CN103980488B - A kind of preparation method of sepiolite/polyaniline nano-composite material - Google Patents
A kind of preparation method of sepiolite/polyaniline nano-composite material Download PDFInfo
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- CN103980488B CN103980488B CN201410216657.1A CN201410216657A CN103980488B CN 103980488 B CN103980488 B CN 103980488B CN 201410216657 A CN201410216657 A CN 201410216657A CN 103980488 B CN103980488 B CN 103980488B
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Abstract
The invention discloses a kind of preparation method of sepiolite/polyaniline nano-composite material, it is characterized in that: by sepiolite and water mix and blend, leave standstill, get upper strata sepiolite suspension filtered, wash with water, dry, obtained washing sepiolite; Sepiolite and mixed in hydrochloric acid will be washed, stirred in water bath, filtration, solids washed with water, dry, obtained acid activation sepiolite; Acid activation sepiolite is mixed with organic solvent, adds the silane coupling agent that band is amino, mixing, stirred in water bath, filter, washing, dry, obtained organic modification sepiolite; Organic modification sepiolite and water are mixed and made into dispersion liquid; Add doping agent and aniline under stirring, cooling, then add oxygenant stirring, reacting rear material is through washing, dry, i.e. obtained product-sepiolite/polyaniline nano-composite material.Matrix material prepared by the present invention has high conductivity, high specific capacitance, is applicable to the fields such as electrode material for super capacitor, secondary cell and electromagnetic shielding material.
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 as one of conducting polymer substance, due to its be easy to prepare, the electric conductivity that high temperature resistant and antioxidant property is good and higher and getting more and more people's extensive concerning, have been widely used at field tools such as secondary cell, electrochemistry and electromagnetic shieldings.But pure polyaniline exists the shortcomings such as insoluble molten, mechanical poor ductility and processing difficulties, limit 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, polyaniline and inorganic nano-particle compound are prepared inorganic/polyaniline nano composite conducting material and becomes the emphasis that people study, in prior art, common inorganic/polyaniline nano-composite material has polynite/polyaniline, silicon-dioxide/polyaniline etc., but because the specific surface area of the material such as silicon-dioxide, polynite is not high, make the ratio capacitance 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, provides a kind of preparation method of sepiolite/polyaniline nano-composite material.The present invention by sepiolite after purification, acid activation, organic modification process, arrive sepiolite fibre surface by the method for in-situ polymerization by polyaniline grafted again, thus prepare 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) crossing 80 mesh sieves and water, by weight the ratio mix and blend 1 ~ 6h of 1:30 ~ 60, then leave standstill 12 ~ 24h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of aqueous hydrochloric acid 1:10 ~ 30 by weight of 0.5 ~ 3mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 25 ~ 60 DEG C of stirred in water bath 8 ~ 24h, filtration, solids are washed with distilled water to neutrality (namely pH is 6 ~ 7), in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:20 ~ 50 by weight to be mixed, add the silane coupling agent that band is amino, (being preferably through ultrasonic disperse) mixes, then at 70 ~ 110 DEG C, 8 ~ 24h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 0.05% ~ 3%; Under stirring, (in dispersion liquid) adds doping agent and aniline, obtains mixed solution after stirring; Mixed solution is cooled to-10 ~ 5 DEG C, again oxygenant joined in mixed solution, stir 6 ~ 24h, reacting rear material is through suction filtration, solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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, wherein the average content of scpiolitc can reach more than 60%.The impurity such as calcium carbonate effectively can be removed in sepiolite after washing and acid activation,
Sepiolite/polyaniline nano-composite material prepared by the present invention has structural formula as follows:
Compared with prior art, the present invention has features 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 orthogonal (tiltedly side) crystallographic system; The existing 1-dimention nano fibrous texture being similar to carbon nanotube of sepiolite unit crystal layer, have again the laminate structure of similar polynite 2:1, the structure of sepiolite uniqueness makes it have larger specific surface area and good rheological etc.; In the preparation process of sepiolite/polyaniline nano-composite material, aniline take sepiolite fibre as template, on the axial direction due of sepiolite fibre, carry out aggregation growth, forms a kind of one-dimensional nano-composite material with nucleocapsid structure of uniqueness;
