CN106623966B - The silver nanowires for preparing the method for silver nanowires based on ionic liquid and being prepared - Google Patents

The silver nanowires for preparing the method for silver nanowires based on ionic liquid and being prepared Download PDF

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CN106623966B
CN106623966B CN201610884305.2A CN201610884305A CN106623966B CN 106623966 B CN106623966 B CN 106623966B CN 201610884305 A CN201610884305 A CN 201610884305A CN 106623966 B CN106623966 B CN 106623966B
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silver
silver nanowires
reaction
ionic liquid
obtains
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CN106623966A (en
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赵涛
梁先文
胡友根
朱朋莉
孙蓉
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B22F2009/245Reduction reaction in an Ionic Liquid [IL]

Abstract

The present invention provides a kind of method based on ionic liquid preparation silver nanowires and the silver nanowiress that are prepared, wherein method includes the following steps: (1), water soluble silver salt, dispersing agent be added in polyhydroxy liquid state organics, obtain mixed liquor;(2), ionic liquid is added in the mixed liquor that step (1) obtains, obtains reaction mother liquor;With the total volume meter of the reaction mother liquor, the concentration of water soluble silver salt is 0.01-1.0mol/L in the reaction mother liquor;The concentration of dispersing agent is 0.01-10.0mol/L;The concentration of ionic liquid is 0.0001-0.005mol/L;(3), the reaction mother liquor that step (2) obtains is reacted, after reaction, obtains the silver nanowires.The diameter for the silver nanowires being prepared by the preparation method of silver nanowires provided by the present invention is less than 60nm.

