CN103633304B - A kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials - Google Patents

A kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials Download PDF

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CN103633304B
CN103633304B CN201310650049.7A CN201310650049A CN103633304B CN 103633304 B CN103633304 B CN 103633304B CN 201310650049 A CN201310650049 A CN 201310650049A CN 103633304 B CN103633304 B CN 103633304B
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manganese
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CN103633304A (en
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杨尊先
郭太良
庞海东
严文焕
吕军
胡海龙
徐胜
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Fuzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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Abstract

The invention discloses a kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials, take carbon nano-tube as the nano composite material that nucleus growth is followed successively by carbon nano-tube, manganese oxide, amorphous carbon from inside to outside, i.e. the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) coaxial composite nano materials, wherein the oxide of manganese is MnO 2, Mn 3o 4and MnO, be abbreviated as MnO x.It is the oxide/carbon nanotube (C/MnO that core prepares one dimension amorphous carbon/manganese that the present invention uses with carbon nano-tube x/ CNTs) coaxial composite nano materials, its preparation technology is simple, and the low and prepared material of equipment requirement has bigger serface, high stability, high power capacity, high conductivity, has huge application potential in lithium secondary battery electrode negative material field.

Description

A kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials
Technical field
The invention belongs to new forms of energy field of nanometer material technology, be specifically related to a kind of oxide/carbon nanotube (C/MnO taking carbon nano-tube as core and prepare amorphous carbon/manganese x/ CNTs) method of coaxial composite nano materials.
Background technology
Along with the exhaustion day by day of the irreversible energy, the research of lithium ion battery serves more and more important effect at new energy field.And lithium ion battery negative material is as the important part of lithium battery, its research is also one of key factor determining performance of lithium ion battery.But traditional material with carbon element, its capacity is only 372mAh/g, can not meet the demand of contemporary society to the practical application of high-performance lithium battery far away.Therefore, recent domestic expert is devoted to study the lithium ion battery negative material with features such as high power capacity, high cycle performance, high stability, economic environmental protection always, and Mn-based material is owing to possessing higher theoretical lithium storage content, be acknowledged as one of lithium ion battery negative material of a kind of most potentiality, therefore, domestic and international lithium electricity expert and scholar's extensive concern is subject to.
But Mn-based material, in the process of repeated charge, due to its poorly conductive, occurs polarity effect, thus significantly reduces its cycle performance and stability in repeated charge process, and then limit its application in lithium electrical domain.In order to improve the conductivity of Mn-based material in lithium ion cell electrode application and cyclical stability further, people are seeking the method improving its conductivity always, improve the object of its cyclical stability to reach.Research shows to weaken polarity effect to a certain extent when Mn-based material is reduced to Nano grade, in addition, adds other materials formation composite material and also can improve its conductivity to a certain extent, and then improve its cyclical stability in Mn-based material.Provide a kind of manganese dioxide/carbon composite cathode material of lithium battery in patent CN1750298A: added by material with carbon element in permanganate solution, react under oil bath temperature, dry after filtration washing.Can be used for former lithium battery and lithium secondary battery negative electrode.Manganese bioxide material electronic conductance can be increased, improve the conductivity of manganese dioxide electrode at charge and discharge process, there is heavy-current discharge performance.In addition, Mn-based material also have cheaper starting materials, environmental protection friendly, without the need to other reagent and high-temperature process and the simple advantage of preparation technology.Provide the preparation method of a kind of lithium ion battery negative material manganese difluoride and Nano graphite compound in patent CN102034965A: it is respectively manganese source and fluorine source with manganese nitrate and ammonium fluoride solution, and to add Macrogol 2000 be surfactant; Under normal temperature condition, the two mix and blend is produced white precipitate; This is deposited in tube furnace and passes into argon gas so that manganese difluoride powder can be obtained through calcining when isolated air.Patent CN103022463A provides a kind of lithium ion battery manganese base composite negative pole material and preparation method thereof: adopt and make solid Mn containing manganese compound, Graphene 3o 4/ graphene composite negative pole, then the Mn made with lithium-containing compound and titanium-containing compound 3o 4/ graphene/lithium titanate nano composite anode material.Document PureAppl.Chem., Vol.80, No.11, pp.2327 – 2343, the researchs such as the Nanostructuredmanganeseoxidesandtheircompositeswithcarbo nnanotubesaselectrodematerials that 2008.doi:10.1351/pac200880112327 proposes, more than in research, although their method improves the conductivity of Mn-based material to a certain extent, but utilize manganese oxide and material with carbon element compound to be exactly utilize material with carbon element to be spread out by manganese oxide electrode active material simply in fact to their what is called, its dispersion and isolation effect more limited.In addition, owing to manganese oxide nano granule not disperseed completely and keeping apart, really effectively cannot play manganese oxide and material with carbon element synergy separately in electrode material, for the limited efficiency promoting the chemical properties such as the conductivity of manganese oxide material and charge-discharge performance.
