CN103633304A - Method for preparing coaxially-composite nano material by using carbon nano tube as core - Google Patents
Method for preparing coaxially-composite nano material by using carbon nano tube as core Download PDFInfo
- Publication number
- CN103633304A CN103633304A CN201310650049.7A CN201310650049A CN103633304A CN 103633304 A CN103633304 A CN 103633304A CN 201310650049 A CN201310650049 A CN 201310650049A CN 103633304 A CN103633304 A CN 103633304A
- Authority
- CN
- China
- Prior art keywords
- tube
- manganese
- carbon
- carbon nano
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a coaxially-composite nano material by using a carbon nano tube as a core. The composite nano material using the carbon nano tube as the core comprises the carbon nano tube, manganese oxide, and amorphous carbon from the inside to the outside in sequence, that is to say, the amorphous carbon/manganese oxides/the carbon nano tube (C/MnOx/CNTs) coaxially compound the nano material, wherein the manganese oxides are MnO2, Mn3O4 and MnO, and are abbreviated to MnOx. The method uses the carbon nano tube as the core to prepare the one-dimensional amorphous carbon/manganese oxides/the carbon nano tube (C/MnOx/CNTs) coaxially-compounded nano material, so that the preparation technology is simple, the device requirement is low, and the prepared material is large in specific surface area, and high in stability, capacity and conductivity, and has huge application potentiality in the field of lithium secondary battery negative electrode materials.
Description
Technical field
The invention belongs to new forms of energy field of nanometer material technology, be specifically related to a kind ofly take carbon nano-tube and prepare the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese as core
x/ CNTs) method of coaxial composite nano materials.
Background technology
Be accompanied by the day by day exhausted of the irreversible energy, the research of lithium ion battery has been played 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 to determine one of key factor of 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 the lithium ion battery negative material that research has the features such as high power capacity, high cycle performance, high stability, economic environmental protection always, and manganese sill is owing to possessing higher theoretical lithium storage content, be acknowledged as one of lithium ion battery negative material of a kind of tool potentiality, therefore, be subject to domestic and international lithium electricity expert and scholar's extensive concern.
Yet in the process of repeated charge, due to its poorly conductive, there is polarity effect in repeated charge process, thereby greatly reduced its cycle performance and stability, and then limited its application in lithium electrical domain in manganese sill.In order further to improve conductivity and the cyclical stability of manganese sill in lithium ion cell electrode application, people are seeking to improve the method for its conductivity always, to reach the object that improves its cyclical stability.Research shows will weaken to a certain extent polarity effect when manganese sill is reduced to Nano grade, in addition, adds other materials to form composite material and also can improve to a certain extent its conductivity, and then improve its cyclical stability in manganese sill.The manganese dioxide/carbon composite cathode material that provides a kind of lithium battery to use in patent CN1750298A: material with carbon element is added in permanganate solution, under oil bath temperature, react, dry after filtration washing.Can be used for former lithium battery and lithium secondary battery negative electrode.Can increase manganese bioxide material electronic conductance, improve manganese dioxide electrode in the conductivity of charge and discharge process, there is heavy-current discharge performance.In addition, manganese sill also have raw material cheapness, environmental protection friendly, without other reagent and high-temperature process and the simple advantage of preparation technology.In patent CN102034965A, provide the preparation method of a kind of lithium ion battery negative material manganese difluoride and Nano graphite compound: it is respectively He Fu source, manganese 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 to white precipitate; This is deposited in and in tube furnace, passes into argon gas and through calcining, can obtain manganese difluoride powder to completely cut off in the situation of air.Patent CN103022463A provides a kind of lithium ion battery manganese base composite negative pole material and preparation method thereof: adopt containing manganese compound, Graphene and make solid Mn
3o
4/ Graphene composite negative pole material, then the Mn making with lithium-containing compound and titanium-containing compound
3o
4/ Graphene/lithium titanate nano composite anode material.Document Pure Appl. Chem., Vol. 80, No. 11, pp. 2327 – 2343, the researchs such as Nanostructured manganese oxides and their composites with carbon nanotubes as electrode materials that 2008.doi:10.1351/pac200880112327 proposes, more than in research, although their method has improved the conductivity of manganese sill to a certain extent, but to their what is called utilize manganese oxide and material with carbon element compound be exactly to utilize simply material with carbon element that manganese oxide electrode active material is spread out in fact, its dispersion and isolation effect are more limited.In addition, owing to manganese oxide nano granule not being disperseed completely and being kept apart, cannot really effectively bring into play manganese oxide and material with carbon element synergy separately in electrode material, limited for the effect that promotes the chemical properties such as the conductivity of manganese oxide material and charge-discharge performance.
