CN101845141B - Method for preparing polyaniline/silver nanometer composite material by using aniline as dispersing agent - Google Patents
Method for preparing polyaniline/silver nanometer composite material by using aniline as dispersing agent Download PDFInfo
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- CN101845141B CN101845141B CN201010199429XA CN201010199429A CN101845141B CN 101845141 B CN101845141 B CN 101845141B CN 201010199429X A CN201010199429X A CN 201010199429XA CN 201010199429 A CN201010199429 A CN 201010199429A CN 101845141 B CN101845141 B CN 101845141B
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Abstract
The invention provides a method for preparing a polyaniline/silver nanometer composite material by using aniline as a dispersing agent. The method comprises the following steps of: preparing nanometer silver powder by using aniline as the dispersing agent and sodium hypophosphite as a reducing agent in water bath at the temperature of 40 DEG C; and moving the reaction system to a room-temperature environment, adding solution of ammonium persulfate into solution of nanometer silver glue dropwise to initiate the polymerization of aniline, and performing in-situ combination to obtain the polyaniline/silver nanometer composite material. The composite material prepared by the method is pure and uniform in grain size and is formed into a coating material with a core-shell structure with polyaniline outside and nanometer silver powder inside; and the nanometer composite material also has the advantages of high thermal property, high conductivity, and high electro-chemical property, and is expected to be applied to electrode materials of electrolytic capacitors or secondary batteries.
Description
Technical field
The present invention relates to the preparation and the manufacture field of inorganic precious metal and conductive polymer composite, be specifically related to a kind of preparation method of polyaniline/argentum nano composite material.
Background technology
The environmental stability that polyaniline has specific conductivity height, doping attitude and the attitude of not mixing is good, be easy to synthesize, the monomer low cost and other advantages, in addition, polyaniline has the active centre, and the matrix material that is formed by polyaniline also demonstrates many excellent properties at aspects such as mechanics, optics, electricity and magnetics.Silver powder possesses good electrical conductivity (oxide compound also conducts electricity), high chemical stability, high-ductility and oxidation-resistance, in polyaniline, introduce the polyaniline/argentum nano composite material that nano silver particles prepares, the natural characteristics that has not only kept polyaniline and nano-silver powder, its electrical property, electrochemical response performance and electrocatalysis characteristic etc. are all had been further upgraded, and at numerous areas important application prospects are arranged all.In the preparation research of polyaniline/argentum nano composite material, the matrix material with core-shell type structure of polyaniline clad nano silver particles has caused researchist's extensive concern.This special structure not only can realize the mutual supplement with each other's advantages of two group element materials, strengthens both composite effects, and polyaniline also can play function of stabilizer to nano silver particles and prevents its reunion.In addition, the polyaniline/argentum nano composite material with nucleocapsid structure can design its application performance and requirement on the both macro and micro yardstick, all has important researching value aspect scientific research field or the application and development.
At present, the preparation method of polyaniline/argentum matrix material mainly comprises two in-situ compositings of a step and stepped combined method.Wherein, for reaching the purpose of two in-situ preparing polyaniline/silver composite materials of a step, the researchist relies on some unconventional technology usually on preparation condition, as in reaction, adopting microwave technology, gamma-rays, ultrasonic wave etc. add subsidiary conditions, and the experiment condition of these preparation means is comparatively harsh, and limitation is bigger.Owing to adopt the pattern and the size of the matrix material of this method preparation to be difficult to control, silver-colored particulate in the matrix material is easy to reunite and disperses uneven in the polyaniline matrix, the productive rate of product is not high, has therefore restricted the suitability for industrialized production of matrix material and the applied research of correlated performance largely.
Summary of the invention
The purpose of this invention is to provide a kind of is the preparation method of the polyaniline/argentum nano composite material of dispersion agent with aniline.Its preparation method is simple, and production cost is low, the matrix material productive rate height of preparation, and product is pure, and uniform particles has formed polyaniline outside, and nano-silver powder is at the coating material of interior nucleocapsid structure; This nano composite material good in thermal property, the specific conductivity height, chemical property is good, is expected to be applied to the electrode materials of electrolytic condenser or secondary cell.
The present invention adopts stepped combined legal system to be equipped with polyaniline/argentum nano composite material.It adopts Silver Nitrate is raw material, is dispersion agent with aniline, and sodium hypophosphite prepares the nanometer elargol earlier as reductive agent, and the original position that drips the ammonium persulfate solution initiation aniline that contains nitric acid again is compound, prepares.
Described Silver Nitrate and aniline and sodium hypophosphite three's mole proportioning is: 1～2: 1～6: 2～4.The mole proportioning of described ammonium persulphate and aniline is: 1: 1～1.5.
