CN106513698B - A kind of gradually addition preparation process of highly concentrated nano silver wire - Google Patents
A kind of gradually addition preparation process of highly concentrated nano silver wire Download PDFInfo
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- CN106513698B CN106513698B CN201610935867.5A CN201610935867A CN106513698B CN 106513698 B CN106513698 B CN 106513698B CN 201610935867 A CN201610935867 A CN 201610935867A CN 106513698 B CN106513698 B CN 106513698B
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Abstract
The invention belongs to field of nano material preparation, specially a kind of gradually addition preparation process of high concentration overlength nano-silver thread.The polyethylene dissolving pyrrolidones specially in ethylene glycol, adds soluble silver salt, and micro nano-silver thread size controlling agent is added, and high-temperature heating obtains nano-silver thread dispersion liquid；The ethylene glycol solution of a certain amount of nitric acid, silver salt, polyvinylpyrrolidone and size controlling agent is added in dispersion liquid again, keeps high temperature certain time, increases nano-silver thread growth；The step for repeating, obtains the nano-silver thread of required size and length.The present invention can prepare the nano-silver thread dispersion liquid of high concentration, facilitate the preparation of nano-silver thread, can obtain the nano-silver thread of specific dimensions as desired.
Description
Technical field
The invention belongs to field of nano material preparation, the gradually addition of specially a kind of highly concentrated nano silver wire prepares work
Skill.
Background technique
Nano-silver thread is a kind of special existence form of elemental silver, special wire shaped, i.e. its great draw ratio
Make it that there is unique application prospect in fields such as electronic material, derived energy chemical, health cares.The draw ratio of nano-silver thread is it
One important parameter, in certain special applications, such as nano silver line style flexible transparent conducting film, nano silver line style electrocondution slurry
Etc., biggish draw ratio has better performance performance.
The mode that existing nano-silver thread preparation method mainly " is treated different things alike ", i.e., in advance dissolve all reactants
It is good, then heating reaction, including the methods of conventional heating methods, microwave heating, hyperbaric heating, the ginseng such as draw ratio of nano-silver thread
Number is mainly adjusted by controlling the type of reactant with concentration.The method of " treating different things alike " is more convenient, but also has nano silver
Line draw ratio is not high, draw ratio be difficult to control, nano-silver thread concentration too the low waste for causing reactant the problems such as.
The present invention is to solve the problems, such as that major diameter is relatively low in nano-silver thread preparation process, concentration is lower.By will be solvable
Property silver salt by several times be added method, nano-silver thread present in solution before being grown in after may make the silver salt of addition to be reduced
On, increase the length and draw ratio of nano-silver thread；Method by repeatedly adding, so that there is the concentration of nano-silver thread in dispersion liquid
Significant raising is generally lower than 1% compared to " treating different things alike " nano-silver thread concentration, this side for gradually adding soluble silver salt
Method can make nano-silver thread concentration be increased to 2%-5%.
Summary of the invention
It is an object of that present invention to provide a kind of gradually addition preparation processes of highly concentrated nano silver wire.
The principle of the present invention is: first using the preparation method of conventional nano-silver thread, preparing initial nano-silver thread
Dispersion liquid, initial dispersion liquid nano-silver thread concentration is lower, and length, draw ratio are relatively low；Contain nitric acid, solubility by addition
Silver salt, polyvinylpyrrolidone, nano-silver thread size controlling agent nano-silver thread increase replenisher, initial nano-silver thread can be made
Further increase.Wherein nitric acid can make nano-Ag particles, shorter nano-silver thread in initial nano-silver thread dispersion liquid first
Ion-solubility is formed again, is then restored at high temperature by ethylene glycol again, is grown on relatively thick longer initial nano-silver thread,
It is improved the purity of nano-silver thread；If increase replenisher in again additionally joined silver ion, can with before with nitre
The silver ion that acid reaction obtains together, is reduced and is grown on relatively thick longer initial nano-silver thread.By repeatedly adding nanometer
Silver wire increases replenisher, and the regulation of nano-silver thread concentration, length, draw ratio may be implemented.
