CN103943838B - The preparation method of metal oxide nano-sheet and CNT composite energy-storage material - Google Patents
The preparation method of metal oxide nano-sheet and CNT composite energy-storage material Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
A kind of preparation method of metal oxide nano-sheet and CNT energy storage material, first, carbon nano-tube modified with sulfonated polystyrene, then on the CNT of modified, grow metal hydroxides presoma by the method for oil bath, in blanket of nitrogen, metal oxide nano-sheet and CNT energy storage material finally after calcining, can be obtained；It is characteristic of the invention that the simple chemosynthesis means of employing, prepare and have high-specific surface area, good conductivity, capacity and stability are superior to metal oxide nano-sheet and the CNT composite energy-storage material of INVENTIONConventional metal-oxide.
Description
Technical field
The present invention relates to the preparation of energy storage material, particularly to the preparation method of a kind of metal oxide nano-sheet Yu CNT composite energy-storage material, it is specifically related to the preparation of zinc oxide, nickel oxide, Cobalto-cobaltic oxide, iron sesquioxide, ferroso-ferric oxide, manganese dioxide, zinc manganate, mangaic acid ferrum, 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, cleaning, chargeable power supply, has the advantages such as running voltage height, energy density height, light weight, self-discharge rate are low, is widely applied on the portable electric appts such as mobile phone, notebook computer.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 372mAhg-1, therefore find the material that can keep high power capacity under low potential to substitute the focus that graphite is research at present.Research worker has attempted a lot of material to substitute graphite as negative material, embed from the lithium of graphite-deintercalation process is different, these materials include, from the effect of lithium metal, the process that following two is different: alloy-removal alloying (such as silicon, stannum/tin ash SnO of lithium and metal2With Al etc.) and the formation-decomposition (such as CoO, NiO, FeO) of reversible lithium oxide nanometer matrix.The limitation of these materials is: after initial circulation several times, has irreversible capacity loss；Repeatedly after circulation, electrode is damaged gradually.Irreversible capacitance loss can be solved by prelithiation technology.The pulsating stress that change in volume produces in charge and discharge process accelerates the mechanical failure of electrode material, battery capacity rapid decrease after repeatedly circulation, a lot of researchs are concentrated on utilizes adjustment structure strategy namely to prepare loose structure such as hollow, nanometer sheet or porous structure material and utilization regulates composition strategy and namely carries out the compound of compound such as carbon with other material to alleviate problem above.
Another strategy improving electrode material lithium ion storage performance is to prepare carbon composite (amorphous carbon, Graphene, CNT (CNTs)).On the one hand, flexible carbon-coating can cushion the stress rupture effect (cushion effect) that in charge and discharge process, change in volume causes；On the other hand, the carbon-coating of high conductivity can also improve the electric conductivity of electrode material.One-dimensional CNT is outside possessing good conductivity, the feature such as flexible, there is again self original advantage: its dispersibility is better than the carbon spherical structure of zero-bit, and compare with the Graphene of two dimension and further shorten lithium ion transport distance, thus there is superior charge-discharge performance and fast charging and discharging can being realized.
In sum, by the composition of inorganic matter, content, the adjustment of microstructure can be effectively improved the lithium ion storage performance of material.CNTs base nanostructure composite material shows the good potentiality as lithium ion battery negative material, but the method preparing this material also exists and forms single, that pattern and structure are not easy to regulate problem.There is research worker to pass through structure middle intermediary such as carbon-coating and polyelectrolyte on CNTs, be prepared for CNTs base nanostructure composite material.But still lacking a kind of effective, the method for universality prepares 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, it is an object of the invention to the preparation method proposing a kind of metal oxide nano-sheet with CNT composite energy-storage material, by the polymer that growth composition, structure and molecular weight on CNTs are controlled, and polymer is carried out functionalization obtain gelatin polymer, the grown mesoporous structure of inducing action of functional group or nanometer sheet structural inorganic thing composite in recycling gelatin polymer.