Description

The silver nanowires for preparing the method for silver nanowires based on ionic liquid and being prepared
Technical field
The present invention relates to a kind of method based on ionic liquid preparation silver nanowires and the silver nanowiress being prepared, and belong to Technical field of nano material.
Background technique
Nano material is had become a hot topic of research in recent years due to its special physical and chemical performance.In one-dimensional metal nanometer In line, silver nanowires is due to studied with good conductance and thermal conductivity most.In many application fields, silver nanoparticle Line all has potential uses, as silver nanowires has been applied to polarizing device, photonic crystal, catalysis and biological and chemical sensing The fields such as device especially have important application prospect in touch screen, transparent electrode and flexible electronic device.
Currently, being based on the brittleness of mainstream transparent electrode material indium doping tin oxide (ITO), complicated technique, high cost etc. The defect of aspect, silver nanowires transparent electrode material have become most potential alternative materials.The size of silver nanowires receives silver The influence of rice noodles transparent electrode material performance is most important, and the diameter of silver nanowires is smaller, smaller to the scattering of visible light, made The transparent electrode material visible light transmittance of work is higher, and mist degree is lower, and optical property is more excellent.Therefore, the lesser silver of diameter is received The preparation of rice noodles is of great significance for the application of transparent electrode material.
Summary of the invention
In order to solve the above shortcomings and deficiencies, silver is prepared based on ionic liquid the purpose of the present invention is to provide one kind to receive The method of rice noodles.
The object of the invention is also to provide what is be prepared by the above-mentioned method based on ionic liquid preparation silver nanowires Silver nanowires.
In order to achieve the above objectives, on the one hand, the present invention provides a kind of method based on ionic liquid preparation silver nanowires, The following steps are included:
(1), water soluble silver salt, dispersing agent are added in polyhydroxy liquid state organics, obtain mixed liquor;
(2), ionic liquid is added in the mixed liquor that step (1) obtains, obtains reaction mother liquor;
With the total volume meter of the reaction mother liquor, the concentration of water soluble silver salt is 0.01-1.0mol/L in the reaction mother liquor;
The concentration of dispersing agent is 0.01-10.0mol/L;
The concentration of ionic liquid is 0.0001-0.005mol/L;
(3), the reaction mother liquor that step (2) obtains is reacted, after reaction, obtains the silver nanowires.
Method according to the present invention, wherein the dosage of polyhydroxy liquid state organics can be according to water soluble silver salt Concentration and each reaction need the quality for the silver salt being added to determine.Such as: in the specific embodiment of the invention, it is assumed that in reaction The concentration of water soluble silver salt is A mol/L, and the quality for the silver salt for needing to be added is B g, then the dosage of polyhydroxy liquid state organics Are as follows: V=(molecular weight of B/ water soluble silver salt)/AL.
It is organic to be added to polyhydroxy liquid in step (1) by method according to the present invention for water soluble silver salt, dispersing agent After object, the uniform mixed liquor of clarification can be obtained by the method for ultrasound;
Ionic liquid is added to after the mixed liquor that step (1) obtains in step (2) system can also be carried out ultrasound with Obtain reaction mother liquor.
Method according to the present invention, it is preferable that the water soluble silver salt includes silver nitrate and/or silver acetate;
It is highly preferred that the water soluble silver salt is silver nitrate.
Method according to the present invention, it is preferable that the dispersing agent includes polyvinylpyrrolidone;
It is highly preferred that the dispersing agent includes PVP K30, polyvinylpyrrolidone K60, polyvinyl pyrrole The combination of one or more of alkanone K90 and polyvinylpyrrolidone K120;
Further preferably PVP K30.
Method according to the present invention, it is preferable that the polyhydroxy liquid state organics include ethylene glycol, glycerine and gather The combination of one or more of ethylene glycol;
It is highly preferred that the polyhydroxy liquid state organics are ethylene glycol.
Method according to the present invention, it is preferable that the ionic liquid includes quaternary ammonium salt ionic liquid;
It is highly preferred that the ionic liquid includes 4-propyl ammonium chloride, 4-propyl bromide, tetrabutylammonium chloride, tetramethyl One or more of ammonium chloride, etamon chloride, 4 bromide, tetraethylammonium bromide and tetrabutylammonium bromide Combination;
It is further preferred that the ionic liquid includes 4-propyl ammonium chloride, 4-propyl bromide and tetrabutylammonium chloride One or more of combination.
Method according to the present invention, it is preferable that the ionic liquid is 4-propyl ammonium chloride.
Wherein, preparation process intermediate ion liquid effects mechanism of the present invention:
1)、Ag+It is reduced into partial size < 50nm Ag nanoparticle first;
2), the Ag nanoparticle of these small sizes is more active, unstable, is easy to re-dissolve into Ag atom;
3), ionic liquid molecules chain can adsorb the resulting Ag atom of these fresh dissolutions, thus these Ag atoms are at it One-dimensional silver nanowires can be formed on strand with ordered fabrication, and during forming silver nanowires, dispersing agent can receive silver The lateral crystal face of rice noodles has certain coating function;
Such as: by taking tetrabutylammonium chloride as an example, shown in structural formula such as following formula (1):