Specifically being prepared as of nanometer elargol: earlier with sodium hypophosphite is water-soluble stir after, adding contains the aniline solution of nitric acid and stirs, under 40 ℃ of water-bath environment, drip the silver nitrate solution that contains nitric acid then and carry out prepared in reaction nanometer elargol by proportioning, rate of addition is 10～15 droplets/minute, 90 minutes reaction times.The reaction process equation is as follows:
4Ag
++H
3PO
2+2H
2O→4Ag↓+H
3PO
4+4H
+
Described concentration of nitric acid is 1M/L, and the pH value of reaction system is controlled at 1～2.
After preparing the nanometer elargol, reaction system is shifted out the water-bath environment, the original position that at room temperature drips the ammonium persulfate solution initiation aniline that contains nitric acid is compound, and rate of addition is 10～15 droplets/minute, 4 hours reaction times.
The concrete preparation method of the present invention is specific as follows:
A. the 0.27g sodium hypophosphite is dissolved in the 40ml distilled water and ultrasonic 10min is uniformly dispersed, the 1M/L salpeter solution 4.5ml that adding contains aniline 0.5g in the solution is made into reduced liquid then; Taking by weighing the 0.85g Silver Nitrate is dissolved in the 10ml water and the salpeter solution that adds 1ml1M/L stirs and is made into oxidation liquid, dropwise add with 10～15 droplets/minute speed and to prepare nano silver particles in the reduced liquid, experimentation keeps stirring, and is reflected in 40 ℃ of water-baths and carries out 90min;
B. after treating that a reaction is finished, reaction system is moved in the room temperature environment, treat that the stable back of system temperature dropwise adds the in-situ polymerization of the aqueous solution 10ml initiation aniline of the ammonium persulphate that contains 1ml1M/L nitric acid and 1.23g in the reaction solution; Continue in the reaction process to stir, carried out 4 hours.
Advantage of the present invention is as follows:
1, adopting aniline is that dispersion agent prepares the nanometer elargol, does not introduce other dispersion agents, and aniline participates in complex reaction as the experiment reactant again, and this method has been simplified production technique, has reduced cost, and experiment productive rate height, and product is pure.
2, adopt aniline original position compound mode to prepare polyaniline/argentum nano composite material, formed polyaniline outside, nano-silver powder is realized the mutual supplement with each other's advantages and the reinforcement of two kinds of group element materials at the stable clad structure of interior nucleocapsid structure.
3. adopt the polyaniline/argentum nano composite material of present method preparation to have high conductivity and good electrochemical, the thermal stability excellence has a good application prospect.
Description of drawings:
Fig. 1 is the XRD figure of polyaniline/argentum nano composite material;
Fig. 1 is a polyaniline/argentum sample XRD figure spectrum, 2 θ are 37.9 among the figure, 44.1,62.3 and 77.3 ° four peaks occurred, being consistent on its peak position and peak shape and the standard crystalline state silver card sheet (JCPDS NO.4-0783), corresponding with silver-colored successively (111), (200), (220) and (300) face, be face-centred cubic structure.
Fig. 2 is the FT-IR collection of illustrative plates of polyaniline/argentum nano composite material;
Fig. 2 is the polyaniline/argentum nano composite material infrared absorpting light spectra, among the figure 1500 and 1600cm
-1Place's absorption peak corresponds respectively to the benzene formula structural unit N-B-N skeleton stretching vibration (B is a phenyl ring) and the N=Q=N skeleton stretching vibration (Q is the quinone ring) of polyaniline, and 1236 and 1292cm
-1The strong absorption peak corresponding polyaniline benzene formula of difference at place and the C-N stretching vibration of benzoquinones structural unit, and at 1120cm
-1The absorption peak at place is corresponding to the flexural deformation in the C-H face on the phenyl ring, 790cm
-1The absorption peak at place is then corresponding to the outer flexural deformation of the C-N face on the contraposition disubstituted benzene ring, 505cm
-1Near the absorption peak then flexural vibration of aromatic ring causes.
Fig. 3 is the TEM figure of polyaniline/argentum nano composite material;
The microscopic appearance of composite material granular mostly is irregular particle among Fig. 3, particle kernel and exterior circumferential exist tangible contrast difference, show the relation that intermediate particle and exterior circumferential circle present parcel and be wrapped, formed comparatively significantly nucleocapsid structure form, as we know from the figure, the particle diameter of composite particles is about 50nm.
Fig. 4 is the TG figure of polyaniline and polyaniline/argentum nano composite material.
A is a polyaniline among the figure; B is a polyaniline/argentum nano composite material.
As can be known from Fig. 4, polyaniline mass loss in initial 100 ℃ mainly is that it is slow that weight reduces speed, all one section platform occurred at 100～180 ℃ because the volatilization of the moisture of sample interior and other impurity causes.Quality further loss after 200 ℃, this is that this variation with the polyaniline form is relevant because due to the dedoping of nitric acid, downtrending slows down near 280 ℃ to some extent.Violent mass loss has appearred in polyaniline after 300 ℃, is because due to the large-scale decomposition of polyaniline molecule chain.And tangible mass loss has not appearred in polyaniline/argentum nano composite material before 200 ℃, the starting temperature that violent mass loss occurs is also brought up near 350 ℃, explanation is after compound with the Ag particle, and the thermal stability of matrix material is improved than polyaniline material.