A kind of gradually addition preparation process of high concentration overlength nano-silver thread proposed by the present invention, the specific steps are as follows:
(1) preparation of initial nano-silver thread dispersion liquid: polyvinylpyrrolidone is dissolved in ethylene glycol, 1g/L- is made
The ethylene glycol solution of the polyvinylpyrrolidone of 25g/L；Then it is added in the ethylene glycol solution of polyvinylpyrrolidone solvable
Property silver salt, control soluble silver salt concentration be 1g/L-25g/L；After dissolution, the soluble chemical combination containing chloride ion is then added
Object makes Chlorine in Solution ion concentration reach 2 μM/L-18mM/L；Add soluble nano-silver thread size controlling agent, nano-silver thread
Size controlling agent is the compound containing iron ion or copper ion, and iron ion or copper ion concentration in solution is made to reach 2 μM/L-
18mM/L；Stirring dissolves all compounds, is again heated to 80 DEG C -200 DEG C, is stirred to react and keeps 30min-48h, obtains initial
Nano-silver thread dispersion liquid；
(2) configuration nano-silver thread increases replenisher: with soluble silver salt, nitric acid, polyvinylpyrrolidone, soluble nanometer
Silver wire size controlling agent and solvent are raw material, and mixing makes all dissolution of raw material；The concentration for controlling soluble silver salt is 0g/L-
200g/L, the concentration of nitric acid are 1mM/L-100mM/L, and the concentration of polyvinylpyrrolidone is 0g/L-250g/L, soluble nanometer
The concentration of silver wire size controlling agent is 0 μM/L-500mM/L, and solvent uses ethylene glycol；
(3) preparation of secondary nano-silver thread dispersion liquid: the nano-silver thread configured in step (2) is increased into replenisher and is added to
In the resulting initial nano-silver thread dispersion liquid of step (1), at a temperature of 80 DEG C -200 DEG C, it is stirred to react and keeps 30min-48h, obtain
To secondary nano-silver thread dispersion liquid；Nano-silver thread increases the 0.5%- that replenisher additional amount is initial nano-silver thread dispersion liquid volume
10%；
(4) nano-silver thread configured in step (2) the preparation with nano-silver thread dispersion liquid more times three times: is increased into supplement
Liquid is added in the resulting secondary nano-silver thread dispersion liquid of step (2), at a temperature of 80 DEG C -200 DEG C, is stirred to react holding
30min-48h obtains nano-silver thread dispersion liquid three times；It is initial nano-silver thread dispersion liquid that nano-silver thread, which increases replenisher additional amount,
The 0.5%-10% of volume；
(5) step (4) are repeated, obtains nano-silver thread dispersion liquid more times.
In the present invention, soluble silver salt used is in silver nitrate, silver cyanide, actol or silver acetate in step (1) and (2)
It is any.
In the present invention, chloride used in step (1) and (2) is chloride ion out may be dissolved in ethylene glycol and ionizable
It is any in compound, specially sodium chloride, potassium chloride, iron chloride, copper chloride or aluminium chloride.
In the present invention, solubility nano-silver thread size controlling agent used in step (1) and (2) is ferric iron, ferrous iron, monovalence
It is any in copper, cupric soluble nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, carboxylic acid or acetylacetonate compound.
The beneficial effects of the present invention are:
1. the present invention can prepare the nano-silver thread dispersion liquid of high concentration, concentration can reach 5%.
2. the present invention can control the parameters such as the length for preparing nano-silver thread, draw ratio, wherein extreme length can be prepared
With very big draw ratio nano-silver thread.
Detailed description of the invention
Fig. 1 shows initial nano-silver threads prepared by embodiment 1；
Fig. 2 indicates secondary nano-silver thread prepared by embodiment 1；
Fig. 3 indicates initial nano-silver thread prepared by embodiment 2；
Fig. 4 indicates secondary nano-silver thread prepared by embodiment 2；
Fig. 5 indicates nano-silver thread three times prepared by embodiment 3；
Fig. 6 indicates four nano-silver threads prepared by embodiment 4.
