CN103980488A - Preparation method of sepiolite/polyaniline nanocomposite material - Google Patents
Preparation method of sepiolite/polyaniline nanocomposite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a sepiolite/polyaniline nanocomposite material. The preparation method is characterized by comprising the following steps: mixing sepiolite with water, standing, filtering an upper-layer sepiolite suspension liquid, washing with water, and drying to obtain washed sepiolite; mixing the washed sepiolite with hydrochloric acid, stirring in a water bath, filtering, washing solids with water, and drying to obtain acid activated sepiolite; mixing the acid activated sepiolite with an organic solvent, adding amino-carrying silane coupling agent, mixing, stirring in the water bath, filtering, washing, and drying to obtain organized modified sepiolite; mixing the organized modified sepiolite with water into a dispersion liquid; adding a dopant and phenylamine while stirring, cooling, adding an oxidant for stirring, reacting and then washing and drying materials, to obtain a product sepiolite/polyaniline nanocomposite material. The prepared composite material has high electric conductivity and high specific capacitance, and is applicable to the fields of a supercapacitor electrode material, a secondary material, an electromagnetic shielding material and the like.
Description
Technical field
The invention belongs to the preparation of a kind of inorganic mineral and Conducting Polymer Nanocomposites, relate to a kind of preparation method of sepiolite/polyaniline nano-composite material.Sepiolite/polyaniline nano-composite material prepared by the present invention has high conductivity, high specific capacitance, can be used for the fields such as electrode material for super capacitor, secondary cell and electromagnetic shielding material.
Background technology
Polyaniline is as one of conducting polymer substance, because it is easy to preparation, high temperature resistant and antioxidant property good and get more and more people's extensive concerning compared with high electric conductivity, at field tools such as secondary cell, electrochemistry and electromagnetic shieldings, has been widely used.But there is the shortcomings such as insoluble molten, mechanical poor ductility and processing difficulties in pure polyaniline, has limited its widespread use in practice.Therefore, people by Molecular Structure Design, prepare the methods such as polyaniline nano-composite material and improve its processing characteristics and expand its range of application.In recent years, by polyaniline and the compound preparation of inorganic nano-particle inorganic/polyaniline nano composite conducting material becomes the emphasis of people research, in prior art, common inorganic/polyaniline nano-composite material has polynite/polyaniline, silicon-dioxide/polyaniline etc., but because the specific surface area of the materials such as silicon-dioxide, polynite is not high, make the ratio electric capacity of material lower, the poor-performing of material.
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, and a kind of preparation method of sepiolite/polyaniline nano-composite material is provided.The present invention by sepiolite after purification, acid activation, organic modification are processed, method by in-situ polymerization arrives sepiolite fibre surface by polyaniline grafted again, thereby prepares a kind of sepiolite/polyaniline nano-composite material with high conductivity, high specific capacitance.
Content of the present invention is: a kind of preparation method of sepiolite/polyaniline nano-composite material, is characterized in that comprising the following steps:
A, the sepiolite (raw material) that will cross 80 mesh sieves and water are by weight the ratio mix and blend 1～6h of 1:30～60, then standing 12～24h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 0.5～3mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:10～30, then in 25～60 ℃ of stirred in water bath 8～24h, filtration, solids are washed with distilled water to neutrality (being that pH is 6～7), in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:20～50 mix, add with amino silane coupling agent, (being preferably through ultrasonic dispersion) mixes, then at 70～110 ℃, stir 8～24h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.03～0.25:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 0.05%～3%; Under stirring, (in dispersion liquid) adds doping agent and aniline, after stirring, obtains mixed solution; Mixed solution is cooled to-10～5 ℃, again oxygenant joined in mixed solution, stir 6～24h, reacting rear material is through suction filtration, solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 0.5～15:1;
Described doping agent and the mol ratio of aniline are 0.5～10:1;
Described oxygenant and the mol ratio of aniline are 0.5～2:1.
In content of the present invention: doping agent described in steps d can be any one in hydrochloric acid, sulfuric acid or perchloric acid.
In content of the present invention: can be any one in 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane or diamino diethoxy silane with amino silane coupling agent described in step c.
