nano-cluster of silicon powder surface regional area is as negative electrode, and silicon is around as anode, the spontaneous galvanic cell that is assembled into nano-scale.Along with the carrying out of electrochemical reaction, some ag nano-clusters fall into the duck eye that silicon powder surface forms because of corrosion, AgNO
3/ HF solution the silica flour that constantly etching exposes downwards, ag nano-cluster particle is constantly grown and is formed the nano silver wire of crystallization.In the process of deposition of silver, silicon powder surface has formed one deck simultaneously and has set crystalline silver, and most tree is crystalline silver is consumed because of the synchronous growth of superfluous depositing silver nano wire.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) preparation process of the present invention is few, simple to operate, environmental friendliness, and productive rate is high, can be used for large-scale production nano silver wire.
(2) the nano silver wire diameter that prepared by the present invention is 20 ~ 90nm, length >=20 μ m.
Accompanying drawing explanation
Fig. 1 is that silica flour is at AgNO
3the schematic diagram of etching process in/HF solution.
Fig. 2 is SEM (SEM) figure of nano silver wire.
Fig. 3 is the dispersion spectrogram of nano silver wire.
Fig. 4 ~ 6 are various HF concentration, different AgNO
3the SEM of the nano silver wire of lower preparation (SEM) figure; Wherein, Fig. 4 represents that HF concentration is 20wt%, AgNO
3concentration is 5 mM; Fig. 5 represents that HF concentration is 20 wt %, AgNO
3concentration is 40mM; Fig. 6 represents AgNO
3concentration is that 35 mM, HF concentration are 15 wt %.
Fig. 7 is the X-ray diffractogram of nano silver wire.
The specific embodiment
Below in conjunction with embodiment, the present invention is done to further detailed description, but embodiments of the present invention are not limited to this.
If no special instructions, the present invention's reagent used is AR.
Embodiment 1
(1) by fineness, be that the silica flour of 5 ~ 5000 μ m is put into beaker, with acetone, ethanol, clean 5 min successively, then use washed with de-ionized water 2～3 times, then put into H
2sO
4/ H
2o
2solution (H
2sO
4/ H
2o
2volume ratio is 3:1) middle immersion 10 min, then insert ultrasonic 12 h in ultrasonic oscillation instrument, to remove the organic matter of silicon powder surface completely.Finally, then by deionized water, clean up standby.
(2) in the autoclave of inner liner polytetrafluoroethylene, preparation contains 5wt% HF and 45 mM AgNO
3solution, the silica flour after cleaning is added in reactor and forms reaction solution, after sealing, be heated to reaction solution boiling, after naturally cooling 24 h, finish to react.The volume of reaction solution accounts for 20% of reactor volume.
(3) from reaction solution, filter out silica flour, and silica flour is joined to standing 48 h in deionized water, be then heated to moisture and volatilize completely, obtain white transparent dough, by its taking-up and immerse the AgNO of 0.5wt%
3in solution, soak 10 min, etching silicon powder surface, makes residual silver catalyst generate nano silver wire, not only can make nano wire depart from silicon powder surface, and further refinement nano silver wire, by deionized water, repeatedly clean three times afterwards, under 140 ℃ of argon atmosphers, dry 10 h obtain nano silver wire.
(1) by fineness, be that the silica flour of 5 ~ 5000 μ m is put into beaker, with acetone, ethanol, clean 5min successively, then use washed with de-ionized water 2～3 times, then put into H
2sO
4/ H
2o
2solution (H
2sO
4/ H
2o
2volume ratio is 3:1) middle immersion 10 min, then insert ultrasonic 12 h in ultrasonic oscillation instrument, to remove the organic matter of silicon powder surface completely.Finally, then by deionized water, clean up standby.
(2) in the autoclave of inner liner polytetrafluoroethylene, preparation contains 20 HF of wt % and the AgNO of 10mM
3solution, the silica flour after cleaning is added in reactor and forms reaction solution, after sealing, be heated to reaction solution boiling, after naturally cooling 48 h, finish to react.The volume of reaction solution accounts for 60% of reactor volume.