In sum, the carbon of mentioning in most of document or patent disperses manganese sill, due to intrinsic defect itself, carbon disperses and is not exclusively coated, conductivity and corresponding chemical property lifting effect thereof for its composite material are limited, also need further to explore the method for the coated manganese sill of new carbon.
Summary of the invention
The object of the invention is to directly that capacity for material with carbon element is low, the poorly conductive of manganese sill, the poor problem of cycle performance, provide a kind of and take carbon nano-tube and prepare the method for high-specific surface area, high conductivity, high power capacity, the flexible controlled one-dimensional composite nano pipe of material composition as core, the present invention be take carbon nano-tube and is prepared the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese as core
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, in lithium secondary battery electrode negative material field, has huge application potential.
For achieving the above object, the present invention adopts following technical scheme:
The carbon nano-tube of take is prepared the method for coaxial composite nano materials as core, and the carbon nano-tube of take is followed successively by the coaxial composite nano materials of carbon nano-tube, manganese oxide, amorphous carbon, i.e. the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese from inside to outside as nucleus growth
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 0.4-0.8g carbon nanotube dispersed in inorganic acid mixed solution and oil bath at a certain temperature, stirring, carry out subsequently suction filtration, cleaning, dry, obtain the carbon nano-tube after acidification;
(2) take carbon nano-tube, the 0.6-1.8g manganese acetate after 0.3-0.7g acidification, under ultrasound condition, be distributed to respectively in 10-30ml, 50-90ml organic solution, ultrasonic processing 1-3h, subsequently manganese acetate organic solution is dropwise splashed in carbon nano-tube organic solution, obtain the organic mixed solution of manganese acetate/carbon nano-tube;
(3) the organic mixed solution of above-mentioned manganese acetate/carbon nano-tube at room temperature after strong stirring 3-9h, through suction filtration, cleaning, dry, and is placed in to high-temperature process under tube furnace Buchholz protection, obtains 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; being placed in baking oven is dried after 12-72h at 60-80 ℃; transfer to and in tube furnace, under protective gas, carry out high-temperature process; be cooled to room temperature, 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 that 1-3h, temperature are 80-120 ℃.
The described organic solution of step (2) (3) (4) is ethanol solution.
Step (3) is described is placed in tube furnace high-temperature process under Buchholz protection, and its processing time is 1-7h, and temperature is 300-700 ℃, and protective gas is argon gas or nitrogen.
Described macromolecule organic is polyvinylpyrrolidone.
In tube furnace described in step (4), under protective gas, carry out high-temperature process, protective gas is argon gas or nitrogen, and high-temperature process condition is 400-600 ℃, and the time is 1-3h.
Beneficial effect of the present invention is: compared with prior art, this invention be take carbon nano-tube as core, 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 design feature.Meanwhile, with carbon, manganese oxide particle effectively wrapped up and isolates to get up, effectively having improved its conductivity, and improved the structural stability of composite material, and then improved its lithium charge and discharge cycles stability.In addition, simple process of the present invention, easy to operate, be easy to regulate, be the effective ways of the good lithium ion battery negative material of preparation.