(2) the present invention adopts the amino silane coupling agent of band to carry out modification to sepiolite, graft polymerization aniline is carried out as avtive spot with the amino on silane coupling agent, make more complete along the polyaniline chain structure on sepiolite axial direction due, the transport of current-carrying is more unobstructed, is conducive to the specific conductivity improving nano composite material; Sepiolite provides larger specific surface area and the short texture of porous, is conducive to the deposition of electroactive substance, improves the charge storage ability of nano composite material;
(3), in preparation method of the present invention, the object of described washing sepiolite is the water-soluble impurity of removing, and sepiolite fibre is farthest disperseed and refinement; The object of acid activation sepiolite to remove in sepiolite the impurity such as calcium carbonate, sloughs part magnesium ion in structure simultaneously, increase specific surface area and surfactivity; The object of organic modification sepiolite is: the amino silane coupling agent of band can with aniline grafting, realize at sepiolite surface grafting polymerization aniline, the wetting ability on sepiolite surface become hydrophobicity, improve and the consistency of polyaniline;
(4) the present invention is adopted, 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, environmental protection, can be controlled specific conductivity and the chemical property of nano composite material by adjustment sepiolite consumption, practical.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of scpiolitc.Can see from this figure, 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 prepared by the present invention.Can see from this figure, 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), can see from this figure:
Acid modified meerschaum: 3675cm
-1for the stretching vibration peak of Mg-OH; 3569cm
-1for the stretching vibration peak of coordination crystal water; 3416cm
-1for the stretching vibration peak of zeolite adsorption water; 1657cm
-1for the stretching vibration peak of-OH in zeolite water; 1022cm
-1shuttle belt be the stretching vibration band of Si-O;
Organic modification sepiolite: compared with sour modified meerschaum, at 2925cm
-1and 2855cm
-1occurring weak absorbing peak, is-the CH of silane coupling agent
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
-1for the stretching vibration absorption peak of C-N; 1122cm
-1for the characteristic peak of imines nitrogen-B-N=Q-structure; 800cm
-1for the c h bond out-of-plane deformation vibration peak of Isosorbide-5-Nitrae-disubstituted benzenes ring; 1016cm
-1for the stretching vibration peak of the Si-O of sepiolite.Fig. 3 describes 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; Ratio capacitance is then obtained by charge-discharge test under the current density of 1A/g; Three-electrode method is adopted during test, sepiolite/polyaniline nano-composite material: acetylene black: tetrafluoroethylene is coated on stainless (steel) wire as working electrode (coat weight is 3 ~ 5mg) for after 80:10:10 Homogeneous phase mixing by weight, platinum electrode is to electrode, full conjunction mercurous chloride electrode is reference electrode, and electrolytic solution is the H of 1mol/L
2sO
4the aqueous solution.
Embodiment 1:
A preparation method for sepiolite/polyaniline nano-composite material, preparation process is as follows:
1) the sepiolite raw material and distilled water of crossing 80 mesh sieves are mixed by weight 1:30, strong stirring mixing 6h, then leaves standstill 24h, gets upper strata sepiolite suspension, suction filtration, distilled water wash, obtains washing sepiolite in 60 DEG C of vacuum-drying 24h;
2) be that the hydrochloric acid soln of 3mol/L mix by weight the ratio of 1:20 by washing sepiolite and the concentration of crossing 200 mesh sieves, then stir 16h in 25 DEG C, filter, distilled water wash extremely neutrality, obtain acid activation sepiolite in 60 DEG C of vacuum-drying 24h;
3) mixed with the ratio of dehydrated alcohol by weight 1:20 by the acid activation sepiolite crossing 200 mesh sieves, add 3-aminopropyl triethoxysilane, the weight ratio of 3-aminopropyl triethoxysilane and acid activation sepiolite is 0.03:1; Ultrasonic disperse is even, then stirs 8h in 70 DEG C, filters, uses chloroform, washing with alcohol in turn, obtain organic modification sepiolite in 60 DEG C of vacuum-drying 24h;
4) by even to the organic modification sepiolite and distilled water ultrasonic disperse of crossing 200 mesh sieves, making organic modification sepiolite weight percent content is the dispersion liquid of 0.05%, under the condition constantly stirred, in dispersion liquid, add aniline, the weight ratio of aniline and organic modification sepiolite is 15:1; Add sulfuric acid again, the mol ratio of sulfuric acid and aniline is 0.5:1, obtains mixed solution; Mixed solution is cooled to 5 DEG C, is joined by iron trichloride in mixed solution, the mol ratio of iron trichloride and aniline is 0.5:1; Then stir 6h, product, through suction filtration, uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, and final vacuum 60 DEG C of dry 24h, obtain sepiolite/polyaniline nano-composite material.
After measured, this material electric conductivity is 2.7S/cm, and ratio capacitance is 293F/g.