(3) from reaction solution, filter out silica flour, and silica flour is joined to standing 20 h in deionized water, be then heated to moisture and volatilize completely, obtain white transparent dough, by its taking-up and immerse the AgNO of 4wt%
3in solution, soak 30 min, etching silicon powder surface, makes residual silver catalyst generate nano silver wire, not only can make nano silver wire depart from silicon face, and further refinement nano silver wire, by deionized water, repeatedly clean three times afterwards, under 100 ℃ of blanket of nitrogen, dry 32 h obtain nano silver wire.
Embodiment 3
(1) by fineness, be that the silica flour of 5 ~ 5000 μ m is put into beaker, with acetone, ethanol, clean 5 min successively, then use washed with de-ionized water 2～3 times, then put into H
2sO
4/ H
2o
2solution (H
2sO
4/ H
2o
2volume ratio is 3:1) middle immersion 10 min, then insert ultrasonic 12 h in ultrasonic oscillation instrument, to remove the organic matter of silicon powder surface completely.Finally, then by deionized water, clean up standby.
(2) HF that preparation contains 30wt% in the autoclave of inner liner polytetrafluoroethylene and the AgNO of 25 mM
3reaction solution, the silica flour after cleaning is added in reactor and forms reaction solution, after sealing, be heated to reaction solution boiling, after naturally cooling 72 h, finish to react.The volume of reaction solution should be no more than 40% of reactor volume.
(3) from reaction solution, filter out silica flour, and silica flour is joined to standing 12 h in deionized water, be then heated to moisture and volatilize completely, obtain white transparent dough, by its taking-up and immerse the AgNO of 10wt%
3in solution, soak 50 min, etching silicon powder surface, makes residual silver catalyst generate nano silver wire, not only can make nano wire depart from silicon face, and further refinement nano silver wire, by deionized water, repeatedly clean three times afterwards, under 210 ℃ of blanket of nitrogen, dry 48 h obtain nano silver wire.
Performance test: adopt SEM (SEM) to analyze the product of embodiment 1 gained.With SEM, observe through HNO
3the silica flour cleaning, we have found dependent nano wire at silicon powder surface, the transparent nano silver wire of these overlength, diameter is 20 ~ 60 nm, result is as shown in Figure 2.The analysis of dispersion spectrum (EDS) by sample learns, the composition of these nano wires is Ag, and EDS analysis result as shown in Figure 3.The diameter of these nano silver wires is 10 ~ 90 nm, length >=20 μ m.Except nano silver wire, we have also found a small amount of silver nanoparticle band at silicon powder surface, and its width is 300 nm～500 nm, and thickness is 10 ~ 90 nm.
Experiment shows, HF and AgNO
3concentration and the surface topography of silica flour the formation of nano silver wire is had to important impact:
Keeping HF concentration is 20wt%, changes AgNO
3content can change even upgrowth situation of the shape on etch silicon surface and the productive rate of nano silver wire.Work as AgNO
3when concentration is 0.5 ~ 3mM, silicon powder surface regional area is Micro Structure of Porous Silicon, and other positions are etched to shallow vestige, as shown in Figure 4.Work as AgNO
3when concentration is 50 ~ 100 mM, at silicon powder surface, formed disorderly structure, as shown in Figure 5.AgNO
3the structure of concentration etch silicon can suppress the growth of nano silver wire, therefore, AgNO
3too low or the too high generation that is all unfavorable for nano silver wire of concentration.
Keep AgNO
3concentration be 35 mM, change the concentration of HF.When the concentration of HF is 0.1wt% ~ 5wt%, silicon powder surface forms porous microstructure, as shown in Figure 6.When the concentration of HF is 34wt%, at silicon powder surface, formed disorderly structure, sometimes also can produce the nano silver wire of single destruction.Same, the too low or too high formation that is also unfavorable for nano silver wire of HF concentration.
Fig. 7 is the X-ray diffractogram of nano silver wire, without other thing phase peak values, illustrates that nano silver wire is very pure, and diffraction maximum is bright and sharp, illustrates and adopts the nano silver wire well-crystallized of preparation in this way.