Specific embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
A. the 0.27g sodium hypophosphite is dissolved in the 40ml distilled water and ultrasonic 10min is uniformly dispersed, salpeter solution (1M/L) 4.5ml that adding contains aniline 0.5g in the solution is made into reduced liquid then; Taking by weighing the 0.85g Silver Nitrate is dissolved in the 10ml water and adds 1ml salpeter solution (1M/L) and stir and be made into oxidation liquid, dropwise add with 10～15 droplets/minute speed and to prepare nano silver particles in the reduced liquid, experimentation keeps stirring, and is reflected in 40 ℃ of waters and carries out 90min.
B. after treating that a reaction is finished, reaction system is moved in the room temperature environment, treat that the stable back of system temperature dropwise adds the in-situ polymerization of the aqueous solution 10ml initiation aniline of the ammonium persulphate that contains 1ml nitric acid (1M/L) and 1.23g in the reaction solution.Reaction continues to stir in the experimentation, and whole experiment was carried out 4 hours.
Claims (6)
1. with aniline the preparation method of the polyaniline/argentum nano composite material of dispersion agent, it is characterized in that, the employing Silver Nitrate is a raw material, with aniline is dispersion agent, sodium hypophosphite prepares the nanometer elargol earlier as reductive agent, the original position that drips the ammonium persulfate solution initiation aniline that contains nitric acid again is compound, prepares; Specifically being prepared as of described nanometer elargol: earlier with sodium hypophosphite is water-soluble stir after, adding contains the aniline solution of nitric acid and stirs, under 40 ℃ of water-bath environment, drip the silver nitrate solution that contains nitric acid then and carry out prepared in reaction nanometer elargol by proportioning, rate of addition is 10～15 droplets/minute, 90 minutes reaction times.
2. preparation method according to claim 1 is characterized in that, described Silver Nitrate and aniline and sodium hypophosphite three's mole proportioning is: 1～2: 1～6: 2～4.
3. preparation method according to claim 1 is characterized in that, the mole proportioning of described ammonium persulphate and aniline is: 1: 1～1.5.
4. preparation method according to claim 1 and 2 is characterized in that, described concentration of nitric acid is 1M, and the pH value of reaction system is controlled at 1～2.
5. preparation method according to claim 1 is characterized in that, prepare the nanometer elargol after, reaction system is shifted out the water-bath environment, the original position that at room temperature drips the ammonium persulfate solution initiation aniline that contains nitric acid is compound, and rate of addition is 10～15 droplets/minute, 4 hours reaction times.
6. preparation method according to claim 1 is characterized in that, described preparation method is specific as follows:
A. the 0.27g sodium hypophosphite is dissolved in the 40ml distilled water and ultrasonic 10mm is uniformly dispersed, the 1M salpeter solution 4.5ml that adding contains aniline 0.5g in the solution is made into reduced liquid then; Taking by weighing the 0.85g Silver Nitrate is dissolved in the 10ml water and the salpeter solution that adds 1ml1M stirs and is made into oxidation liquid, dropwise add with 10～15 droplets/minute speed and to prepare nano silver particles in the reduced liquid, experimentation keeps stirring, and is reflected in 40 ℃ of water-baths and carries out 90mm;
B. after treating that a reaction is finished, reaction system is moved in the room temperature environment, treat that the stable back of system temperature dropwise adds the in-situ polymerization of the aqueous solution 10ml initiation aniline of the ammonium persulphate that contains 1ml1M nitric acid and 1.23g in the reaction solution; Continue in the reaction process to stir, carried out 4 hours.
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| CN102161103B (en) * | 2011-03-02 | 2013-01-09 | 中南大学 | Preparation method of micrometer-level piece-shaped nano silver powder |
| CN102276831B (en) * | 2011-07-08 | 2013-04-24 | 东北师范大学 | Polyaniline nanometer strip compound and preparation method thereof |
| CN105542157B (en) * | 2015-12-22 | 2018-03-02 | 温州大学 | A kind of method that cladding process prepares polyaniline/argentum nano material |
| CN108774430A (en) * | 2018-06-21 | 2018-11-09 | 京东方科技集团股份有限公司 | Electrically conductive composition and preparation method thereof, conductive ink and flexible display apparatus |
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| CN101353477B (en) * | 2008-09-10 | 2010-10-13 | 中南大学 | Preparation of polyaniline / argentum nano composite material |
| CN101669519A (en) * | 2009-09-23 | 2010-03-17 | 昆明理工大学 | Polyaniline compound antibacterial agent and preparation method thereof |
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