Embodiment 2:
A preparation method for sepiolite/polyaniline nano-composite material, preparation process is as follows:
1) the sepiolite raw material crossing 80 mesh sieves is mixed by weight 1:40 with distilled water, strong stirring mixing 3h, then leave standstill 16h, get upper strata sepiolite suspension, suction filtration, distilled water wash, obtain washing sepiolite in 60 DEG C of vacuum-drying 24h;
2) be that the aqueous hydrochloric acid of 1mol/L mix by weight the ratio of 1:10 by washing sepiolite and the concentration of crossing 200 mesh sieves, then stir 24h in 40 DEG C, filter, distilled water wash extremely neutrality, obtain acid activation sepiolite in 60 DEG C of vacuum-drying 24h;
3) mixed with the ratio of dehydrated alcohol by weight 1:30 by the acid activation sepiolite crossing 200 mesh sieves, add 3-aminopropyl trimethoxysilane, the weight ratio of 3-aminopropyl trimethoxysilane and acid activation sepiolite is 0.08:1; Ultrasonic disperse is even, then stirs 10h in 75 DEG C, filters, uses chloroform, washing with alcohol in turn, obtain organic modification sepiolite in 60 DEG C of vacuum-drying 24h.
4) by even to the organic modification sepiolite and distilled water ultrasonic disperse of crossing 200 mesh sieves, making organic modification sepiolite weight percent content is the dispersion liquid of 0.1%, under the condition constantly stirred, in dispersion liquid, add aniline, the weight ratio of aniline and organic modification sepiolite is 10:1; Add hydrochloric acid again, the mol ratio of hydrochloric acid and aniline is 10:1, obtains mixed solution; Mixed solution is cooled to-5 DEG C, is joined by ammonium persulphate in mixed solution, the mol ratio of ammonium persulphate and aniline is 1:1; Then stir 8h, product, through suction filtration, uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, and final vacuum 60 DEG C of dry 24h, obtain sepiolite/polyaniline nano-composite material;
After measured, this material electric conductivity is 3.4S/cm, and ratio capacitance is 445F/g.
Embodiment 3:
A preparation method for sepiolite/polyaniline nano-composite material, preparation process is as follows:
1) the sepiolite raw material crossing 80 mesh sieves is added 1:60 by weight with distilled water to mix, strong stirring mixing 1h, then leaves standstill 12h, gets upper strata sepiolite suspension, suction filtration, distilled water wash, obtains washing sepiolite in 60 DEG C of vacuum-drying 24h;
2) be that the aqueous hydrochloric acid of 2mol/L mix by weight the ratio of 1:30 by washing sepiolite and the concentration of crossing 200 mesh sieves, then stir 8h in 60 DEG C, filter, distilled water wash extremely neutrality, obtain acid activation sepiolite in 60 DEG C of vacuum-drying 24h;
3) mixed with the ratio of dry toluene by weight 1:40 by the acid activation sepiolite crossing 200 mesh sieves, add diamino diethoxy silane, the weight ratio of diamino diethoxy silane and acid activation sepiolite is 0.15:1; Ultrasonic disperse is even, then stirs 16h in 100 DEG C, filters, uses chloroform, washing with alcohol in turn, obtain organic modification sepiolite in 60 DEG C of vacuum-drying 24h;
4) by even to the organic modification sepiolite and distilled water ultrasonic disperse of crossing 200 mesh sieves, making organic modification sepiolite weight percent content is the dispersion liquid of 1%, under the condition constantly stirred, in dispersion liquid, add aniline, the weight ratio of aniline and organic modification sepiolite is 5:1; Add perchloric acid again, the mol ratio of perchloric acid and aniline is 5:1, obtains mixed solution; Mixed solution is cooled to 0 DEG C, 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, uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, and final vacuum 60 DEG C of dry 24h, obtain sepiolite/polyaniline nano-composite material.
After measured, this material electric conductivity is 2.5S/cm, and ratio capacitance is 245F/g.