Wherein, Cl-The effect of ion: a, as sustained release agent to fix silver ion, the reaction initial stage can be reduced The concentration of free silver ions, is conducive to the formation of nano-silver thread crystal seed, b, its can be adsorbed in newly-generated Ag nano particle table Face keeps nano particle negatively charged and mutually exclusive, avoids generating biggish Ag particle due to reuniting, make Ag nano particle keep compared with Small size is conducive to the dissolution of subsequent Argent grain;
The effect of tetrabutylammonium: it is used as soft template, the silver atoms of dissolution are self-assembly of one-dimensional again in the soft template Silver nanowires.
Method according to the present invention, it is preferable that water-soluble in the reaction mother liquor with the total volume meter of the reaction mother liquor Property silver salt concentration be 0.4mol/L, the concentration of dispersing agent is 0.6mol/L, and the concentration of ionic liquid is 0.001mol/L.
Method according to the present invention, it is preferable that reaction temperature described in step (3) is 80-200 DEG C, the reaction time For 1h-12h.
Method according to the present invention, it is preferable that reaction temperature described in step (3) is 130 DEG C, and the reaction time is 5h。
Method according to the present invention, in specific embodiment of the present invention, step (3) after reaction can be right Reaction products therefrom is centrifuged to obtain the silver nanowires.
On the other hand, the present invention also provides be prepared by the above-mentioned method based on ionic liquid preparation silver nanowires The diameter of silver nanowires, the silver nanowires is less than 60nm.
The preparation method of silver nanowires provided by the present invention is generated using ionic liquid as soft template, initial reaction stage Silver nano-grain dissolution, is assembled on ionic liquid molecules chain again, and then forms the silver nanowires that diameter is less than 60nm.
Method and process provided by the present invention based on ionic liquid preparation silver nanowires is simple, at low cost, can obtain straight The lesser silver nanowires of diameter.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 2;
Fig. 3 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 3;
Fig. 4 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 4;
Fig. 5 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 5;
Fig. 6 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 6;
Fig. 7 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 7;
Fig. 8 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 8;
Fig. 9 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 9;
Figure 10 is the scanning electron microscope (SEM) photograph for the silver nanowires being prepared in the embodiment of the present invention 10.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now in conjunction in detail below Embodiment and Figure of description carry out following detailed description to technical solution of the present invention, but should not be understood as can to of the invention The restriction of practical range.
Embodiment 1
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 66.6g are weighed respectively, and are added it to In the ethylene glycol of 1000mL, ultrasound obtains clarifying uniform mixed liquor;
(2), the 4-propyl ammonium chloride of 0.2218g is weighed, and is added it in the mixed liquor, it is female that ultrasound obtains reaction Liquid;
(3), the reaction mother liquor is obtained into mixture in 130 DEG C of reaction 5h;It is heavy that the mixture is collected after centrifugation It forms sediment, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in Figure 1, by Fig. 1 is it is found that the average diameter for the silver nanowires that the present embodiment is prepared is about 40nm (average diameter in the embodiment of the present invention Measurement method is method well known in the art, i.e., the diameter of 50 silver nanowiress is usually measured, then again by this 50 silver nanoparticles The average diameter for the silver nanowires that the average value of linear diameter is prepared as embodiment).
Embodiment 2
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 66.6g are weighed respectively, and are added it to In 1000mL ethylene glycol, ultrasound obtains clarifying uniform mixed liquor;
(2), the 4-propyl bromide of 0.0111g is weighed, and is added it in the mixed liquor, it is female that ultrasound obtains reaction Liquid;
(3), the reaction mother liquor is obtained into mixture in 130 DEG C of reaction 5h;The mixture is collected after centrifugation again Precipitating, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in Fig. 2, by Fig. 2 is it is found that the average diameter for the silver nanowires that the present embodiment is prepared is about 40nm, but there are the silver of a few granules shape, The reason for this is that: ionic liquid 4-propyl bromide additive amount is very few, and then causes the amount of bromide ion very few, initial reaction stage, bromine from The silver ion amount that son is fixed significantly reduces, and causes dramatically increasing for free silver ions amount, and then be easy to cause particle seeds It is formed and grows up to particle.
Embodiment 3
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 66.6g are weighed respectively, and are added it to In 1000mL ethylene glycol, ultrasound obtains clarifying uniform mixed liquor;
(2), the tetrabutylammonium chloride of 11.1089g is weighed, and is added it in the mixed liquor, ultrasound is reacted Mother liquor;
(3), the reaction mother liquor is obtained into mixture in 130 DEG C of reaction 5h;The mixture is collected after centrifugation again Precipitating, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in figure 3, by Fig. 3 is it is found that the average diameter for the silver nanowires that the present embodiment is prepared is about 40nm, but there are the silver of a few granules shape; The reason for this is that: ionic liquid tetrabutylammonium chloride additive amount is excessive, causes the amount of chloride ion excessive, since there are oxygen in reaction Gas, so that the silver wire crystal seed formed easily forms particle by oxygen and chloride ion oxide etch.
Embodiment 4