In sum, major part document or patent in mention carbon dispersion Mn-based material, due to defect inherently, carbon dispersion and not exclusively coated, for conductivity and the corresponding chemical property lifting limited efficiency thereof of its composite material, also need the method exploring the coated Mn-based material of new carbon further.
Summary of the invention
The object of the invention is to that capacity directly for material with carbon element is low, the poorly conductive of Mn-based material, the problem of cycle performance difference, there is provided a kind of with carbon nano-tube be core to prepare the method for high-specific surface area, high conductivity, high power capacity, the flexible controlled one-dimensional composite nano pipe of material composition, the present invention take carbon nano-tube as the oxide/carbon nanotube (C/MnO that core prepares amorphous carbon/manganese x/ CNTs) coaxial composite nano materials, preparation technology is simple, equipment requirement is low, and prepared material has bigger serface, good conductivity, capacity advantages of higher, has huge application potential in lithium secondary battery electrode negative material field.
For achieving the above object, the present invention adopts following technical scheme:
Being the method that core prepares coaxial composite nano materials with carbon nano-tube, take carbon nano-tube as the coaxial composite nano materials that nucleus growth is followed successively by carbon nano-tube, manganese oxide, amorphous carbon from inside to outside, i.e. the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) coaxial composite nano materials.
Wherein the oxide of manganese is MnO 2, Mn 3o 4and MnO, be abbreviated as MnO x.
Described preparation method comprises the following steps:
(1) get also oil bath at a certain temperature, stirring in 0.4-0.8g carbon nanotube dispersed to inorganic acid mixed solution, carry out suction filtration, cleaning, drying subsequently, obtain the carbon nano-tube after acidification;
(2) carbon nano-tube after 0.3-0.7g acidification, 0.6-1.8g manganese acetate is taken, be distributed to respectively under ultrasound condition in 10-30ml, 50-90ml organic solution, ultrasonic process 1-3h, subsequently manganese acetate organic solution is dropwise instilled in carbon nano-tube organic solution, namely obtain the organic mixed solution of manganese acetate/carbon nano-tube;
(3) by after the organic mixed solution of above-mentioned manganese acetate/carbon nano-tube at room temperature strong stirring 3-9h, through suction filtration, cleaning, drying, and high-temperature process under being placed in tube furnace Buchholz protection, namely obtain the coaxial composite nano materials of oxide/carbon nanotube of manganese;
(4) taking 0.1-0.3g macromolecule organic dissolves in 10-30ml organic solution; the coaxial composite nano materials of above-mentioned manganese oxide/carbon nano-tube is distributed to wherein; strong stirring 1-3h; to be placed in baking oven at 60-80 DEG C after dry 12-72h; transfer in tube furnace and carry out high-temperature process under protective gas; be cooled to room temperature, namely obtain the coaxial composite nano materials of oxide/carbon nanotube of amorphous carbon/manganese.