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
Embodiment 1:
(1) 0.2g polyvinylpyrrolidone is dissolved in 25ml ethylene glycol, stirring and dissolving；Equal polyvinylpyrrolidones are complete
0.25g silver nitrate, stirring and dissolving are added after fully dissolved；Iron chloride is added after being completely dissolved in equal silver nitrates, makes iron concentration
50 μM/L, chlorine ion concentration is 150 μM/L.After stirring and dissolving is complete, solution is heated to 160 DEG C and is stirred to react 1h, solution from
It is transparent to become grey, obtain initial nano-silver thread dispersion liquid；
(2) configuration nano-silver thread increases replenishers, and wherein nitric acid 0.2M/L, solvent are ethylene glycol；
(3) 5ml nano-silver thread growth replenishers are added directly into initial nano-silver thread, 160 after stirring at normal temperature 30min
DEG C it is stirred to react 1h, obtains secondary nano-silver thread dispersion liquid.
Embodiment 2
(1) 0.3g polyvinylpyrrolidone is dissolved in 30ml ethylene glycol, stirring and dissolving；Equal polyvinylpyrrolidones are complete
0.20g silver nitrate, stirring and dissolving are added after fully dissolved；Copper nitrate and sodium chloride is added after being completely dissolved in equal silver nitrates, make copper from
Sub- concentration is 100 μM/L, and chlorine ion concentration is 200 μM/L.After stirring and dissolving is complete, solution is heated to 180 DEG C and is stirred to react
45min, solution become grey from transparent, obtain initial nano-silver thread dispersion liquid；
(2) configuration nano-silver thread increases replenishers, wherein silver nitrate 40g/L, nitric acid 0.08M/L, polyvinylpyrrolidone
20g/L, copper nitrate 0.5mM/L, solvent are ethylene glycol；
(3) 5ml nano-silver thread replenishers are added directly into initial nano-silver thread dispersion liquid, after stirring at normal temperature 30min
180 DEG C are stirred to react 45min, obtain secondary nano-silver thread dispersion liquid.
Embodiment 3:
Increase replenishers for nano-silver thread is added in the secondary nano-silver thread dispersion liquid prepared in embodiment (1) again,
Ingredient is silver nitrate 50g/L, nitric acid 0.2M/L, polyvinylpyrrolidone 10g/L, and solvent is ethylene glycol, after stirring at normal temperature 30min
160 degree of reaction 1h, just obtain nano-silver thread dispersion liquid three times.
Embodiment 4:
Increase replenishers for nano-silver thread is added in the dispersion liquid of nano-silver thread three times prepared in embodiment (3) again,
Ingredient is silver nitrate 50g/L, nitric acid 0.2M/L, polyvinylpyrrolidone 10g/L, and solvent is ethylene glycol, after stirring at normal temperature 30min
160 degree of reaction 1h, just obtain four nano-silver thread dispersion liquids.
Claims (4)
1. a kind of gradually addition preparation process of high concentration overlength nano-silver thread, it is characterised in that specific step is as follows:
(1) preparation of initial nano-silver thread dispersion liquid: polyvinylpyrrolidone is dissolved in ethylene glycol, 1g/L-25g/L is made
Polyvinylpyrrolidone ethylene glycol solution；Then silver soluble is added in the ethylene glycol solution of polyvinylpyrrolidone
Salt, the concentration for controlling soluble silver salt is 1g/L-25g/L；After dissolution, the soluble compound containing chloride ion is then added,
Chlorine in Solution ion concentration is set to reach 2 μM/L-18mM/L；Add soluble nano-silver thread size controlling agent, nano-silver thread ruler
Very little controlling agent is the compound containing iron ion or copper ion, and iron ion or copper ion concentration in solution is made to reach 2 μM/L-
18mM/L；Stirring dissolves all compounds, is again heated to 80 DEG C -200 DEG C, is stirred to react and keeps 30min-48h, obtains initial
Nano-silver thread dispersion liquid；
(2) configuration nano-silver thread increases replenisher: with soluble silver salt, nitric acid, polyvinylpyrrolidone, soluble nano-silver thread
Size controlling agent and solvent are raw material, and mixing makes all dissolution of raw material；The concentration for controlling soluble silver salt is 0g/L-
200g/L, the concentration of nitric acid are 1mM/L-100mM/L, and the concentration of polyvinylpyrrolidone is 0g/L-250g/L, soluble nanometer
The concentration of silver wire size controlling agent is 0 μM/L-500mM/L, and solvent uses ethylene glycol；
(3) preparation of secondary nano-silver thread dispersion liquid: the nano-silver thread configured in step (2) is increased into replenisher and is added to step
(1) it in resulting initial nano-silver thread dispersion liquid, at a temperature of 80 DEG C -200 DEG C, is stirred to react and keeps 30min-48h, obtain two
Secondary nano-silver thread dispersion liquid；Nano-silver thread increases the 0.5%-10% that replenisher additional amount is initial nano-silver thread dispersion liquid volume；
(4) preparation with nano-silver thread dispersion liquid more times three times: the nano-silver thread configured in step (2) is increased into replenisher and is added
Enter into the resulting secondary nano-silver thread dispersion liquid of step (3), at a temperature of 80 DEG C -200 DEG C, is stirred to react and keeps 30min-
48h obtains nano-silver thread dispersion liquid three times；It is initial nano-silver thread dispersion liquid volume that nano-silver thread, which increases replenisher additional amount,
0.5%-10%；
(5) step (4) are repeated, obtains nano-silver thread dispersion liquid more times.