In content of the present invention: oxygenant described in steps d can be ammonium persulphate (being called for short APS), iron trichloride (FeCl
3) or potassium bichromate (K
2cr
2o
7) in any one.
In content of the present invention: the distilled water described in step a and/or step b can replace with deionized water.
In content of the present invention: described sepiolite raw material picks up from Yi County, Hebei, and wherein the average content of scpiolitc can reach more than 60%.After washing and acid activation, can effectively remove in sepiolite the impurity such as calcium carbonate,
Sepiolite/polyaniline nano-composite material prepared by the present invention has structural formula as follows:
Compared with prior art, the present invention has following feature and beneficial effect:
(1) adopt the present invention, the theoretical construct formula of sepiolite is Mg
8si
12o
30(OH)
4(OH
2)
48H
2o, its structural unit forms by silicon-oxy tetrahedron with by the magnesium ion of octahedral coordination, has the transition type constitutional features of chain and stratiform, belongs to the layer silicate mineral of quadrature (tiltedly side) crystallographic system; The existing 1-dimention nano fibrous texture that is similar to carbon nanotube of sepiolite unit's crystal layer, has again the laminate structure of similar polynite 2:1, the structure of sepiolite uniqueness to make it have larger specific surface area and rheological etc. preferably; In the preparation process of sepiolite/polyaniline nano-composite material, aniline be take sepiolite fibre as template, on the axial direction due of sepiolite fibre, carries out aggregation growth, forms a kind of one-dimensional nano-composite material with nucleocapsid structure of uniqueness;
(2) the present invention adopts with amino silane coupling agent sepiolite is carried out to modification, with the amino on silane coupling agent, as avtive spot, carry out graft polymerization aniline, make in the polyaniline chain structure on sepiolite axial direction due more complete, the transportation of current-carrying is more unobstructed, is conducive to improve the specific conductivity of nano composite material; Sepiolite provides the short texture of larger specific surface area and porous, is conducive to the deposition of electroactive substance, has improved the charge storage ability of nano composite material;
(3) in preparation method of the present invention, the object of described washing sepiolite is to remove water-soluble impurity, and sepiolite fibre is farthest disperseed and refinement; The object of acid activation sepiolite is to remove in sepiolite the impurity such as calcium carbonate, sloughs part magnesium ion in structure simultaneously, increases specific surface area and surfactivity; The object of organic modification sepiolite is: with amino silane coupling agent, can, with aniline grafting, realization at sepiolite surface grafting polymerization aniline, the wetting ability on sepiolite surface be become to the consistency of hydrophobicity, raising and polyaniline;
(4) adopt the present invention, sepiolite/the polyaniline nano-composite material of preparation has high conductivity (1.5S/cm～3.4S/cm) and high specific capacitance (192F/g～445F/g), can be used for the fields such as electrode material for super capacitor, secondary cell and electromagnetic shielding material, composite property is good, has the characteristic of natural inorganic nano-mineral and conduction high polymer concurrently;
(5) product preparation process of the present invention is simple, and operation is easy, is easy to control, and raw material is easy to get, with low cost, and environmental protection can be controlled specific conductivity and the chemical property of nano composite material by adjusting sepiolite consumption, practical.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of scpiolitc.From this figure, can see, sepiolite rule of surface and smooth, individual fiber diameter is 30～100nm;
Fig. 2 is the transmission electron microscope picture of sepiolite/polyaniline nano-composite material of preparing of the present invention.From this figure, can see, sepiolite/polyaniline nano-composite material is unique one-dimensional nano-composite material with nucleocapsid structure;
Fig. 3 is the infrared spectrogram of sour modified meerschaum (A), organic modification sepiolite (B) and sepiolite/polyaniline nano-composite material (C), from this figure, can see:
Acid modified meerschaum: 3675cm
-1stretching vibration peak for Mg-OH; 3569cm
-1stretching vibration peak for coordination crystal water; 3416cm
-1stretching vibration peak for zeolite adsorption water; 1657cm
-1for in zeolite water-stretching vibration peak of OH; 1022cm