Described inorganic acid mixed solution is hydrochloric acid and sulfuric acid or hydrochloric acid and nitric acid mixed solution, and its volume ratio is 1:3 or 3:1, and the oil bath processing time is 1-3h, temperature is 80-120 DEG C.
Organic solution described in step (2) (3) (4) is ethanol solution.
To be placed in tube furnace high-temperature process under Buchholz protection described in step (3), its processing time is 1-7h, and temperature is 300-700 DEG C, and protective gas is argon gas or nitrogen.
Described macromolecule organic is polyvinylpyrrolidone.
Carry out high-temperature process under protective gas in tube furnace described in step (4), protective gas is argon gas or nitrogen, and high-temperature process condition is 400-600 DEG C, and the time is 1-3h.
Beneficial effect of the present invention is: compared with prior art, and this invention is core with carbon nano-tube, prepares the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) coaxial composite nano tube, it not only has high-specific surface area but also have 1-dimention nano functional material structure feature.Meanwhile, with carbon manganese oxide particle effectively wrapped up and isolate, effectively improve its conductivity, and improve the structural stability of composite material, and then improve its lithium charge and discharge cycles stability.In addition, present invention process is easy, easy to operate, be easy to regulate, and is the effective ways preparing good lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is carbon nano-tube (CNTs) structural representation.Wherein, in Fig. 1, " 1 " is carbon nano-tube.
Fig. 2 is the oxide/carbon nanotube (MnO of manganese x/ CNTs) coaxial composite nano materials structural representation.Wherein, in Fig. 2, " 1 " is carbon nano-tube; Oxide (the MnO that " 2 " are manganese x).
Fig. 3 is the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) coaxial composite nano materials structural representation.Wherein, in Fig. 3, " 1 " is carbon nano-tube; Oxide (the MnO that " 2 " are manganese x); " 3 " are amorphous carbon.
Fig. 4 is the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) scanning electron microscope (SEM) photograph of coaxial composite nano materials.
Embodiment
The present invention aims to provide a kind of oxide/carbon nanotube (C/MnO taking carbon nano-tube as core and prepare amorphous carbon/manganese x/ CNTs) method of coaxial composite nano materials, existing by reference to the accompanying drawings and concrete execution mode a kind of oxide/carbon nanotube (C/MnO taking carbon nano-tube as core and prepare amorphous carbon/manganese is described x/ CNTs) concrete steps of method of coaxial composite nano materials are:
embodiment 1
It is in the hydrochloric acid of 1:3, sulfuric acid mixed solution that step 1) gets 0.5g carbon nanotube dispersed to volume ratio, 100 DEG C of oil bath process 1h, carry out suction filtration to it, after ethanol, deionized water clean successively subsequently, transfer to 50 DEG C of drying box inner drying 2h, namely obtain pure carbon nano-tube; Fig. 1 is carbon nano-tube (CNTs) structural representation;
Step 2) take 0.3g acidification after carbon nano-tube, be distributed in 20ml, 80ml ethanol solution respectively under 0.6g manganese acetate ultrasound condition, ultrasonic process 1h, subsequently manganese acetate organic solution is dropwise instilled in carbon nano-tube organic solution, namely obtain the organic mixed solution of manganese acetate/carbon nano-tube;
Step 3): after above-mentioned manganese acetate/carbon nano-tube organic mixed solution strong stirring 3h; carry out suction filtration, ethanol, deionized water clean successively, dry; be placed in high-temperature heat treatment 2h under 450 DEG C of tube furnace Buchholz protections, namely obtain the oxide/carbon nanotube (MnO of manganese x/ CNTs) composite nano materials; Fig. 2 is the oxide/carbon nanotube (MnO of manganese x/ CNTs) structural representation of coaxial composite nano materials, wherein 2 is the oxide (MnO of manganese x);
Step 4): take 0.1g polyvinylpyrrolidone and dissolve in 20ml ethanolic solution, by the oxide/carbon nanotube (MnO of manganese x/ CNTs) coaxial composite nano materials is distributed to wherein, strong stirring 2h, and to be placed in baking oven after 60 DEG C of dry 12h, to transfer to the lower 450 DEG C of high-temperature process of argon shield in tube furnace, be cooled to room temperature, namely obtain the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) coaxial composite nano materials; Fig. 3 is the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) structural representation of coaxial composite nano materials, wherein 3 is amorphous carbon; Fig. 4 is the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) scanning electron microscope (SEM) photograph of coaxial composite nano materials.