Embodiment 4:
A preparation method for sepiolite/polyaniline nano-composite material, preparation process is as follows:
1) the sepiolite raw material crossing 80 mesh sieves is mixed by weight 1:50 with distilled water, strong stirring mixing 2h, then leave standstill 16h, get upper strata sepiolite suspension, suction filtration, distilled water wash, obtain washing sepiolite in 60 DEG C of vacuum-drying 24h;
2) be that the aqueous hydrochloric acid of 0.5mol/L mix by weight the ratio of 1:20 by washing sepiolite and the concentration of crossing 200 mesh sieves, then stir 10h in 25 DEG C, filter, distilled water wash extremely neutrality, obtain acid activation sepiolite in 60 DEG C of vacuum-drying 24h;
3) mixed with the ratio of dry toluene by weight 1:50 by the acid activation sepiolite crossing 200 mesh sieves, add 3-aminopropyl trimethoxysilane, the weight ratio of 3-aminopropyl trimethoxysilane and acid activation sepiolite is 0.25:1; Ultrasonic disperse is even, then stirs 24h in 110 DEG C, filters, uses chloroform, washing with alcohol in turn, obtain organic modification sepiolite in 60 DEG C of vacuum-drying 24h;
4) by even to the organic modification sepiolite and distilled water ultrasonic disperse of crossing 200 mesh sieves, making organic modification sepiolite weight percent content is the dispersion liquid of 3%, under the condition constantly stirred, in dispersion liquid, add aniline, the weight ratio of aniline and organic modification sepiolite is 0.5:1; Add hydrochloric acid again, the mol ratio of hydrochloric acid and aniline is 1:1, obtains mixed solution; Mixed solution is cooled to-10 DEG C, is joined by ammonium persulphate in mixed solution, the mol ratio of ammonium persulphate and aniline is 1:1; Then stir 24h, product, through suction filtration, uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, and final vacuum 60 DEG C of dry 24h, obtain sepiolite/polyaniline nano-composite material.
After measured, this material electric conductivity is 1.5S/cm, and ratio capacitance is 192F/g.
Embodiment 5:
A preparation method for sepiolite/polyaniline nano-composite material, comprises the following steps:
A, the sepiolite (raw material) crossing 80 mesh sieves and water, by weight the ratio mix and blend 3.5h of 1:45, then leave standstill 18h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of the aqueous hydrochloric acid 1:20 by weight of 1.75mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 43 DEG C of stirred in water bath 16h, filtration, solids are washed with distilled water to neutrality (namely pH is 6 ~ 7), in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:35 by weight to be mixed, add the silane coupling agent that band is amino, (being preferably through ultrasonic disperse) mixes, then at 90 DEG C, 16h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 1.52%; Under stirring, (in dispersion liquid) adds doping agent and aniline, obtains mixed solution after stirring; Mixed solution is cooled to-2 DEG C, joined by oxygenant in mixed solution again, stir 15h, reacting rear material is through suction filtration, and solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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) crossing 80 mesh sieves and water, by weight the ratio mix and blend 1h of 1:30, then leave standstill 12h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of the aqueous hydrochloric acid 1:10 by weight of 0.5mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 25 DEG C of stirred in water bath 24h, filtration, solids are washed with distilled water to neutrality (namely pH is 6 ~ 7), in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:20 by weight to be mixed, add the silane coupling agent that band is amino, (being preferably through ultrasonic disperse) mixes, then at 70 DEG C, 24h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 0.05%; Under stirring, (in dispersion liquid) adds doping agent and aniline, obtains mixed solution after stirring; Mixed solution is cooled to-10 DEG C, joined by oxygenant in mixed solution again, stir 24h, reacting rear material is through suction filtration, and solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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) crossing 80 mesh sieves and water, by weight the ratio mix and blend 6h of 1:60, then leave standstill 24h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of the aqueous hydrochloric acid 1:30 by weight of 3mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 60 DEG C of stirred in water bath 8h, filtration, solids are washed with distilled water to neutrality (namely pH is 6 ~ 7), in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:50 by weight to be mixed, add the silane coupling agent that band is amino, (being preferably through ultrasonic disperse) mixes, then at 110 DEG C, 8h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 3%; Under stirring, (in dispersion liquid) adds doping agent and aniline, obtains mixed solution after stirring; Mixed solution is cooled to 5 DEG C, joined by oxygenant in mixed solution again, stir 6h, reacting rear material is through suction filtration, and solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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) crossing 80 mesh sieves and water, by weight the ratio mix and blend 12h of 1:35, then leave standstill 16h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of the aqueous hydrochloric acid 1:15 by weight of 1mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 30 DEG C of stirred in water bath 15h, filtration, solids are washed with distilled water to neutrality (namely pH is 6 ~ 7), in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:30 by weight to be mixed, add the silane coupling agent that band is amino, (being preferably through ultrasonic disperse) mixes, then at 80 DEG C, 14h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 1%; Under stirring, (in dispersion liquid) adds