CN103943838A - Preparation method of metal oxide nanosheet and carbon nanotube composite energy-storage material - Google Patents
Preparation method of metal oxide nanosheet and carbon nanotube composite energy-storage material Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a preparation method of a metal oxide nanosheet and carbon nanotube composite energy-storage material. The preparation method comprises the following steps: firstly, modifying a carbon nanotube by sulfonated polystyrene; secondly, growing a metal hydroxide precursor on the modified carbon nanotube by adopting an oil bath process; and finally, calcining the precursor in the atmosphere of nitrogen gas, thereby obtaining the metal oxide nanosheet and carbon nanotube composite energy-storage material. The preparation method is characterized in that the composite energy-storage material is prepared by adopting a simple chemical synthesis means and has a high specific surface area and the good conductivity, and both the capacity and the stability of the energy-storage material are superior to those of a traditional metal oxide nanosheet and carbon nanotube composite energy-storage material.
Description
Technical field
The present invention relates to the preparation of energy storage material, be particularly related to the preparation method of a kind of metal oxide nano-sheet and carbon nano-tube composite energy-storage material, be specifically related to the preparation of zinc oxide, nickel oxide, cobaltosic oxide, di-iron trioxide, tri-iron tetroxide, manganese dioxide, zinc manganate, mangaic acid iron, mangaic acid cobalt, mangaic acid nickel and sub-cobalt acid nickel nano film and carbon nano tube compound material.
Technical background
Lithium ion battery, as a kind of novel, clean, chargeable power supply, has the advantages such as operating voltage is high, energy density is high, quality is light, self-discharge rate is low, on the portable electric appts such as mobile phone, notebook computer, is widely applied.Widely used electrode material in lithium ion, through optimization for many years, performance has reached its limit.In the exploitation of lithium ion battery of future generation, main target is to extend cycle life, improves energy density and charging and discharging capacity.Graphite is widely used negative material in current lithium ion battery, and theoretical specific capacity only has 372mA h g
-1, therefore find and can under low potential, keep the material of high power capacity to substitute the focus that graphite is current research.Researcher has attempted a lot of materials and has substituted graphite as negative material, different from the lithium embedding-deintercalation process of graphite, these materials and the effect of lithium metal comprise following two different processes: alloy-removal alloying (for example silicon, tin/tin ash SnO of lithium and metal
2with Al etc.) and the formation-decomposition (for example CoO, NiO, FeO) of reversible lithia nanometer matrix.The limitation of these materials is: after initial circulation several times, have irreversible capacity loss; Repeatedly, after circulation, electrode is damaged gradually.Irreversible capacitance loss can solve by pre-lithiation techniques.The pulsating stress that change in volume produces in charge and discharge process has accelerated the mechanical failure of electrode material, make the battery capacity fast-descending after repeatedly circulating, a lot of research concentrates on and utilizes adjustment structure strategy to prepare loose structure compoundly to alleviate above problem with other material carries out compound for example carbon as hollow, nanometer sheet or porous structure material and utilization regulate composition strategy.
Another strategy that improves electrode material lithium ion storage performance is to prepare carbon composite (amorphous carbon, Graphene, carbon nano-tube (CNTs)).On the one hand, flexible carbon-coating can cushion the stress rupture effect that in charge and discharge process, change in volume causes (cushion effect); On the other hand, the carbon-coating of high conductivity can also improve the conductivity of electrode material.The carbon nano-tube of one dimension is possessing outside good conductivity, the feature such as flexible, there is again self original advantage: its dispersiveness is better than the carbon spherical structure of zero-bit, further shorten lithium ion transmission range and compare with two-dimentional Graphene, thereby there is superior charge-discharge performance and can realize fast charging and discharging.
In sum, by the composition to inorganic matter, content, the adjusting of microstructure can improve the lithium ion storage performance of material effectively.CNTs base nanostructure composite material has demonstrated the good potentiality as lithium ion battery negative material, single but the method for preparing this material exists composition, and pattern and structure are not easy the problem regulating.There is researcher to pass through to build for example carbon-coating of middle intermediary and polyelectrolyte on CNTs, prepared CNTs base nanostructure composite material.But still lack one effectively, the method for universality is prepared inorganic matter composition, content, the CNTs base nanostructure composite material that microstructure is controlled.