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 66.6g are weighed respectively, and are added it to In 1000mL ethylene glycol, ultrasound obtains clarifying uniform mixed liquor;
(2), the 4-propyl ammonium chloride of 0.1108g and the 4-propyl bromide of 0.1330g are weighed, and is added it to described In mixed liquor, ultrasound obtains reaction mother liquor;
(3), the reaction mother liquor is obtained into mixture in 130 DEG C of reaction 5h;The mixture is collected after centrifugation again Precipitating, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in figure 4, by Fig. 4 is it is found that the average diameter for the silver nanowires that the present embodiment is prepared is about 40nm.
Embodiment 5
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 66.6g are weighed respectively, and are added it to In the ethylene glycol of 1000mL, ultrasound obtains clarifying uniform mixed liquor;
(2), the 4-propyl ammonium chloride of 0.2218g is weighed, and is added it in the mixed liquor, it is female that ultrasound obtains reaction Liquid;
(3), the reaction mother liquor is obtained into mixture in 70 DEG C of reaction 5h;It is heavy that the mixture is collected after centrifugation It forms sediment, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in figure 5, by For Fig. 5 it is found that having only generated a small number of silver nanowiress in the present embodiment products therefrom, the average diameter of the silver nanowires is about 35nm, But generate some granular silver.The reason for this is that: the present embodiment preparation process reaction temperature is lower, so that reaction carried out Compare slowly, it is small to be formed by silver wire seed sized, and grow up to thinner silver wire, simultaneously as temperature is too low, reaction power is not Foot, is formed by graininess crystal seed and is difficult to grow up to silver wire, so with the presence of granular silver in product.
Embodiment 6
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 66.6g are weighed respectively, and are added it to In the ethylene glycol of 1000mL, ultrasound obtains clarifying uniform mixed liquor;
(2), the 4-propyl ammonium chloride of 0.2218g is weighed, and is added it in the mixed liquor, it is female that ultrasound obtains reaction Liquid;
(3), the reaction mother liquor is obtained into mixture in 210 DEG C of reaction 5h;It is heavy that the mixture is collected after centrifugation It forms sediment, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in fig. 6, by Fig. 6 is it is found that the average diameter for the silver nanowires that the present embodiment is prepared is about 135nm.The reason for this is that: it is prepared by the present embodiment Reaction temperature is higher in journey, and acutely, the silver wire seed sized that initial reaction stage obtains is larger for reaction, so last gained silver is caused to be received Rice noodles are relatively large in diameter.
Embodiment 7
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 444g are weighed respectively, and add it to 1000mL Ethylene glycol in, ultrasound, obtain clarifying uniform mixed liquor;
(2), the 4-propyl ammonium chloride of 0.2218g is weighed, and is added it in the mixed liquor, it is female that ultrasound obtains reaction Liquid;
(3), the reaction mother liquor is obtained into mixture in 130 DEG C of reaction 5h;It is heavy that the mixture is collected after centrifugation It forms sediment, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in fig. 7, by For Fig. 7 it is found that only generating the silver of a small number of corynebacteriums in the product that the present embodiment is prepared, most in product is graininess Silver.The reason for this is that: the additive amount of polyethylene of dispersing agent pyrrolidones K30 is excessive in the present embodiment preparation process, so that being formed The all surface of silver wire crystal seed be all wrapped by, may eventually lead to the formation of more granular silver.
Embodiment 8
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 66.6g are weighed respectively, and are added it to In the ethylene glycol of 1000mL, ultrasound obtains clarifying uniform mixed liquor;
(2), the 4-propyl ammonium chloride of 0.2218g is weighed, and is added it in the mixed liquor, it is female that ultrasound obtains reaction Liquid;
(3), the reaction mother liquor is obtained into mixture in 190 DEG C of reaction 2h;It is heavy that the mixture is collected after centrifugation It forms sediment, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in figure 8, by Fig. 8 is it is found that the average diameter for the silver nanowires that the present embodiment is prepared is about 55nm.
Embodiment 9
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 66.6g are weighed respectively, and are added it to In the ethylene glycol of 1000mL, ultrasound obtains clarifying uniform mixed liquor;
(2), the 4-propyl ammonium chloride of 0.2218g is weighed, and is added it in the mixed liquor, it is female that ultrasound obtains reaction Liquid;
(3), the reaction mother liquor is obtained into mixture in 90 DEG C of reaction 10h;It is heavy that the mixture is collected after centrifugation It forms sediment, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph as shown in figure 9, by Fig. 9 is it is found that the average diameter for the silver nanowires that the present embodiment is prepared is about 35nm.
Embodiment 10
Present embodiments provide a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), the silver nitrate of 67.9g and the PVP K30 of 221.8g are weighed respectively, and are added it to In the ethylene glycol of 1000mL, ultrasound obtains clarifying uniform mixed liquor;
(2), the 4-propyl ammonium chloride of 0.2218g is weighed, and is added it in the mixed liquor, it is female that ultrasound obtains reaction Liquid;
(3), the reaction mother liquor is obtained into mixture in 130 DEG C of reaction 5h;It is heavy that the mixture is collected after centrifugation It forms sediment, obtains the silver nanowires.
Electron microscope analysis is scanned to the silver nanowires that the present embodiment is prepared, scanning electron microscope (SEM) photograph is as shown in Figure 10, As shown in Figure 10, the average diameter for the silver nanowires that the present embodiment is prepared is about 40nm.