-1the shuttle belt stretching vibration band that is Si-O;
Organic modification sepiolite: compare with sour modified meerschaum, at 2925cm
-1and 2855cm
-1there is weak absorption peak, for silane coupling agent-CH
2-asymmetric and symmetrical stretching vibration;
Sepiolite/polyaniline nano-composite material: 3446cm
-1for-NH-stretching vibration peak; 1564cm
-1and 1486cm
-1for representing the characteristic peak of quinoid structure-N=Q=N-and benzene formula structure-N-B-N-; 1297cm
-1and 1240cm
-1stretching vibration absorption peak for C-N; 1122cm
-1characteristic peak for imines nitrogen-B-N=Q-structure; 800cm
-1c h bond out-of-plane deformation vibration peak for Isosorbide-5-Nitrae-disubstituted benzenes ring; 1016cm
-1stretching vibration peak for the Si-O of sepiolite.Fig. 3 has illustrated the successful preparation of sepiolite/polyaniline nano-composite material.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
What deserves to be explained is: the specific conductivity of the sepiolite/polyaniline nano-composite material of following examples gained is tested by four probe method; Than electric capacity, be to be obtained by charge-discharge test under the current density of 1A/g; During test, adopt three-electrode method, sepiolite/polyaniline nano-composite material: acetylene black: tetrafluoroethylene is coated on stainless (steel) wire as working electrode (coat weight is 3～5mg) after evenly mixing for 80:10:10, platinum electrode is to electrode, full to close mercurous chloride electrode be reference electrode, the H that electrolytic solution is 1mol/L
2sO
4the aqueous solution.
Embodiment 1:
A preparation method for sepiolite/polyaniline nano-composite material, preparation process is as follows:
1) sepiolite raw material and the distilled water of crossing 80 mesh sieves are mixed by weight 1:30, strong stirring mixing 6h, then standing 24h, gets upper strata sepiolite suspension, and suction filtration, distilled water wash obtain washing sepiolite in 60 ℃ of vacuum-drying 24h;
2) hydrochloric acid soln that is 3mol/L by the washing sepiolite of crossing 200 mesh sieves with concentration mixes by weight the ratio of 1:20, and then, in 25 ℃ of stirring 16h, filtration, distilled water wash, to neutral, obtain acid activation sepiolite in 60 ℃ of vacuum-drying 24h;
3) the acid activation sepiolite of crossing 200 mesh sieves is mixed by weight the ratio of 1:20 with dehydrated alcohol, add 3-aminopropyl triethoxysilane, the weight ratio of 3-aminopropyl triethoxysilane and acid activation sepiolite is 0.03:1; Ultrasonic being uniformly dispersed, then, in 70 ℃ of stirring 8h, filters, and uses in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, obtains organic modification sepiolite;
4) will cross the organic modification sepiolite of 200 mesh sieves and distilled water is ultrasonic is uniformly dispersed, make the dispersion liquid that organic modification sepiolite weight percent content is 0.05%, under the condition constantly stirring, in dispersion liquid, add aniline, the weight ratio of aniline and organic modification sepiolite is 15:1; Add sulfuric acid, the mol ratio of sulfuric acid and aniline is 0.5:1, obtains mixed solution again; Mixed solution is cooled to 5 ℃, iron trichloride is joined in mixed solution, the mol ratio of iron trichloride and aniline is 0.5:1; Then stir 6h, product, through suction filtration, is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, and 60 ℃ of dry 24h of final vacuum, obtain sepiolite/polyaniline nano-composite material.
After measured, this material electric conductivity is 2.7S/cm, than electric capacity, is 293F/g.
Embodiment 2:
A preparation method for sepiolite/polyaniline nano-composite material, preparation process is as follows:
1) the sepiolite raw material of crossing 80 mesh sieves is mixed by weight 1:40 with distilled water, strong stirring mixing 3h, then standing 16h, gets upper strata sepiolite suspension, and suction filtration, distilled water wash obtain washing sepiolite in 60 ℃ of vacuum-drying 24h;
2) aqueous hydrochloric acid that is 1mol/L by the washing sepiolite of crossing 200 mesh sieves with concentration mixes by weight the ratio of 1:10, and then, in 40 ℃ of stirring 24h, filtration, distilled water wash, to neutral, obtain acid activation sepiolite in 60 ℃ of vacuum-drying 24h;
3) the acid activation sepiolite of crossing 200 mesh sieves is mixed by weight the ratio of 1:30 with dehydrated alcohol, add 3-aminopropyl trimethoxysilane, the weight ratio of 3-aminopropyl trimethoxysilane and acid activation sepiolite is 0.08:1; Ultrasonic being uniformly dispersed, then, in 75 ℃ of stirring 10h, filters, and uses in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, obtains organic modification sepiolite.