embodiment 2
It is in the hydrochloric acid of 1:3, nitric acid mixed solution that step 1) gets 0.5g carbon nanotube dispersed to volume ratio, 110 DEG C of oil bath process 1.5h, carry out suction filtration to it, after ethanol, deionized water clean successively subsequently, transfer to 60 DEG C of drying box inner drying 2h, namely obtain pure carbon nano-tube; Fig. 1 is carbon nano-tube (CNTs) structural representation;
Step 2) take 0.3g acidification after carbon nano-tube, be distributed in 20ml, 100ml ethanol solution respectively under 1.2g manganese acetate ultrasound condition, ultrasonic process 2h, subsequently manganese acetate organic solution is dropwise instilled in carbon nano-tube organic solution, namely obtain the organic mixed solution of manganese acetate/carbon nano-tube;
Step 3): after above-mentioned manganese acetate/carbon nano-tube organic mixed solution strong stirring 6h; carry out suction filtration; ethanol, deionized water clean successively, dry, be placed in high-temperature heat treatment 4h under 500 DEG C of tube furnace Buchholz protections, namely obtain the oxide/carbon nanotube (MnO of manganese x/ CNTs) coaxial composite nano materials; Fig. 2 is the oxide/carbon nanotube (MnO of manganese x/ CNTs) structural representation of coaxial composite nano materials, wherein 2 is the oxide (MnO of manganese x);
Step 4): take 0.15g polyvinylpyrrolidone and dissolve in 20ml ethanolic solution, by the oxide/carbon nanotube (MnO of manganese x/ CNTs) coaxial composite nano materials is distributed to wherein, strong stirring 3h, and to be placed in baking oven after 70 DEG C of dry 24h, to transfer to the lower 500 DEG C of high-temperature process of argon shield in tube furnace, be cooled to room temperature, namely obtain the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) coaxial composite nano materials; Fig. 3 is the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) structural representation of coaxial composite nano materials, wherein 3 is amorphous carbon; Fig. 4 is the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) scanning electron microscope (SEM) photograph of coaxial composite nano materials.
embodiment 3
It is in the sulfuric acid of 3:1, hydrochloric acid mixed solution that step 1) gets 0.5g carbon nanotube dispersed to volume ratio, 120 DEG C of oil bath process 2h, carry out suction filtration to it, after ethanol, deionized water clean successively subsequently, transfer to 50 DEG C of drying box inner drying 4h, namely obtain pure carbon nano-tube; Fig. 1 is carbon nano-tube (CNTs) structural representation, and wherein 1 is carbon nano-tube;
Step 2) take 0.3g acidification after carbon nano-tube, be distributed in 20ml, 90ml ethanol solution under 1.8g manganese acetate ultrasound condition, ultrasonic process 2h, subsequently manganese acetate organic solution is dropwise instilled in carbon nano-tube organic solution, namely obtain the organic mixed solution of manganese acetate/carbon nano-tube;
Step 3): after above-mentioned manganese acetate/carbon nano-tube organic mixed solution strong stirring 9h; carry out suction filtration; ethanol, deionized water clean successively, dry, to transfer in 550 DEG C of tube furnaces high-temperature heat treatment 5h under Buchholz protection, namely obtain the oxide/carbon nanotube (MnO of manganese x/ CNTs) coaxial composite nano materials; Fig. 2 is the oxide/carbon nanotube (MnO of manganese x/ CNTs) structural representation of coaxial composite nano materials, wherein 2 is manganese oxide (MnO x);