Claims (11)

1. a kind of method based on ionic liquid preparation silver nanowires comprising following steps:
(1), water soluble silver salt, dispersing agent are added in polyhydroxy liquid state organics, obtain mixed liquor;
(2), ionic liquid is added in the mixed liquor that step (1) obtains, obtains reaction mother liquor;
With the total volume meter of the reaction mother liquor, the concentration of water soluble silver salt is 0.01-1.0mol/L in the reaction mother liquor;
The concentration of dispersing agent is 0.01-10.0mol/L;
The concentration of ionic liquid is 0.0001-0.005mol/L;
The ionic liquid is the combination of 4-propyl ammonium chloride and 4-propyl bromide;
(3), the reaction mother liquor that step (2) obtains is reacted, after reaction, obtains the silver nanowires;
The diameter of the silver nanowires is 40nm.
2. the method according to claim 1, wherein the water soluble silver salt includes silver nitrate and/or silver acetate.
3. method according to claim 1 or 2, which is characterized in that the water soluble silver salt is silver nitrate.
4. the method according to claim 1, wherein the dispersing agent includes polyvinylpyrrolidone.
5. according to the method described in claim 4, it is characterized in that, the dispersing agent includes PVP K30, poly- second The combination of one or more of alkene pyrrolidone K60, PVP K90 and polyvinylpyrrolidone K120.
6. according to the method described in claim 5, it is characterized in that, the dispersing agent is PVP K30.
7. the method according to claim 1, wherein the polyhydroxy liquid state organics include ethylene glycol, the third three The combination of one or more of alcohol and polyethylene glycol.
8. the method according to the description of claim 7 is characterized in that the polyhydroxy liquid state organics are ethylene glycol.
9. the method according to claim 1, wherein with the total volume meter of the reaction mother liquor, the reaction mother liquor The concentration of middle water soluble silver salt is 0.4mol/L, and the concentration of dispersing agent is 0.6mol/L, and the concentration of ionic liquid is 0.001mol/ L。
10. the method according to claim 1, wherein reaction temperature described in step (3) is 80-200oC, reaction Time is 1h-12h.
11. the method according to claim 1, wherein reaction temperature described in step (3) is 130oC, when reaction Between be 5h.
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CN111299604A (en) * 2020-03-02 2020-06-19 华南理工大学 Room-temperature coated ultra-long silver nanowire for flexible substrate and preparation method thereof
CN111545768A (en) * 2020-04-17 2020-08-18 华南理工大学 Large-diameter silver nanoring and preparation method thereof
CN113351877B (en) * 2021-06-04 2023-05-23 深圳先进电子材料国际创新研究院 Preparation method of silver nano ring

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