Oxidant plays an important role in the generative process of nano silver wire, selects other oxidants to come and AgNO
3the mixing of/HF solution is reacted.When selecting Co (NO
3)
3and K
2ptCl
6with AgNO
3when/HF solution mixes, reaction finishes rear silicon powder surface many duck eyes that have been corroded out, has nano silver wire to generate simultaneously, at silicon powder surface, produces silicon branch, with trickleer nano silver wire, generates.When selecting Fe (NO
3)
3, Mn (NO
3)
3or Co (NO
3)
3as oxidant and AgNO
3when/HF solution mixes, there is not deposition of silver in silicon powder surface, and only at silicon powder surface, generated the micro-structural of some columns, coniform and fire pit shape, shown to set crystalline silicon and be absolutely necessary in the generative process of nano silver wire.
Above embodiments of the present invention are explained in detail, but ratio of the present invention is not limited to above-mentioned embodiment, in the ken that one skilled in the relevant art possesses, can also under the prerequisite that does not depart from aim of the present invention, makes a variety of changes.
Claims (5)
1. a preparation method for nano silver wire, is characterized in that, comprises the steps: silica flour to clean, and then silica flour is put into and filled HF/AgNO
3in the reactor of the aqueous solution, form reaction solution, after sealing, be heated to reaction solution boiling, after naturally cooling 24 ~ 48 h, finish reaction; From reaction solution, filter out silica flour, and silica flour is joined to standing 12 ~ 48 h in deionized water, by its taking-up and immerse the AgNO of 0.5 ~ 10wt%
3in solution, soak 10 ~ 50 min, repeatedly clean three times afterwards by deionized water, under 100 ~ 210 ℃ of argon atmosphers, dry 10 ~ 72 h obtain nano silver wire.
2. preparation method according to claim 1, is characterized in that, the cleaning way of described silica flour comprises the steps: to use successively acetone, ethanol, washed with de-ionized water silica flour, then puts into H
2sO
4/ H
2o
2standing 10 ~ 50 min in solution (volume ratio is 3:1), after ultrasonic 12 ~ 48 h, clean up by deionized water.
3. preparation method according to claim 1 and 2, is characterized in that, described silica flour, and its fineness is 5 ~ 5000 μ m.
4. preparation method according to claim 1 and 2, is characterized in that, described HF/AgNO
3the aqueous solution, accounts for 20 ~ 60% of reactor volume, and the content of HF is 5wt% ~ 20wt%, AgNO
3molar concentration be 10 ~ 45mM.
5. preparation method according to claim 1 and 2, is characterized in that, described inert gas is nitrogen or argon gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106546720A (en) * | 2016-10-31 | 2017-03-29 | 山东师范大学 | A kind of preparation method of the stretchable biosensor material of three-dimensional grapheme/silver nano flower-like |
| CN107598183A (en) * | 2017-08-14 | 2018-01-19 | 嘉兴尚能光伏材料科技有限公司 | A kind of magnanimity preparation method of nano-Ag particles |
| CN109215848A (en) * | 2018-07-31 | 2019-01-15 | 华南师范大学 | A kind of preparation method of high-bond transparent conductive electrode |
| CN112059203A (en) * | 2020-09-03 | 2020-12-11 | 南昌大学 | Porous silver and preparation method thereof |
-
2013
- 2013-12-23 CN CN201310714543.5A patent/CN103639422B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106546720A (en) * | 2016-10-31 | 2017-03-29 | 山东师范大学 | A kind of preparation method of the stretchable biosensor material of three-dimensional grapheme/silver nano flower-like |
| CN107598183A (en) * | 2017-08-14 | 2018-01-19 | 嘉兴尚能光伏材料科技有限公司 | A kind of magnanimity preparation method of nano-Ag particles |
| CN109215848A (en) * | 2018-07-31 | 2019-01-15 | 华南师范大学 | A kind of preparation method of high-bond transparent conductive electrode |
| CN112059203A (en) * | 2020-09-03 | 2020-12-11 | 南昌大学 | Porous silver and preparation method thereof |
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| CN103639422B (en) | 2016-05-11 |
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