4) will cross the organic modification sepiolite of 200 mesh sieves and distilled water is ultrasonic is uniformly dispersed, make the dispersion liquid that organic modification sepiolite weight percent content is 0.1%, under the condition constantly stirring, in dispersion liquid, add aniline, the weight ratio of aniline and organic modification sepiolite is 10:1; Add hydrochloric acid, the mol ratio of hydrochloric acid and aniline is 10:1, obtains mixed solution again; Mixed solution is cooled to-5 ℃, ammonium persulphate is joined in mixed solution, the mol ratio of ammonium persulphate and aniline is 1:1; Then stir 8h, product, through suction filtration, is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, and 60 ℃ of dry 24h of final vacuum, obtain sepiolite/polyaniline nano-composite material;
After measured, this material electric conductivity is 3.4S/cm, than electric capacity, is 445F/g.
Embodiment 3:
A preparation method for sepiolite/polyaniline nano-composite material, preparation process is as follows:
1) the sepiolite raw material of crossing 80 mesh sieves is added by weight 1:60 and mixed with distilled water, strong stirring mixing 1h, then standing 12h, gets upper strata sepiolite suspension, and suction filtration, distilled water wash obtain washing sepiolite in 60 ℃ of vacuum-drying 24h;
2) aqueous hydrochloric acid that is 2mol/L by the washing sepiolite of crossing 200 mesh sieves with concentration mixes by weight the ratio of 1:30, and then, in 60 ℃ of stirring 8h, filtration, distilled water wash, to neutral, obtain acid activation sepiolite in 60 ℃ of vacuum-drying 24h;
3) the acid activation sepiolite of crossing 200 mesh sieves is mixed by weight the ratio of 1:40 with dry toluene, add diamino diethoxy silane, the weight ratio of diamino diethoxy silane and acid activation sepiolite is 0.15:1; Ultrasonic being uniformly dispersed, then, in 100 ℃ of stirring 16h, filters, and uses in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, obtains organic modification sepiolite;
4) will cross the organic modification sepiolite of 200 mesh sieves and distilled water is ultrasonic is uniformly dispersed, make the dispersion liquid that organic modification sepiolite weight percent content is 1%, under the condition constantly stirring, in dispersion liquid, add aniline, the weight ratio of aniline and organic modification sepiolite is 5:1; Add perchloric acid, the mol ratio of perchloric acid and aniline is 5:1, obtains mixed solution again; Mixed solution is cooled to 0 ℃, potassium bichromate is joined in mixed solution, the mol ratio of potassium bichromate and aniline is 2:1; Then stir 16h, product, through suction filtration, is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, and 60 ℃ of dry 24h of final vacuum, obtain sepiolite/polyaniline nano-composite material.
After measured, this material electric conductivity is 2.5S/cm, than electric capacity, is 245F/g.