Step 4): take 0.2g polyvinylpyrrolidone and dissolve in 30ml ethanolic solution, by the oxide/carbon nanotube (MnO of manganese x/ CNTs) coaxial composite nano materials is distributed to wherein, strong stirring 3h, and to be placed in baking oven after 60 DEG C of dry 48h, to transfer to the lower 550 DEG C of high-temperature process of argon shield in tube furnace, be cooled to room temperature, namely obtain the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) coaxial composite nano materials; Fig. 3 is the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) structural representation of coaxial composite nano materials, wherein 3 is amorphous carbon; Fig. 4 is the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese x/ CNTs) scanning electron microscope (SEM) photograph of coaxial composite nano materials.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (5)

1. one kind is the method that core prepares coaxial composite nano materials with carbon nano-tube, it is characterized in that: take carbon nano-tube as core, growth is followed successively by carbon nano-tube, the oxide of manganese, the coaxial composite nano materials of amorphous carbon, i.e. the coaxial composite nano materials of oxide/carbon nanotube of amorphous carbon/manganese from inside to outside; Described preparation method comprises the following steps:
(1) get oil bath in 0.4-0.8g carbon nanotube dispersed to inorganic acid mixed solution, stirring, carry out suction filtration, cleaning, drying subsequently, obtain the carbon nano-tube after acidification;
(2) carbon nano-tube after 0.3-0.7g acidification, 0.6-1.8g manganese acetate is taken, be distributed to respectively under ultrasound condition in 10-30ml, 50-90ml organic solution, ultrasonic process 1-3h, subsequently manganese acetate organic solution is dropwise instilled in carbon nano-tube organic solution, namely obtain the organic mixed solution of manganese acetate/carbon nano-tube;
(3) by after the organic mixed solution of above-mentioned manganese acetate/carbon nano-tube at room temperature strong stirring 3-9h, through suction filtration, cleaning, drying, and high-temperature process under being placed in tube furnace Buchholz protection, namely obtain the coaxial composite nano materials of oxide/carbon nanotube of manganese;
(4) taking 0.1-0.3g macromolecule organic dissolves in 10-30ml organic solution, the coaxial composite nano tube of oxide/carbon nanotube of above-mentioned manganese is distributed to wherein, strong stirring 1-3h, to be placed in baking oven at 60-80 DEG C after dry 12-72h, transfer in tube furnace and carry out high-temperature process under protective gas, be cooled to room temperature, namely obtain the coaxial composite nano materials of oxide/carbon nanotube of amorphous carbon/manganese;
Described inorganic acid mixed solution is hydrochloric acid and sulfuric acid or hydrochloric acid and nitric acid mixed solution, and its volume ratio is 1:3 or 3:1, and the oil bath processing time is 1-3h, and temperature is 80-120 DEG C; Described macromolecule organic is polyvinylpyrrolidone.
2. according to claim 1 is the method that core prepares coaxial composite nano materials with carbon nano-tube, it is characterized in that: the oxide of described manganese is MnO 2, Mn 3o 4and MnO.
3. according to claim 1 is the method that core prepares coaxial composite nano materials with carbon nano-tube, it is characterized in that: the organic solution described in (2) (4) is ethanol solution.
4. according to claim 1 take carbon nano-tube as the method that core prepares coaxial composite nano materials; it is characterized in that: described in (3), be placed in high-temperature process under tube furnace Buchholz protection; its processing time is 1-7h, and temperature is 300-700 DEG C, and protective gas is argon gas or nitrogen.
5. according to claim 1 take carbon nano-tube as the method that core prepares coaxial composite nano materials; it is characterized in that: in the tube furnace described in (4), under protective gas, carry out high-temperature process; protective gas is argon gas or nitrogen, and high-temperature process condition is 400-600 DEG C, and the time is 1-3h.
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