doping agent and aniline, obtains mixed solution after stirring; Mixed solution is cooled to-5 DEG C, joined by oxygenant in mixed solution again, stir 14h, reacting rear material is through suction filtration, and solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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) crossing 80 mesh sieves and water, by weight the ratio mix and blend 3h of 1:40, then leave standstill 16h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of the aqueous hydrochloric acid 1:18 by weight of 1.5mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 40 DEG C of stirred in water bath 16h, filtration, solids are washed with distilled water to neutrality (namely pH is 6 ~ 7), in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:30 by weight to be mixed, add the silane coupling agent that band is amino, (being preferably through ultrasonic disperse) mixes, then at 90 DEG C, 16h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 1.5%; Under stirring, (in dispersion liquid) adds doping agent and aniline, obtains mixed solution after stirring; Mixed solution is cooled to 0 DEG C, joined by oxygenant in mixed solution again, stir 16h, reacting rear material is through suction filtration, and solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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) crossing 80 mesh sieves and water, by weight the ratio mix and blend 4h of 1:50, then leave standstill 20h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of the aqueous hydrochloric acid 1:22 by weight of 2mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 50 DEG C of stirred in water bath 18h, filtration, solids are washed with distilled water to neutrality (namely pH is 6 ~ 7), in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:40 by weight to be mixed, add the silane coupling agent that band is amino, (being preferably through ultrasonic disperse) mixes, then at 100 DEG C, 13h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 2%; Under stirring, (in dispersion liquid) adds doping agent and aniline, obtains mixed solution after stirring; Mixed solution is cooled to 1 DEG C, joined by oxygenant in mixed solution again, stir 10h, reacting rear material is through suction filtration, and solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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) crossing 80 mesh sieves and water, by weight the ratio mix and blend 5h of 1:55, then leave standstill 22h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of the aqueous hydrochloric acid 1:25 by weight of 2.5mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 50 DEG C of stirred in water bath 13h, filtration, solids are washed with distilled water to neutrality (namely pH is 6 ~ 7), in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:45 by weight to be mixed, add the silane coupling agent that band is amino, (being preferably through ultrasonic disperse) mixes, then at 110 DEG C, 9h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 2.6%; Under stirring, (in dispersion liquid) adds doping agent and aniline, obtains mixed solution after stirring; Mixed solution is cooled to 2 DEG C, joined by oxygenant in mixed solution again, stir 16h, reacting rear material is through suction filtration, and solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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, and effectively can to remove in sepiolite the impurity such as calcium carbonate after washing and acid activation, the average content of scpiolitc can reach more than 60%.
Sepiolite/polyaniline nano-composite material prepared by above-described embodiment 5 ~ 11 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 adopted is commercially available prod.
In above-described embodiment: in the percentage adopted, 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 (temperature, time, concentration etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (8)
1. a preparation method for sepiolite/polyaniline nano-composite material, is characterized in that comprising the following steps:
A, sepiolite and the water ratio mix and blend 1 ~ 6h by weight 1:30 ~ 60 of 80 mesh sieves will be crossed, then standing 12 ~ 24h; Get upper strata sepiolite suspension, filter, solids distilled water wash, in 60 DEG C of vacuum-drying 24h, obtained washing sepiolite;
B, be that the ratio of aqueous hydrochloric acid 1:10 ~ 30 by weight of 0.5 ~ 3mol/L mixes by washing sepiolite and the concentration of crossing 200 mesh sieves, then in 25 ~ 60 DEG C of stirred in water bath 8 ~ 24h, filtration, solids are washed with distilled water to neutrality, in 60 DEG C of vacuum-drying 24h, obtained acid activation sepiolite;
C, the ratio of acid activation sepiolite and the organic solvent of crossing 200 mesh sieves 1:20 ~ 50 by weight to be mixed, add the silane coupling agent that band is amino, mix, then at 70 ~ 110 DEG C, 8 ~ 24h is stirred, filter, solids uses chloroform, washing with alcohol in turn, in 60 DEG C of vacuum-drying 24h, and obtained 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, will cross the organic modification sepiolite of 200 mesh sieves and distilled water mixes, the weight percent content making organic modification sepiolite is the dispersion liquid of 0.05% ~ 3%; Under stirring, add doping agent and aniline, after stirring, obtain mixed solution; Mixed solution is cooled to-10 ~ 5 DEG C, again oxygenant joined in mixed solution, stir 6 ~ 24h, reacting rear material is through suction filtration, solids uses deionized water, N-Methyl pyrrolidone, absolute ethanol washing in turn, in vacuum 60 DEG C of dry 24h, i.e. obtained 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: be any one in 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane or diamino diethoxy silane with amino silane coupling agent described in step c.
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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