Embodiment 4:
A preparation method for sepiolite/polyaniline nano-composite material, preparation process is as follows:
1) the sepiolite raw material of crossing 80 mesh sieves is mixed by weight 1:50 with distilled water, strong stirring mixing 2h, then standing 16h, gets upper strata sepiolite suspension, and suction filtration, distilled water wash obtain washing sepiolite in 60 ℃ of vacuum-drying 24h;
2) aqueous hydrochloric acid that is 0.5mol/L by the washing sepiolite of crossing 200 mesh sieves with concentration mixes by weight the ratio of 1:20, and then, in 25 ℃ of stirring 10h, filtration, distilled water wash, to neutral, obtain acid activation sepiolite in 60 ℃ of vacuum-drying 24h;
3) the acid activation sepiolite of crossing 200 mesh sieves is mixed by weight the ratio of 1:50 with dry toluene, add 3-aminopropyl trimethoxysilane, the weight ratio of 3-aminopropyl trimethoxysilane and acid activation sepiolite is 0.25:1; Ultrasonic being uniformly dispersed, then, in 110 ℃ of stirring 24h, filters, and uses in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, obtains organic modification sepiolite;
4) will cross the organic modification sepiolite of 200 mesh sieves and distilled water is ultrasonic is uniformly dispersed, make the dispersion liquid that organic modification sepiolite weight percent content is 3%, under the condition constantly stirring, in dispersion liquid, add aniline, the weight ratio of aniline and organic modification sepiolite is 0.5:1; Add hydrochloric acid, the mol ratio of hydrochloric acid and aniline is 1:1, obtains mixed solution again; Mixed solution is cooled to-10 ℃, ammonium persulphate is joined in mixed solution, the mol ratio of ammonium persulphate and aniline is 1:1; Then stir 24h, product, through suction filtration, is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, and 60 ℃ of dry 24h of final vacuum, obtain sepiolite/polyaniline nano-composite material.
After measured, this material electric conductivity is 1.5S/cm, than electric capacity, is 192F/g.
Embodiment 5:
A preparation method for sepiolite/polyaniline nano-composite material, comprises the following steps:
A, the sepiolite (raw material) that will cross 80 mesh sieves and water are by weight the ratio mix and blend 3.5h of 1:45, then standing 18h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 1.75mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:20, then in 43 ℃ of stirred in water bath 16h, filtration, solids are washed with distilled water to neutrality (being that pH is 6～7), in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:35 mix, add with amino silane coupling agent, (being preferably through ultrasonic dispersion) mixes, then at 90 ℃, stir 16h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.14:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 1.52%; Under stirring, (in dispersion liquid) adds doping agent and aniline, after stirring, obtains mixed solution; Mixed solution is cooled to-2 ℃, oxygenant joined in mixed solution again, stir 15h, reacting rear material is through suction filtration, and solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 8:1;
Described doping agent and the mol ratio of aniline are 5.2:1;
Described oxygenant and the mol ratio of aniline are 1.2:1.
Embodiment 6:
A preparation method for sepiolite/polyaniline nano-composite material, comprises the following steps:
A, the sepiolite (raw material) that will cross 80 mesh sieves and water are by weight the ratio mix and blend 1h of 1:30, then standing 12h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 0.5mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:10, then in 25 ℃ of stirred in water bath 24h, filtration, solids are washed with distilled water to neutrality (being that pH is 6～7), in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:20 mix, add with amino silane coupling agent, (being preferably through ultrasonic dispersion) mixes, then at 70 ℃, stir 24h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.03:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 0.05%; Under stirring, (in dispersion liquid) adds doping agent and aniline, after stirring, obtains mixed solution; Mixed solution is cooled to-10 ℃, oxygenant joined in mixed solution again, stir 24h, reacting rear material is through suction filtration, and solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 0.5:1;
Described doping agent and the mol ratio of aniline are 0.5:1;
Described oxygenant and the mol ratio of aniline are 0.5:1.
Embodiment 7:
A preparation method for sepiolite/polyaniline nano-composite material, comprises the following steps:
A, the sepiolite (raw material) that will cross 80 mesh sieves and water are by weight the ratio mix and blend 6h of 1:60, then standing 24h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 3mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:30, then in 60 ℃ of stirred in water bath 8h, filtration, solids are washed with distilled water to neutrality (being that pH is 6～7), in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:50 mix, add with amino silane coupling agent, (being preferably through ultrasonic dispersion) mixes, then at 110 ℃, stir 8h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.25:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 3%; Under stirring, (in dispersion liquid) adds doping agent and aniline, after stirring, obtains mixed solution; Mixed solution is cooled to 5 ℃, oxygenant joined in mixed solution again, stir 6h, reacting rear material is through suction filtration, and solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 15:1;
Described doping agent and the mol ratio of aniline are 10:1;
Described oxygenant and the mol ratio of aniline are 2:1.