Summary of the invention
In order to overcome the defect of prior art, improve the lithium ion storge quality of metal oxide, the object of the invention is to propose the preparation method of a kind of metal oxide nano-sheet and carbon nano-tube composite energy-storage material, by the controlled polymer of the composition of growing on CNTs, structure and molecular weight, and polymer is carried out to functionalization obtain gelatin polymer, the grown mesoporous structure of induction or the nanometer sheet structure composite material of inorganic matter of functional group in recycling gelatin polymer.
In order to achieve the above object, technical scheme of the present invention is:
The preparation method of metal oxide nano-sheet and carbon nano-tube composite energy-storage material, comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 0.4～40mg is put into flask, add 60～5000mL acetone, ultrasonic dispersion 5～25 minutes, then add 0.8～80mg maleic anhydride, stirring reaction 10～12 hours at 25～30 DEG C, obtain the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 0.127～12.7g modified, join in the anhydrous toluene solution of 30～3000mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 80～8000mg is added to 3.82～382g, ultrasonic 10 minutes, is designated as B liquid; A liquid B liquid is mixed, and 70～75 DEG C of stirring reactions 7～10 hours under blanket of nitrogen, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 30～3000mg polystyrene layer is modified, join 50～5000mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 10～25 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 5～500mg, join in 40～4000mL deionized water, ultrasonic dispersion 10 minutes, add successively again 7.2～725mg natrium citricum, 35.5～3550mg hexamethylenetetramine, the salt of 75～7500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 400～450 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
Utilize metal oxide nano-sheet and the carbon nano tube compound material that the present invention prepares to there is following characteristics: 1 higher specific area, thus more active reaction sites can be provided, thus electrochemical efficiency improved; 2 good conductivity, have than the better electronics of the pure metal oxides speed of preaching; 3 have higher capacity and better cyclical stability with respect to traditional material.This method will greatly be enriched kind and the character of CNTs@nanostructure composite material of inorganic matter, greatly expand their range of application, for industrial production and the extensive use with new structure and excellent properties nanostructure inorganic matter/CNTs composite material lay the foundation.
Brief description of the drawings
Fig. 1 is the first, the second and the 5th cyclic curve that cyclic voltammetry is tested sub-cobalt acid nickel nano film and composite structure of carbon nano tube material.
Fig. 2 is sub-cobalt acid nickel nano film and the voltage capacity curve of composite structure of carbon nano tube material under 400 milliamperes of/gram of current densities.
Fig. 3 is sub-cobalt acid nickel nano film and the capacity-cycle-index curve of the sub-cobalt acid nickel nanometer blocks material of composite structure of carbon nano tube material (I) (II) under 400 milliamperes of/gram of current densities.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment mono-
The present embodiment comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 0.4mg is put into flask, adds 60mL acetone, ultrasonic dispersion 5 minutes, then adds 0.8mg maleic anhydride, and stirring reaction 10 hours at 25 DEG C obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 0.127g modified, join in the anhydrous toluene solution of 30mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 80mg is added to 3.82g, ultrasonic 10 minutes, is designated as B liquid; A liquid B liquid is mixed, and 70 DEG C of stirring reactions 7 hours under blanket of nitrogen, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 30mg polystyrene layer is modified, join 50mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 10 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 5mg, join in 40mL deionized water, ultrasonic dispersion 10 minutes, add successively again 7.2mg natrium citricum, 35.5mg hexamethylenetetramine, the salt of 75mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 400 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
The sub-cobalt acid nickel nano film that the present embodiment obtains and composite structure of carbon nano tube material properties test be as shown in FIG. 1 to 3: Fig. 1 is the first, the second and the 5th cyclic curve that cyclic voltammetry is tested the sour nickel nano film of sub-cobalt and composite structure of carbon nano tube material; The sub-cobalt acid nickel nano film of Fig. 2 and the voltage capacity curve of composite structure of carbon nano tube material under 400 milliamperes of/gram of current densities; Fig. 3 is sub-cobalt acid nickel nano film and the capacity-cycle-index curve of the sub-cobalt acid nickel nanometer blocks material of composite structure of carbon nano tube material (I) (II) under 400 milliamperes of/gram of current densities.Can find out that in conjunction with three figure the carbon nanotube-based metal oxide nano-sheet sandwich that the present embodiment obtains is the lithium ion battery negative material with high power capacity and excellent cycle performance.