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; " 2 " are the oxide (MnO of 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; " 2 " are the oxide (MnO of 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 ofly take carbon nano-tube and prepares the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese as core
x/ CNTs) method of coaxial composite nano materials, existing by reference to the accompanying drawings and concrete execution mode illustrate and a kind ofly take carbon nano-tube and prepare the oxide/carbon nanotube (C/MnO of amorphous carbon/manganese as core
x/ CNTs) concrete steps of the method for coaxial composite nano materials are:
Step 1) is got in hydrochloric acid that 0.5g carbon nanotube dispersed is 1:3 to volume ratio, sulfuric acid mixed solution, 1h is processed in 100 ℃ of oil baths, subsequently it is carried out to suction filtration, after ethanol, deionized water clean successively, transfer to 50 ℃ of drying box inner drying 2h, obtain pure carbon nano-tube; Fig. 1 is carbon nano-tube (CNTs) structural representation;
Step 2) take under carbon nano-tube after 0.3g acidification, 0.6g manganese acetate ultrasound condition and be distributed to respectively in 20ml, 80ml ethanol solution, ultrasonic processing 1h, subsequently manganese acetate organic solution is dropwise splashed in carbon nano-tube organic solution, obtain the organic mixed solution of manganese acetate/carbon nano-tube;
Step 3): by after the organic mixed solution strong stirring of above-mentioned manganese acetate/carbon nano-tube 3h; carry out suction filtration, ethanol, deionized water clean successively, dry; be placed in high-temperature heat treatment 2h under 450 ℃ of tube furnace Buchholz protections, 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, the wherein 2 oxide (MnO that are 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, and strong stirring 2h is placed in after the interior 60 ℃ of dry 12h of baking oven, transfers to the lower 450 ℃ of high-temperature process of argon shield in tube furnace, is cooled to room temperature, obtains 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.
Step 1) is got in hydrochloric acid that 0.5g carbon nanotube dispersed is 1:3 to volume ratio, nitric acid mixed solution, 1.5h is processed in 110 ℃ of oil baths, subsequently it is carried out to suction filtration, after ethanol, deionized water clean successively, transfer to 60 ℃ of drying box inner drying 2h, obtain pure carbon nano-tube; Fig. 1 is carbon nano-tube (CNTs) structural representation;
Step 2) take under carbon nano-tube after 0.3g acidification, 1.2g manganese acetate ultrasound condition and be distributed to respectively in 20ml, 100ml ethanol solution, ultrasonic processing 2h, subsequently manganese acetate organic solution is dropwise splashed in carbon nano-tube organic solution, obtain the organic mixed solution of manganese acetate/carbon nano-tube;
Step 3): by after the organic mixed solution strong stirring of above-mentioned manganese acetate/carbon nano-tube 6h; carry out suction filtration; ethanol, deionized water clean successively, are dried, and are placed in high-temperature heat treatment 4h under 500 ℃ of tube furnace Buchholz protections, 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, the wherein 2 oxide (MnO that are 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, and strong stirring 3h is placed in after the interior 70 ℃ of dry 24h of baking oven, transfers to the lower 500 ℃ of high-temperature process of argon shield in tube furnace, is cooled to room temperature, obtains 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.
Step 1) is got in sulfuric acid that 0.5g carbon nanotube dispersed is 3:1 to volume ratio, hydrochloric acid mixed solution, 2h is processed in 120 ℃ of oil baths, subsequently it is carried out to suction filtration, after ethanol, deionized water clean successively, transfer to 50 ℃ of drying box inner drying 4h, obtain pure carbon nano-tube; Fig. 1 is carbon nano-tube (CNTs) structural representation, and wherein 1 is carbon nano-tube;
Step 2) take under carbon nano-tube after 0.3g acidification, 1.8g manganese acetate ultrasound condition and be distributed in 20ml, 90ml ethanol solution, ultrasonic processing 2h, subsequently manganese acetate organic solution is dropwise splashed in carbon nano-tube organic solution, obtain the organic mixed solution of manganese acetate/carbon nano-tube;
Step 3): by after the organic mixed solution strong stirring of above-mentioned manganese acetate/carbon nano-tube 9h; carry out suction filtration; ethanol, deionized water clean successively, dry, transfer in 550 ℃ of tube furnaces high-temperature heat treatment 5h under Buchholz protection, 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 0.2 g 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, and strong stirring 3h is placed in after the interior 60 ℃ of dry 48h of baking oven, transfers to the lower 550 ℃ of high-temperature process of argon shield in tube furnace, is cooled to room temperature, obtains 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 of doing 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 (8)
1. take carbon nano-tube and prepare the method for coaxial composite nano materials as core for one kind, it is characterized in that: take carbon nano-tube as core, growth is followed successively by the oxide of carbon nano-tube, manganese, the coaxial composite nano materials of amorphous carbon, the i.e. coaxial composite nano materials of oxide/carbon nanotube of amorphous carbon/manganese from inside to outside.