2. the gradually addition preparation process of high concentration overlength nano-silver thread according to claim 1, it is characterised in that step
(1) soluble silver salt used is any in silver nitrate, silver cyanide, actol or silver acetate and in (2).
3. the gradually addition preparation process of high concentration overlength nano-silver thread according to claim 1, it is characterised in that step
(1) soluble compound containing chloride ion is any in sodium chloride, potassium chloride, iron chloride, copper chloride or aluminium chloride.
4. the gradually addition preparation process of high concentration overlength nano-silver thread according to claim 1, it is characterised in that step
(1) and solubility nano-silver thread size controlling agent used in (2) is ferric iron, ferrous iron, monovalence copper, cupric soluble nitre
It is any in acid, hydrochloric acid, sulfuric acid, phosphoric acid, carboxylic acid or acetylacetonate compound.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610935867.5A CN106513698B (en) | 2016-11-01 | 2016-11-01 | A kind of gradually addition preparation process of highly concentrated nano silver wire |
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| CN201610935867.5A CN106513698B (en) | 2016-11-01 | 2016-11-01 | A kind of gradually addition preparation process of highly concentrated nano silver wire |
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| CN106513698B true CN106513698B (en) | 2019-02-26 |
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| CN108453267B (en) * | 2018-01-22 | 2020-04-10 | 深圳清华大学研究院 | Preparation method of surface roughened nano silver wire |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6537344B2 (en) * | 2001-03-20 | 2003-03-25 | Council Of Scientific & Industrial Research | Process for the preparation of a nanosized colloidal metal particle |
| CN102303124A (en) * | 2011-08-24 | 2012-01-04 | 浙江科创新材料科技有限公司 | Method for preparing length-diameter-ratio nano-silver wire by pH-value regulation solvothermal method |
| CN102423808A (en) * | 2011-12-14 | 2012-04-25 | 天津工业大学 | Quick high concentration synthesizing method of silver nanometer line |
| CN102744417A (en) * | 2011-06-16 | 2012-10-24 | 浙江科创新材料科技有限公司 | Method for preparing nano-silver wire with high length-diameter ratio |
| CN104759634A (en) * | 2015-03-04 | 2015-07-08 | 江苏大学 | Preparation method for superfine silver nanowire |
-
2016
- 2016-11-01 CN CN201610935867.5A patent/CN106513698B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6537344B2 (en) * | 2001-03-20 | 2003-03-25 | Council Of Scientific & Industrial Research | Process for the preparation of a nanosized colloidal metal particle |
| CN102744417A (en) * | 2011-06-16 | 2012-10-24 | 浙江科创新材料科技有限公司 | Method for preparing nano-silver wire with high length-diameter ratio |
| CN102303124A (en) * | 2011-08-24 | 2012-01-04 | 浙江科创新材料科技有限公司 | Method for preparing length-diameter-ratio nano-silver wire by pH-value regulation solvothermal method |
| CN102423808A (en) * | 2011-12-14 | 2012-04-25 | 天津工业大学 | Quick high concentration synthesizing method of silver nanometer line |
| CN104759634A (en) * | 2015-03-04 | 2015-07-08 | 江苏大学 | Preparation method for superfine silver nanowire |
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