Embodiment bis-
The present embodiment comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 2mg is put into flask, adds 300mL acetone, ultrasonic dispersion 5 minutes, then adds 4mg maleic anhydride, and stirring reaction 10 hours at 25 DEG C obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 0.635g modified, join in the anhydrous toluene solution of 150mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 400mg is added to 19.1g, ultrasonic 10 minutes, is designated as B liquid; A liquid B liquid is mixed, and 70 DEG C of stirring reactions 9 hours under blanket of nitrogen, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 150mg polystyrene layer is modified, join 200mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 10 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 15mg, join in 120mL deionized water, ultrasonic dispersion 10 minutes, add successively again 36.2mg natrium citricum, 177.5mg hexamethylenetetramine, the salt of 177.5mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 400 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
The carbon nanotube-based metal oxide nano-sheet sandwich obtaining is the lithium ion battery negative material with high power capacity and excellent cycle performance.
Embodiment tri-
The present embodiment comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 4mg is put into flask, adds 500mL acetone, ultrasonic dispersion 10 minutes, then adds 8mg maleic anhydride, and stirring reaction 10 hours at 25 DEG C obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 1.27g modified, join in the anhydrous toluene solution of 300mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 800mg is added to 38.2g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 70 DEG C of stirring reactions 10 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 300mg polystyrene layer is modified, join 500mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 25 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 50mg, join in 400mL deionized water, ultrasonic dispersion 10 minutes, add successively again 72.5mg natrium citricum, 355mg hexamethylenetetramine, the salt of 750mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
The carbon nanotube-based metal oxide nano-sheet sandwich obtaining is the lithium ion battery negative material with high power capacity and excellent cycle performance.
Embodiment tetra-
The present embodiment comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 8mg is put into flask, adds 1000mL acetone, ultrasonic dispersion 20 minutes, then add 16mg maleic anhydride, then stirring reaction 10 hours at 25 DEG C, obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 2.54g modified, join in the anhydrous toluene solution of 500mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 1500mg is added to 76.4g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 75 DEG C of stirring reactions 6 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 600mg polystyrene layer is modified, join 1000mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 25 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 100mg, join in 750mL deionized water, ultrasonic dispersion 10 minutes, add successively again 145mg natrium citricum, 750mg hexamethylenetetramine, the salt of 1500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
The carbon nanotube-based metal oxide nano-sheet sandwich obtaining is the lithium ion battery negative material with high power capacity and excellent cycle performance.
Embodiment five
The present embodiment comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 40mg is put into flask, adds 5000mL acetone, ultrasonic dispersion 25 minutes, then add 80mg maleic anhydride, then stirring reaction 10 hours at 25 DEG C, obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 12.7g modified, join in the anhydrous toluene solution of 3000mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 8000mg is added to 382g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 75 DEG C of stirring reactions 10 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 3000mg polystyrene layer is modified, join 5000mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 30 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 500mg, join in 4000mL deionized water, ultrasonic dispersion 10 minutes, add successively again 725mg natrium citricum, 3550mg hexamethylenetetramine, the salt of 7500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
The carbon nanotube-based metal oxide nano-sheet sandwich obtaining is the lithium ion battery negative material with high power capacity and excellent cycle performance.
Claims (6)
1. a preparation method for metal oxide nano-sheet and carbon nano-tube composite energy-storage material, is characterized in that, comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 0.4～40mg is put into flask, add 60～5000mL acetone, ultrasonic dispersion 5～25 minutes, then add 0.8～80mg maleic anhydride, stirring reaction 10～12 hours at 25～30 DEG C, obtain the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 0.127～12.7g modified, join in the anhydrous toluene solution of 30～3000mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 80～8000mg is added to 3.82～382g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 70～75 DEG C of stirring reactions 7～10 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 30～3000mg polystyrene layer is modified, join 50～5000mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 10～25 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 5～500mg, join in 40～4000mL deionized water, ultrasonic dispersion 10 minutes, add successively again 7.2～725mg natrium citricum, 35.5～3550mg hexamethylenetetramine, the salt of 75～7500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 400～450 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