In order to achieve the above object, the technical scheme is that
Metal oxide nano-sheet and the preparation method of CNT composite energy-storage material, comprise the following steps:
The first step: the CNT with hydroxyl weighing 0.4～40mg puts into flask, add 60～5000mL acetone, ultrasonic disperse 5～25 minutes, it is subsequently adding 0.8～80mg maleic anhydride, stirring reaction 10～12 hours at 25～30 DEG C, obtain the CNT of modified, and with washing with acetone 4 times；
Second step: weigh the CNT of 0.127～12.7g modified, joins in the anhydrous toluene solution of 30～3000mL, and ultrasonic disperse 10 minutes is designated as A liquid；The azo-bis-isobutyl cyanide of 80～8000mg is added inside the styrene of 3.82～382g, ultrasonic 10 minutes, is designated as B liquid；A liquid B liquid is mixed, under nitrogen atmosphere 70～75 DEG C of stirring reactions 7～10 hours, obtain the CNT that polystyrene layer is modified, by washing with alcohol 5 times；
3rd step: weigh the CNT that 30～3000mg polystyrene layer is modified, join in the concentrated sulphuric acid that 50～5000mL concentration is 98%, ultrasonic disperse 10 minutes, 70 DEG C of oil bath stirring reactions 10～25 minutes, obtain the CNT that sulfonated polystyrene layer is modified；
4th step: weigh the sulfonated polystyrene modified carbon nano-tube of the above-mentioned preparation of 5～500mg, join in 40～4000mL deionized water, ultrasonic disperse 10 minutes, sequentially add 7.2～725mg sodium citrate, 35.5～3550mg hexamethylenetetramine, the salt of 75～7500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom washing with alcohol 5 times, obtains the presoma of CNT based composite metal oxidate material；Metal ion contained by the salt of described metal ion includes zinc, nickel, cobalt, ferrum, manganese；
5th step: by the 4th step products therefrom in inert atmosphere stove 400～450 DEG C calcine 2 hours, heating rate is 1 DEG C of min-1；Obtained product is exactly CNT metal oxides nanometer sheet sandwich.
The metal oxide nano-sheet that the present invention prepares is utilized to have the following characteristics that 1 higher specific surface area with carbon nano tube compound material, such that it is able to provide more active reaction sites, thus improving electrochemical efficiency；2 good conductivity, have and preach speed than the better electronics of pure metal oxides；3 have higher capacity and better cyclical stability relative to traditional material.This method, by the kind of extreme enrichment CNTs nanostructured composite material of inorganic matter and character, is significantly expanded their range of application, is laid the foundation for the commercial production and extensive use with new structure and excellent properties nanostructured inorganic matter/CNTs composite.
Accompanying drawing explanation
Fig. 1 is the first, the second and the five cyclic curve of the sub-cobalt acid nickel nano film of cyclic voltammetry test and composite structure of carbon nano tube material.
Fig. 2 is sub-cobalt acid nickel nano film and composite structure of carbon nano tube material voltage capacity curve under 400 milliampere/gram electric current densities.
Fig. 3 is sub-cobalt acid nickel nano film and composite structure of carbon nano tube material (I) sub-cobalt acid nickel nanometer blocks material (II) capacity versus cycle frequency curve under 400 milliampere/gram electric current densities.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment one
The present embodiment comprises the following steps:
The first step: weigh the CNT with hydroxyl of 0.4mg and put into flask, add 60mL acetone, ultrasonic disperse 5 minutes, be subsequently adding 0.8mg maleic anhydride, stirring reaction 10 hours at 25 DEG C, obtain the CNT of modified, and with washing with acetone 4 times；
Second step: weigh the CNT of 0.127g modified, joins in the anhydrous toluene solution of 30mL, and ultrasonic disperse 10 minutes is designated as A liquid；The azo-bis-isobutyl cyanide of 80mg is added inside the styrene of 3.82g, ultrasonic 10 minutes, is designated as B liquid；A liquid B liquid is mixed, under nitrogen atmosphere 70 DEG C of stirring reactions 7 hours, obtain the CNT that polystyrene layer is modified, by washing with alcohol 5 times；
3rd step: weigh the CNT that 30mg polystyrene layer is modified, join in the concentrated sulphuric acid that 50mL concentration is 98%, ultrasonic disperse 10 minutes, 70 DEG C of oil bath stirring reactions 10 minutes, obtain the CNT that sulfonated polystyrene layer is modified；
4th step: weigh the sulfonated polystyrene modified carbon nano-tube of the above-mentioned preparation of 5mg, join in 40mL deionized water, ultrasonic disperse 10 minutes, sequentially add 7.2mg sodium citrate, 35.5mg hexamethylenetetramine, the salt of 75mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom washing with alcohol 5 times, obtains the presoma of CNT based composite metal oxidate material；Metal ion contained by the salt of described metal ion includes zinc, nickel, cobalt, ferrum, manganese；
5th step: by the 4th step products therefrom in inert atmosphere stove 400 DEG C calcine 2 hours, heating rate is 1 DEG C of min-1；Obtained product is exactly CNT metal oxides nanometer 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 five cyclic curve of the sub-cobalt acid nickel nano film of cyclic voltammetry test and composite structure of carbon nano tube material；Fig. 2 Asia cobalt acid nickel nano film and composite structure of carbon nano tube material voltage capacity curve under 400 milliampere/gram electric current densities；Fig. 3 is sub-cobalt acid nickel nano film and composite structure of carbon nano tube material (I) sub-cobalt acid nickel nanometer blocks material (II) capacity versus cycle frequency curve under 400 milliampere/gram electric current densities.Can be seen that the CNT metal oxides nanometer sheet sandwich that the present embodiment obtains is the lithium ion battery negative material with high power capacity and excellent cycle performance in conjunction with three figure.
Embodiment two
The present embodiment comprises the following steps:
The first step: weigh the CNT with hydroxyl of 2mg and put into flask, add 300mL acetone, ultrasonic disperse 5 minutes, be subsequently adding 4mg maleic anhydride, stirring reaction 10 hours at 25 DEG C, obtain the CNT of modified, and with washing with acetone 4 times；
Second step: weigh the CNT of 0.635g modified, joins in the anhydrous toluene solution of 150mL, and ultrasonic disperse 10 minutes is designated as A liquid；The azo-bis-isobutyl cyanide of 400mg is added inside the styrene of 19.1g, ultrasonic 10 minutes, is designated as B liquid；A liquid B liquid is mixed, under nitrogen atmosphere 70 DEG C of stirring reactions 9 hours, obtain the CNT that polystyrene layer is modified, by washing with alcohol 5 times；
3rd step: weigh the CNT that 150mg polystyrene layer is modified, join in the concentrated sulphuric acid that 200mL concentration is 98%, ultrasonic disperse 10 minutes, 70 DEG C of oil bath stirring reactions 10 minutes, obtain the CNT that sulfonated polystyrene layer is modified；
4th step: weigh the sulfonated polystyrene modified carbon nano-tube of the above-mentioned preparation of 15mg, join in 120mL deionized water, ultrasonic disperse 10 minutes, sequentially add 36.2mg sodium citrate, 177.5mg hexamethylenetetramine, the salt of 177.5mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom washing with alcohol 5 times, obtains the presoma of CNT based composite metal oxidate material；Metal ion contained by the salt of described metal ion includes zinc, nickel, cobalt, ferrum, manganese；
5th step: by the 4th step products therefrom in inert atmosphere stove 400 DEG C calcine 2 hours, heating rate is 1 DEG C of min-1；Obtained product is exactly CNT metal oxides nanometer sheet sandwich.
Obtained CNT metal oxides nanometer sheet sandwich is the lithium ion battery negative material with high power capacity and excellent cycle performance.
Embodiment three
The present embodiment comprises the following steps:
The first step: weigh the CNT with hydroxyl of 4mg and put into flask, add 500mL acetone, ultrasonic disperse 10 minutes, be subsequently adding 8mg maleic anhydride, stirring reaction 10 hours at 25 DEG C, obtain the CNT of modified, and with washing with acetone 4 times；
Second step: weigh the CNT of 1.27g modified, joins in the anhydrous toluene solution of 300mL, and ultrasonic disperse 10 minutes is designated as A liquid；The azo-bis-isobutyl cyanide of 800mg is added inside the styrene of 38.2g, ultrasonic 10 minutes, is designated as B liquid；A liquid and B liquid being mixed, 70 DEG C of stirring reactions 10 hours, obtain the CNT that polystyrene layer is modified under nitrogen atmosphere, by washing with alcohol 5 times；
3rd step: weigh the CNT that 300mg polystyrene layer is modified, join in the concentrated sulphuric acid that 500mL concentration is 98%, ultrasonic disperse 10 minutes, 70 DEG C of oil bath stirring reactions 25 minutes, obtain the CNT that sulfonated polystyrene layer is modified；
4th step: weigh the sulfonated polystyrene modified carbon nano-tube of the above-mentioned preparation of 50mg, join in 400mL deionized water, ultrasonic disperse 10 minutes, sequentially add 72.5mg sodium citrate, 355mg hexamethylenetetramine, the salt of 750mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom washing with alcohol 5 times, obtains the presoma of CNT based composite metal oxidate material；Metal ion contained by the salt of described metal ion includes zinc, nickel, cobalt, ferrum, manganese；
5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcine 2 hours, heating rate is 1 DEG C of min-1；Obtained product is exactly CNT metal oxides nanometer sheet sandwich.
Obtained CNT metal oxides nanometer sheet sandwich is the lithium ion battery negative material with high power capacity and excellent cycle performance.
Embodiment four
The present embodiment comprises the following steps:
The first step: weigh the CNT with hydroxyl of 8mg and put into flask, add 1000mL acetone, ultrasonic disperse 20 minutes, be subsequently adding 16mg maleic anhydride, then stirring reaction 10 hours at 25 DEG C, obtains the CNT of modified, and with washing with acetone 4 times；
Second step: weigh the CNT of 2.54g modified, joins in the anhydrous toluene solution of 500mL, and ultrasonic disperse 10 minutes is designated as A liquid；The azo-bis-isobutyl cyanide of 1500mg is added inside the styrene of 76.4g, ultrasonic 10 minutes, is designated as B liquid；A liquid and B liquid being mixed, 75 DEG C of stirring reactions 6 hours, obtain the CNT that polystyrene layer is modified under nitrogen atmosphere, by washing with alcohol 5 times；
3rd step: weigh the CNT that 600mg polystyrene layer is modified, join in the concentrated sulphuric acid that 1000mL concentration is 98%, ultrasonic disperse 10 minutes, 70 DEG C of oil bath stirring reactions 25 minutes, obtain the CNT that sulfonated polystyrene layer is modified；
4th step: weigh the sulfonated polystyrene modified carbon nano-tube of the above-mentioned preparation of 100mg, join in 750mL deionized water, ultrasonic disperse 10 minutes, sequentially add 145mg sodium citrate, 750mg hexamethylenetetramine, the salt of 1500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom washing with alcohol 5 times, obtains the presoma of CNT based composite metal oxidate material；Metal ion contained by the salt of described metal ion includes zinc, nickel, cobalt, ferrum, manganese；
5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcine 2 hours, heating rate is 1 DEG C of min-1；Obtained product is exactly CNT metal oxides nanometer sheet sandwich.
Obtained CNT metal oxides nanometer sheet sandwich 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: weigh the CNT with hydroxyl of 40mg and put into flask, add 5000mL acetone, ultrasonic disperse 25 minutes, be subsequently adding 80mg maleic anhydride, then stirring reaction 10 hours at 25 DEG C, obtains the CNT of modified, and with washing with acetone 4 times；
Second step: weigh the CNT of 12.7g modified, joins in the anhydrous toluene solution of 3000mL, and ultrasonic disperse 10 minutes is designated as A liquid；The azo-bis-isobutyl cyanide of 8000mg is added inside the styrene of 382g, ultrasonic 10 minutes, is designated as B liquid；A liquid and B liquid being mixed, 75 DEG C of stirring reactions 10 hours, obtain the CNT that polystyrene layer is modified under nitrogen atmosphere, by washing with alcohol 5 times；
3rd step: weigh the CNT that 3000mg polystyrene layer is modified, join in the concentrated sulphuric acid that 5000mL concentration is 98%, ultrasonic disperse 10 minutes, 70 DEG C of oil bath stirring reactions 30 minutes, obtain the CNT that sulfonated polystyrene layer is modified；
4th step: weigh the sulfonated polystyrene modified carbon nano-tube of the above-mentioned preparation of 500mg, join in 4000mL deionized water, ultrasonic disperse 10 minutes, sequentially add 725mg sodium citrate, 3550mg hexamethylenetetramine, the salt of 7500mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom washing with alcohol 5 times, obtains the presoma of CNT based composite metal oxidate material；Metal ion contained by the salt of described metal ion includes zinc, nickel, cobalt, ferrum, manganese；
5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcine 2 hours, heating rate is 1 DEG C of min-1；Obtained product is exactly CNT metal oxides nanometer sheet sandwich.
Obtained CNT metal oxides nanometer sheet sandwich is the lithium ion battery negative material with high power capacity and excellent cycle performance.
Claims (2)
1. the preparation method of a metal oxide nano-sheet and CNT composite energy-storage material, it is characterised in that comprise the following steps:
The first step: weigh the CNT with hydroxyl of 0.4mg and put into flask, add 60mL acetone, ultrasonic disperse 5 minutes, be subsequently adding 0.8mg maleic anhydride, stirring reaction 10 hours at 25 DEG C, obtain the CNT of modified, and with washing with acetone 4 times；
Second step: weigh the CNT of 0.127g modified, joins in the anhydrous toluene solution of 30mL, and ultrasonic disperse 10 minutes is designated as A liquid；The azodiisobutyronitrile of 80mg is added inside the styrene of 3.82g, ultrasonic 10 minutes, is designated as B liquid；A liquid and B liquid being mixed, 70 DEG C of stirring reactions 7 hours, obtain the CNT that polystyrene layer is modified under nitrogen atmosphere, by washing with alcohol 5 times；
3rd step: weigh the CNT that 30mg polystyrene layer is modified, join in the concentrated sulphuric acid that 50mL concentration is 98%, ultrasonic disperse 10 minutes, 70 DEG C of oil bath stirring reactions 10 minutes, obtain the CNT that sulfonated polystyrene layer is modified；
4th step: weigh the CNT that the sulfonated polystyrene layer of the above-mentioned preparation of 5mg is modified, join in 40mL deionized water, ultrasonic disperse 10 minutes, sequentially add 7.2mg sodium citrate, 35.5mg hexamethylenetetramine, the salt of 75mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom washing with alcohol 5 times, obtains the presoma of metal oxide nano-sheet and CNT composite energy-storage material；Metal ion contained by the salt of described metal ion is nickel and cobalt；
5th step: by the 4th step products therefrom in inert atmosphere stove 400 DEG C calcine 2 hours, heating rate is 1 DEG C of min-1；Obtained product is exactly metal oxide nano-sheet and CNT composite energy-storage material.
2. the preparation method of a metal oxide nano-sheet and CNT composite energy-storage material, it is characterised in that comprise the following steps:
The first step: weigh the CNT with hydroxyl of 4mg and put into flask, add 500mL acetone, ultrasonic disperse 10 minutes, be subsequently adding 8mg maleic anhydride, stirring reaction 10 hours at 25 DEG C, obtain the CNT of modified, and with washing with acetone 4 times；
Second step: weigh the CNT of 1.27g modified, joins in the anhydrous toluene solution of 300mL, and ultrasonic disperse 10 minutes is designated as A liquid；The azodiisobutyronitrile of 800mg is added inside the styrene of 38.2g, ultrasonic 10 minutes, is designated as B liquid；A liquid and B liquid being mixed, 70 DEG C of stirring reactions 10 hours, obtain the CNT that polystyrene layer is modified under nitrogen atmosphere, by washing with alcohol 5 times；
3rd step: weigh the CNT that 300mg polystyrene layer is modified, join in the concentrated sulphuric acid that 500mL concentration is 98%, ultrasonic disperse 10 minutes, 70 DEG C of oil bath stirring reactions 25 minutes, obtain the CNT that sulfonated polystyrene layer is modified；
4th step: weigh the CNT that the sulfonated polystyrene layer of the above-mentioned preparation of 50mg is modified, join in 400mL deionized water, ultrasonic disperse 10 minutes, sequentially add 72.5mg sodium citrate, 355mg hexamethylenetetramine, the salt of 750mg metal ion, 90 DEG C of oil bath stirring reactions 6 hours, products therefrom washing with alcohol 5 times, obtains the presoma of metal oxide nano-sheet and CNT composite energy-storage material；Metal ion contained by the salt of described metal ion is nickel and cobalt；
5th step: by the 4th step products therefrom in inert atmosphere stove 450 DEG C calcine 2 hours, heating rate is 1 DEG C of min-1；Obtained product is exactly metal oxide nano-sheet and CNT composite energy-storage material.
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| CN107352528B (en) * | 2017-08-31 | 2020-01-14 | 清华大学 | Preparation method of metal oxide nanochain and nanochain |
| CN107622880B (en) * | 2017-10-26 | 2018-12-28 | 上海应用技术大学 | A kind of MnCoO2/ carbon nanotube electrode material and preparation method thereof |
| CN108529691B (en) * | 2018-04-24 | 2020-10-27 | 电子科技大学 | Flaky metal oxide and controllable synthesis method and application thereof |
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