2. according to claim 1ly take carbon nano-tube and prepare the method for coaxial composite nano materials as core, it is characterized in that: the oxide of described manganese is MnO
2, Mn
3o
4and MnO.
3. according to claim 1ly take carbon nano-tube and prepare the method for coaxial composite nano materials as core, it is characterized in that: described preparation method comprises the following steps:
(1) get 0.4-0.8g carbon nanotube dispersed to oil bath in inorganic acid mixed solution, stirring, carry out subsequently suction filtration, cleaning, dry, obtain the carbon nano-tube after acidification;
(2) take carbon nano-tube, the 0.6-1.8g manganese acetate after 0.3-0.7g acidification, under ultrasound condition, be distributed to respectively in 10-30ml, 50-90ml organic solution, ultrasonic processing 1-3h, subsequently manganese acetate organic solution is dropwise splashed in carbon nano-tube organic solution, obtain the organic mixed solution of manganese acetate/carbon nano-tube;
(3) the organic mixed solution of above-mentioned manganese acetate/carbon nano-tube at room temperature after strong stirring 3-9h, through suction filtration, cleaning, dry, and is placed in to high-temperature process under tube furnace Buchholz protection, obtains 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 above-mentioned manganese oxide/carbon nano-tube is distributed to wherein; strong stirring 1-3h; being placed in baking oven is dried after 12-72h at 60-80 ℃; transfer to and in tube furnace, under protective gas, carry out high-temperature process; be cooled to room temperature, obtain the coaxial composite nano materials of oxide/carbon nanotube of amorphous carbon/manganese.
4. according to claim 3ly take carbon nano-tube and prepare the method for coaxial composite nano materials as core, it is characterized in that: described inorganic acid mixed solution is hydrochloric acid and sulfuric acid or hydrochloric acid and nitric acid mixed solution, its volume ratio is 1:3 or 3:1, and the oil bath processing time is that 1-3h, temperature are 80-120 ℃.
5. according to claim 3ly take carbon nano-tube and prepare the method for coaxial composite nano materials as core, it is characterized in that: the described organic solution of step (2) (3) (4) is ethanol solution.
6. according to claim 3ly take carbon nano-tube and prepare the method for coaxial composite nano materials as core; it is characterized in that: step (3) is described is placed in tube furnace high-temperature process under Buchholz protection; its processing time is 1-7h, and temperature is 300-700 ℃, and protective gas is argon gas or nitrogen.
7. according to claim 3ly take carbon nano-tube and prepare the method for coaxial composite nano materials as core, it is characterized in that: described macromolecule organic is polyvinylpyrrolidone.