2. the preparation method of a kind of metal oxide nano-sheet according to claim 1 and carbon nano-tube composite energy-storage material, is characterized in that, comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 0.4mg is put into flask, adds 60mL acetone, ultrasonic dispersion 5 minutes, then adds 0.8mg maleic anhydride, and stirring reaction 10 hours at 25 DEG C obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 0.127g modified, join in the anhydrous toluene solution of 30mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 80mg is added to 3.82g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 70 DEG C of stirring reactions 7 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 30mg polystyrene layer is modified, join 50mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 10 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 5mg, join in 40mL deionized water, ultrasonic dispersion 10 minutes, add successively again 7.2mg natrium citricum, 35.5mg hexamethylenetetramine, the salt of 75mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 400 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
3. the preparation method of a kind of metal oxide nano-sheet according to claim 1 and carbon nano-tube composite energy-storage material, is characterized in that, comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 2mg is put into flask, adds 300mL acetone, ultrasonic dispersion 5 minutes, then adds 4mg maleic anhydride, and stirring reaction 10 hours at 25 DEG C obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 0.635g modified, join in the anhydrous toluene solution of 150mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 400mg is added to 19.1g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 70 DEG C of stirring reactions 9 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 150mg polystyrene layer is modified, join 200mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 10 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 15mg, join in 120mL deionized water, ultrasonic dispersion 10 minutes, add successively again 36.2mg natrium citricum, 177.5mg hexamethylenetetramine, the salt of 177.5mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 400 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
4. the preparation method of a kind of metal oxide nano-sheet according to claim 1 and carbon nano-tube composite energy-storage material, is characterized in that, comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 4mg is put into flask, adds 500mL acetone, ultrasonic dispersion 10 minutes, then adds 8mg maleic anhydride, and stirring reaction 10 hours at 25 DEG C obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take the carbon nano-tube of 1.27g modified, join in the anhydrous toluene solution of 300mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 800mg is added to 38.2g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 70 DEG C of stirring reactions 10 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 300mg polystyrene layer is modified, join 500mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 25 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 50mg, join in 400mL deionized water, ultrasonic dispersion 10 minutes, add successively again 72.5mg natrium citricum, 355mg hexamethylenetetramine, the salt of 750mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
5. the preparation method of a kind of metal oxide nano-sheet according to claim 1 and carbon nano-tube composite energy-storage material, is characterized in that, comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 8mg is put into flask, adds 1000mL acetone, ultrasonic dispersion 20 minutes, then adds 16mg maleic anhydride, and stirring reaction 10 hours at 25 DEG C obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take 2.54g carbon nano-tube modified, join in the anhydrous toluene solution of 500mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 1500mg is added to 76.4g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 75 DEG C of stirring reactions 6 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 600mg polystyrene layer is modified, join 1000mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 25 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 100mg, join in 750mL deionized water, ultrasonic dispersion 10 minutes, add successively again 145mg natrium citricum, 750mg hexamethylenetetramine, the salt of 1500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
6. the preparation method of a kind of metal oxide nano-sheet according to claim 1 and carbon nano-tube composite energy-storage material, is characterized in that, comprises the following steps:
The first step: the carbon nano-tube with hydroxyl that takes 40mg is put into flask, adds 5000mL acetone, ultrasonic dispersion 25 minutes, then adds 80mg maleic anhydride, and stirring reaction 10 hours at 25 DEG C obtains the carbon nano-tube of modified, and with acetone washing 4 times;
Second step: take 12.7g carbon nano-tube modified, join in the anhydrous toluene solution of 3000mL, ultrasonic dispersion 10 minutes, is designated as A liquid; The styrene the inside that the azo-bis-isobutyl cyanide of 8000mg is added to 382g, ultrasonic 10 minutes, is designated as B liquid; A liquid and B liquid are mixed, and under blanket of nitrogen, 75 DEG C of stirring reactions 10 hours, obtain the carbon nano-tube that polystyrene layer is modified, with ethanol washing 5 times;
The 3rd step: take the carbon nano-tube that 3000mg polystyrene layer is modified, join 5000mL concentration and be in 98% the concentrated sulfuric acid, ultrasonic dispersion 10 minutes, 70 DEG C of oil bath stirring reactions 30 minutes, obtain the carbon nano-tube that sulfonated polystyrene layer is modified;
The 4th step: the sulfonated polystyrene modified carbon nano-tube that takes the above-mentioned preparation of 500mg, join in 4000mL deionized water, ultrasonic dispersion 10 minutes, add successively again 725mg natrium citricum, 3550mg hexamethylenetetramine, the salt of 7500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, for products therefrom, ethanol washs 5 times, obtains the presoma of carbon nanotube-based composite metal oxide material; The contained metal ion of salt of described metal ion comprises zinc, nickel, cobalt, iron, manganese;
The 5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcining 2 hours, heating rate is 1 DEG C of min
-1; The product obtaining is exactly carbon nanotube-based metal oxide nano-sheet sandwich.
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