Embodiment 8:
A preparation method for sepiolite/polyaniline nano-composite material, comprises the following steps:
A, the sepiolite (raw material) that will cross 80 mesh sieves and water are by weight the ratio mix and blend 12h of 1:35, then standing 16h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 1mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:15, then in 30 ℃ of stirred in water bath 15h, filtration, solids are washed with distilled water to neutrality (being that pH is 6～7), in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:30 mix, add with amino silane coupling agent, (being preferably through ultrasonic dispersion) mixes, then at 80 ℃, stir 14h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.1:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 1%; Under stirring, (in dispersion liquid) adds doping agent and aniline, after stirring, obtains mixed solution; Mixed solution is cooled to-5 ℃, oxygenant joined in mixed solution again, stir 14h, reacting rear material is through suction filtration, and solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 3:1;
Described doping agent and the mol ratio of aniline are 2:1;
Described oxygenant and the mol ratio of aniline are 0.8:1.
Embodiment 9:
A preparation method for sepiolite/polyaniline nano-composite material, comprises the following steps:
A, the sepiolite (raw material) that will cross 80 mesh sieves and water are by weight the ratio mix and blend 3h of 1:40, then standing 16h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 1.5mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:18, then in 40 ℃ of stirred in water bath 16h, filtration, solids are washed with distilled water to neutrality (being that pH is 6～7), in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:30 mix, add with amino silane coupling agent, (being preferably through ultrasonic dispersion) mixes, then at 90 ℃, stir 16h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.15:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 1.5%; Under stirring, (in dispersion liquid) adds doping agent and aniline, after stirring, obtains mixed solution; Mixed solution is cooled to 0 ℃, oxygenant joined in mixed solution again, stir 16h, reacting rear material is through suction filtration, and solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 5:1;
Described doping agent and the mol ratio of aniline are 3:1;
Described oxygenant and the mol ratio of aniline are 1:1.
Embodiment 10:
A preparation method for sepiolite/polyaniline nano-composite material, comprises the following steps:
A, the sepiolite (raw material) that will cross 80 mesh sieves and water are by weight the ratio mix and blend 4h of 1:50, then standing 20h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 2mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:22, then in 50 ℃ of stirred in water bath 18h, filtration, solids are washed with distilled water to neutrality (being that pH is 6～7), in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:40 mix, add with amino silane coupling agent, (being preferably through ultrasonic dispersion) mixes, then at 100 ℃, stir 13h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.20:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 2%; Under stirring, (in dispersion liquid) adds doping agent and aniline, after stirring, obtains mixed solution; Mixed solution is cooled to 1 ℃, oxygenant joined in mixed solution again, stir 10h, reacting rear material is through suction filtration, and solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 10:1;
Described doping agent and the mol ratio of aniline are 7:1;
Described oxygenant and the mol ratio of aniline are 1.3:1.
Embodiment 11:
A preparation method for sepiolite/polyaniline nano-composite material, comprises the following steps:
A, the sepiolite (raw material) that will cross 80 mesh sieves and water are by weight the ratio mix and blend 5h of 1:55, then standing 22h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 2.5mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:25, then in 50 ℃ of stirred in water bath 13h, filtration, solids are washed with distilled water to neutrality (being that pH is 6～7), in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:45 mix, add with amino silane coupling agent, (being preferably through ultrasonic dispersion) mixes, then at 110 ℃, stir 9h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.23:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 2.6%; Under stirring, (in dispersion liquid) adds doping agent and aniline, after stirring, obtains mixed solution; Mixed solution is cooled to 2 ℃, oxygenant joined in mixed solution again, stir 16h, reacting rear material is through suction filtration, and solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 13:1;
Described doping agent and the mol ratio of aniline are 8:1;
Described oxygenant and the mol ratio of aniline are 1.8:1.
Doping agent described in steps d is any one in hydrochloric acid, sulfuric acid or perchloric acid.
In above-described embodiment 5～11: can be any one in 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane or diamino diethoxy silane with amino silane coupling agent described in step c.
In above-described embodiment 5～11: oxygenant described in steps d can be ammonium persulphate (being called for short APS), iron trichloride (FeCl
3) or potassium bichromate (K
2cr
2o
7) in any one.
In above-described embodiment 5～11: described in step a and/or step b, distilled water can replace with deionized water.
The present invention's sepiolite raw material used picks up from Yi County, Hebei, can effectively remove in sepiolite the impurity such as calcium carbonate after washing and acid activation, and the average content of scpiolitc can reach more than 60%.
Sepiolite/the polyaniline nano-composite material of above-described embodiment 5～11 preparations has high conductivity (1.5S/cm～3.4S/cm) and high specific capacitance (192F/g～445F/g), can be used for the fields such as electrode material for super capacitor, secondary cell and electromagnetic shielding material.
In above-described embodiment: each raw material adopting is commercially available prod.
In above-described embodiment: in the percentage adopting, do not indicate especially, be quality (weight) percentage or well known to a person skilled in the art percentage; Described quality (weight) part can be all gram or kilogram.
In above-described embodiment: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement and have described good result described in content of the present invention.
Claims (8)
1. a preparation method for sepiolite/polyaniline nano-composite material, is characterized in that comprising the following steps:
A, by the sepiolite of crossing 80 mesh sieves and water the ratio mix and blend 1～6h of 1:30～60, then standing 12～24h by weight; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 ℃ of vacuum-drying 24h, makes washing sepiolite;
B, the aqueous hydrochloric acid that is 0.5～3mol/L with concentration by the washing sepiolite of crossing 200 mesh sieves mix by weight the ratio of 1:10～30, then in 25～60 ℃ of stirred in water bath 8～24h, filtration, solids are washed with distilled water to neutrality, in 60 ℃ of vacuum-drying 24h, make acid activation sepiolite;
C, by the acid activation sepiolite of crossing 200 mesh sieves and organic solvent by weight the ratio of 1:20～50 mix, add with amino silane coupling agent, mix, then at 70～110 ℃, stir 8～24h, filter, solids, with using in turn chloroform, washing with alcohol, in 60 ℃ of vacuum-drying 24h, makes organic modification sepiolite;
Described organic solvent is dry toluene or dehydrated alcohol;
The weight ratio of the silane coupling agent that described band is amino and acid activation sepiolite is 0.03～0.25:1;
D, organic modification sepiolite and the distilled water of crossing 200 mesh sieves are mixed to the dispersion liquid that the weight percent content of making organic modification sepiolite is 0.05%～3%; Under stirring, add doping agent and aniline, after stirring, obtain mixed solution; Mixed solution is cooled to-10～5 ℃, again oxygenant joined in mixed solution, stir 6～24h, reacting rear material is through suction filtration, solids is used deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in 60 ℃ of dry 24h of vacuum, make product-sepiolite/polyaniline nano-composite material;
The weight ratio of described aniline and organic modification sepiolite is 0.5～15:1;
Described doping agent and the mol ratio of aniline are 0.5～10:1;
Described oxygenant and the mol ratio of aniline are 0.5～2:1.
2. by the preparation method of sepiolite/polyaniline nano-composite material described in claim 1, it is characterized in that: doping agent described in steps d is any one in hydrochloric acid, sulfuric acid or perchloric acid.
3. by the preparation method of sepiolite/polyaniline nano-composite material described in claim 1 or 2, it is characterized in that: described in step c, with amino silane coupling agent, be any one in 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane or diamino diethoxy silane.
4. by the preparation method of sepiolite/polyaniline nano-composite material described in claim 1 or 2, it is characterized in that: oxygenant described in steps d is any one in ammonium persulphate, iron trichloride or potassium bichromate.
5. by the preparation method of sepiolite/polyaniline nano-composite material described in claim 3, it is characterized in that: in described steps d, oxygenant is any one in ammonium persulphate, iron trichloride or potassium bichromate.
6. by the preparation method of sepiolite/polyaniline nano-composite material described in claim 1,2 or 5, it is characterized in that: described in step a and/or step b, distilled water replaces with deionized water.
7. by the preparation method of sepiolite/polyaniline nano-composite material described in claim 3, it is characterized in that: described in step a and/or step b, distilled water replaces with deionized water.
8. by the preparation method of sepiolite/polyaniline nano-composite material described in claim 4, it is characterized in that: described in step a and/or step b, distilled water replaces with deionized water.
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