8. according to claim 3ly take carbon nano-tube and prepare the method for coaxial composite nano materials as core; it is characterized in that: in the tube furnace described in step (4), under protective gas, carry out high-temperature process; protective gas is argon gas or nitrogen, and high-temperature process condition is 400-600 ℃, and the time is 1-3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310650049.7A CN103633304B (en) | 2013-12-06 | 2013-12-06 | A kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310650049.7A CN103633304B (en) | 2013-12-06 | 2013-12-06 | A kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103633304A true CN103633304A (en) | 2014-03-12 |
| CN103633304B CN103633304B (en) | 2016-01-27 |
Family
ID=50214096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310650049.7A Expired - Fee Related CN103633304B (en) | 2013-12-06 | 2013-12-06 | A kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103633304B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110350179A (en) * | 2019-07-17 | 2019-10-18 | 中国科学院福建物质结构研究所 | A kind of Fe2O3Nano carbon composite material and its preparation method and application |
| CN111348685A (en) * | 2020-03-02 | 2020-06-30 | 新奥石墨烯技术有限公司 | Graphene-based composite material and preparation method and application thereof |
| CN111554932A (en) * | 2020-05-11 | 2020-08-18 | 中科廊坊过程工程研究院 | High-performance composite positive electrode material, preparation method and application thereof |
| CN112599348A (en) * | 2020-12-09 | 2021-04-02 | 中国计量大学 | Preparation method of coaxial magnetic nano cable |
| CN113422051A (en) * | 2021-06-15 | 2021-09-21 | 杭州职业技术学院 | Carbon nanotube-string carbon hollow polyhedron nanosphere material and preparation and application thereof |
| CN113422011A (en) * | 2021-06-09 | 2021-09-21 | 杭州职业技术学院 | Carbon nanotube-in-tube @ manganese dioxide nanosheet composite material and preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173117A (en) * | 2007-10-19 | 2008-05-07 | 浙江大学 | Method for producing manganese dioxide coating carbon nano-tube core-shell type composite material |
| CN101284228A (en) * | 2008-05-23 | 2008-10-15 | 山东轻工业学院 | Preparation method of meso-porous titanium dioxide/activated carbon in-situ composite material |
| CN102646457A (en) * | 2012-04-28 | 2012-08-22 | 苏州新动能源材料有限公司 | Composite nanometer coaxial cable and manufacture method thereof |
| CN102983321A (en) * | 2012-12-24 | 2013-03-20 | 福州大学 | Carbon-coated MnOx nano energy storage material with one-dimensional core-shell structure and preparation method thereof |
| CN102983308A (en) * | 2012-12-17 | 2013-03-20 | 中国科学院上海硅酸盐研究所 | Carbon nanotube array/nickel oxide nanoparticle coaxial composite cathode material and preparation method thereof |
| CN103165862A (en) * | 2013-03-22 | 2013-06-19 | 浙江瓦力新能源科技有限公司 | High-performance negative material of lithium ion cell and preparation method of material |
-
2013
- 2013-12-06 CN CN201310650049.7A patent/CN103633304B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173117A (en) * | 2007-10-19 | 2008-05-07 | 浙江大学 | Method for producing manganese dioxide coating carbon nano-tube core-shell type composite material |
| CN101284228A (en) * | 2008-05-23 | 2008-10-15 | 山东轻工业学院 | Preparation method of meso-porous titanium dioxide/activated carbon in-situ composite material |
| CN102646457A (en) * | 2012-04-28 | 2012-08-22 | 苏州新动能源材料有限公司 | Composite nanometer coaxial cable and manufacture method thereof |
| CN102983308A (en) * | 2012-12-17 | 2013-03-20 | 中国科学院上海硅酸盐研究所 | Carbon nanotube array/nickel oxide nanoparticle coaxial composite cathode material and preparation method thereof |
| CN102983321A (en) * | 2012-12-24 | 2013-03-20 | 福州大学 | Carbon-coated MnOx nano energy storage material with one-dimensional core-shell structure and preparation method thereof |
| CN103165862A (en) * | 2013-03-22 | 2013-06-19 | 浙江瓦力新能源科技有限公司 | High-performance negative material of lithium ion cell and preparation method of material |
Non-Patent Citations (2)
| Title |
|---|
| PING WU等: "CNTs@SnO2@C Coaxial Nanocables with Highly Reversible Lithium Storage", 《THE JOURNAL OF CHEMICAL PHYSICS》 * |
| PING WU等: "CNTs@SnO2@C Coaxial Nanocables with Highly Reversible Lithium Storage", 《THE JOURNAL OF CHEMICAL PHYSICS》, vol. 114, 23 November 2010 (2010-11-23) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110350179A (en) * | 2019-07-17 | 2019-10-18 | 中国科学院福建物质结构研究所 | A kind of Fe2O3Nano carbon composite material and its preparation method and application |
| CN110350179B (en) * | 2019-07-17 | 2021-04-02 | 中国科学院福建物质结构研究所 | Fe2O3Nano carbon composite material and preparation method and application thereof |
| CN111348685A (en) * | 2020-03-02 | 2020-06-30 | 新奥石墨烯技术有限公司 | Graphene-based composite material and preparation method and application thereof |
| CN111348685B (en) * | 2020-03-02 | 2023-01-10 | 新奥集团股份有限公司 | Graphene-based composite material and preparation method and application thereof |
| CN111554932A (en) * | 2020-05-11 | 2020-08-18 | 中科廊坊过程工程研究院 | High-performance composite positive electrode material, preparation method and application thereof |
| CN111554932B (en) * | 2020-05-11 | 2021-12-28 | 廊坊绿色工业技术服务中心 | High-performance composite positive electrode material, preparation method and application thereof |
| CN112599348A (en) * | 2020-12-09 | 2021-04-02 | 中国计量大学 | Preparation method of coaxial magnetic nano cable |
| CN113422011A (en) * | 2021-06-09 | 2021-09-21 | 杭州职业技术学院 | Carbon nanotube-in-tube @ manganese dioxide nanosheet composite material and preparation and application thereof |
| CN113422051A (en) * | 2021-06-15 | 2021-09-21 | 杭州职业技术学院 | Carbon nanotube-string carbon hollow polyhedron nanosphere material and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103633304B (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20220376235A1 (en) | Composite Negative Electrode Material and Method for Preparing Composite Negative Electrode Material, Negative Electrode Plate of Lithium Ion Secondary Battery, and Lithium Ion Secondary Battery | |
| CN103633304B (en) | A kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials | |
| CN102683710B (en) | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof | |
| Xiao et al. | A facile PVP-assisted hydrothermal fabrication of Fe2O3/Graphene composite as high performance anode material for lithium ion batteries | |
| CN103682302B (en) | The method of the nano-electrode material of atomization drying synchronized compound porous graphene parcel | |
| CN103641174B (en) | Nano-sheet MnO 2-graphene composite material, its preparation method and ultracapacitor | |
| CN102983321B (en) | Carbon-coated MnOx nano energy storage material with one-dimensional core-shell structure and preparation method thereof | |
| CN103682296B (en) | A kind of preparation method of nanoscale lithium titanate material with high specific capacity | |
| Wang et al. | Aligned arrays of Na2Ti3O7 nanobelts and nanowires on carbon nanofiber as high‐rate and long‐cycling anodes for sodium‐ion hybrid capacitors | |
| Sun et al. | Fe2O3/CNTs composites as anode materials for lithium-ion batteries | |
| CN104528722A (en) | Two-dimensional layered titanium carbide nanosheet and preparation method and application thereof | |
| WO2015021789A1 (en) | High-magnification anode material of aqueous alkali metal electrochemical cell, and preparation method thereof | |
| CN105552369B (en) | The method for preparing three-dimensional porous niobic acid titanium oxide using template and its application in lithium ion battery | |
| CN104900861B (en) | A kind of lithium hydrogentitanate Li H Ti O material and preparation method thereof | |
| CN105161696B (en) | A kind of preparation method of graphene silicon nano composite material | |
| CN104852028A (en) | Lithium titanate/graphene composite cathode material for lithium ion battery | |
| CN109494360B (en) | Silicon monoxide composite material and preparation method thereof | |
| CN105098148A (en) | Preparation method of nanoscale silicon and silicon/carbon composite materials and application thereof | |
| CN104037393A (en) | Preparation method for tin/graphene/carbon fiber composite lithium battery cathode material | |
| CN104810515A (en) | Preparation method of doped Li4Ti5O12 anode material | |
| Zou et al. | Insights into the storage mechanism of novel mesoporous hollow TiO2-x/C nanofibers as a high-performance anode material for sodium-ion batteries | |
| CN102163711A (en) | Method for preparing lithium ion battery negative material by utilizing mesoporous carbon supported nano particles | |
| Feng et al. | Se/CNTs microspheres as improved performance for cathodes in Li-Se batteries | |
| Yao et al. | Embedding anatase TiO2 nanoparticles into holely carbon nanofibers for high-performance sodium/lithium ion batteries | |
| CN104752073A (en) | Preparation method of ferromanganese oxide/carbon composite materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160127 Termination date: 20191206 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |