CN104009215B - A kind of vanadium dioxide-graphene complex and the purposes as anode material for lithium-ion batteries thereof - Google Patents
A kind of vanadium dioxide-graphene complex and the purposes as anode material for lithium-ion batteries thereof Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
<b> the present invention relates to a kind of vanadium dioxide </b><bGreatT.Gre aT.GT-</b><bGrea tT.GreaT.GT graphene complex and is used as the purposes of anode material for lithium-ion batteries, this compound is made up of vanadium dioxide </b><bGreatT.Gre aT.GT-</b><bGrea tT.GreaT.GT Graphene composite band or sheet, and specific area is </b><bGreatT.Gre aT.GT20 ~ 800m
2/ g</b><bGreatT.Gr eaT.GT; In compound, vanadium dioxide is </b><bGreatT.Gre aT.GTVO
2(B) crystal of </b><bGreatT.Gre aT.GT, </b><bGreatT.Gre aT.GTC2/m</b><bG reatT.GreaT.GT structure; On composite band or sheet, Graphene is loose structure; when this compound is used as anode material for lithium-ion batteries, charge and discharge platform is </b><bGreatT.Gre aT.GT2.5V</b><bG reatT.GreaT.GT, specific capacity is at </b><bGreatT.Gre aT.GT1C</b><bGre atT.GreaT.GT and </b><bGreatT.Gre aT.GT200C</b><bG reatT.GreaT.GT, respectively higher than </b><bGreatT.Gre aT.GT400mAh/g</b>LEssT.LTssT. LTb> and </b><bGreatT.Gre aT.GT200mAh/g</b>LEssT.LTssT. LTb> after </b><bGreatT.Gre aT.GT1100</b><bG reatT.GreaT.GT repeated charge.Compound of the present invention has high conductivity, low dimension, super excellent high rate capability and good circulation stability, is ideal anode material for lithium-ion batteries; In addition, this compound can from the low raw material of price, high by repeatability, process is simple, few technique consuming time prepares, and is suitable for suitability for industrialized production.</b>
Description
Technical field
The present invention relates to a kind of vanadium dioxide-graphene complex that can be used as lithium ion electronics positive electrode newly.
Background technology
Along with the continuous breakthrough of electronics technology with in the world to the great attention of the energy, environmental protection, the novel secondary energy is just by leaps and bounds flourish in world wide.Wherein, lithium rechargeable battery with its excellent specific property, and becomes the first-selected power supply of the walkie electronic apparatus such as video camera, mobile phone, notebook computer, is also the potential power-supply system of ideal of future space technology and high-end energy-storage system.Lithium rechargeable battery is formed primarily of positive pole, negative pole, barrier film and electrolyte, and have high charge storage density, fast charging and discharging feature, good efficiency for charge-discharge and high cycle life and low cost the preparation of lithium rechargeable battery novel anode material be one of branch that this research direction is most active at present.
So far, anode material for lithium ion battery mainly contains cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2), LiMn2O4 (LiMn
2o
4), LiFePO4 (Li
xmPO
4, M=Fe, Mn, V, Ni, Co) etc.Although above-mentioned material all to a certain extent or the practical application of certain scale, but all there is specific capacity low (~ 160mAh/g), cycle life short (<1000 time), especially there is the shortcoming of chemical property difference when high power charging-discharging.Therefore, the research in this field now concentrates in high-energy, high power, long-life, the research of low cost new positive electrode, exploitation and technology of preparing.
In recent years, the oxide (V of transition metal alum
2o
5, VO
2, V
2o
3deng) studied for anode material for lithium-ion batteries, and show higher specific capacity (200-500mAh/g).But the oxide of alum generally has lower conductivity, in charge and discharge process, resistance is comparatively large, especially produces very large polarization during high power charging-discharging, finally causes cycle performance poor.And large polarization easily causes electrochemical dissolution, causes poor safety performance.In all oxides of alum, titanium dioxide alum (VO
2) (B) have unique edge atom and share (edge-sharingVO
6octahedra) structure, highly stable in charge and discharge process.But cycle performance and the limited preparation method of current titanium dioxide alum difference still limit its practical application.
Summary of the invention
The deficiency of cyclicity difference when technical problem to be solved by this invention is vanadium dioxide poorly conductive and the storage lithium overcoming prior art, provides a kind of and has high power capacity, high rate capability, excellent cycling performance, can be used as the vanadium dioxide-graphene complex of anode material for lithium-ion batteries.
For solving above technical problem, the present invention takes following technical scheme:
A kind of vanadium dioxide-graphene complex, this compound with the oxide of vanadium and graphene oxide for raw material, be prepared from by hydro thermal method or solvent-thermal method, its by length between 1 ~ 100 μm, width between 20nm ~ 100 μm, the thickness vanadium dioxide between 1 ~ 50nm-Graphene composite band or sheet form, the specific area of described compound is 20 ~ 800m
2/ g, in compound, vanadium dioxide is VO
2(B), the crystal of C2/m structure, crystal parameter is:
β=106.6 °, the Graphene on composite band or sheet is loose structure, when this compound is used as anode material for lithium-ion batteries, specific capacity at 1C and 200C, respectively higher than 400mAh/g and 200mAh/g after 1100 repeated charge.
According to a concrete and preferred aspect of the present invention, the preparation method of described compound comprises the steps:
(1), make the oxide of alum and graphene oxide in water and/or organic solvent, carry out hydro-thermal reaction and/or solvent thermal reaction in water heating kettle and at temperature 100 DEG C ~ 300 DEG C, wherein the oxide of alum and the mass ratio that feeds intake of graphene oxide are 0.8 ~ 10:1;
(2), adopt any one seasoning be selected from vacuumize, freeze drying and supercritical drying to carry out drying to the product system of front step, obtain solid product, be vanadium dioxide-graphene complex;
This preparation method also optionally comprises step (3): after step (1), before step (2), add reducing agent, make generation reduction reaction in the system after step (1).
Further: in step (1), the oxide of described alum can be the various oxides of the vanadium except vanadic oxide, such as can for be selected from titanium dioxide alum, three oxidation two alum, one oxidation two alum, four oxidation two alum in one or more.Wherein consider from cost angle, preferred vanadic oxide.
Further, the oxide (such as vanadic oxide) of alum and the mass ratio preferably 2 ~ 8:1 that feeds intake of graphene oxide, be more preferably 2 ~ 5:1, most preferably be 3 ~ 5:1.
Further, in step (1), described organic solvent is that any oxide to vanadium and graphene oxide have better dispersiveness and solvent material, includes but not limited to ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, methyl pyrrolidone etc.In these organic solvents, some has reproducibility, such as ethylene glycol.
Further, when the solvent adopted in step (1) does not have reproducibility, preferred implementation step (3); When the solvent adopted in step (1) has reproducibility, can select to implement or not implementation step (3).
According to the present invention, the reducing agent added in step (3) can for various reducing agents common in organic chemistry, include but not limited to hydrazine hydrate, sodium borohydride, potassium borohydride, hydrogen etc., the temperature of the reduction reaction of step (3) is generally 50 DEG C ~ 100 DEG C.The consumption of reducing agent is generally the 0.01-0.1wt% of products therefrom.
Preferably, the reaction of step (1) is made to carry out at temperature 150 DEG C ~ 250 DEG C.More preferably, carry out at temperature 150 DEG C ~ 200 DEG C.The setting of reaction temperature is by the design temperature that is directly heated in described scope or be warming up to design temperature stage by stage and at each stage constant temperature certain hour, these are not particularly limited.The size of reaction temperature to prepared composite band or sheet has certain influence.
According to the concrete and preferred aspect of the present invention one, described compound by length between 1 ~ 100 μm, width between 20nm-500nm, the thickness vanadium dioxide between 1 ~ 50nm-Graphene composite band forms, when this compound is used as anode material for lithium-ion batteries, charge and discharge platform is 2.5V, specific capacity at 1C and 200C, respectively higher than 400mAh/g and 200mAh/g after 1400 repeated charge.
According to the present invention, step (2) preferably adopts freeze drying or supercritical drying.Freeze-dried Medium and supercritical medium can be all water, ethanol, propyl alcohol, isopropyl alcohol, carbon dioxide etc.
The invention still further relates to the purposes that a kind of above-mentioned vanadium dioxide-graphene complex is used as anode material for lithium-ion batteries.
According to a concrete aspect, take following steps to prepare lithium ion cell positive work electrode:
(1), by titanium dioxide alum-graphene complex, binder PVDF, acetylene black mix in the ratio of 100:10:1, spread upon uniformly after being modulated into paste with N-2 methyl-pyrrolidon on aluminium foil or stainless steel substrates;
(2), dry 8-15 hour at 120 DEG C in vacuum drying oven;
(3), the aluminium foil or stainless steel that scribble titanium dioxide alum-graphene complex are cut into disk and make work electrode.
As follows to the method for testing of the chemical property of electrode material:
(1), simulated battery adopts is button CR2032 type system, and be wherein metal lithium sheet to electrode, the assembling of simulated battery completes in German M. Braun company Unilab type glove box.
(2), the reversible capacity of electrode material, coulombic efficiency, cycle performance, experiment adopt constant current charge-discharge carry out test analysis.Discharge and recharge system is: voltage range: 1.5-3.5V (vs.Li
+/ Li); Cycle-index is generally 1-3000 time.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
(1) the present invention's alum oxidation thing of adopting price low and graphene oxide are raw material; (2) the titanium dioxide alum-Graphene composite band utilizing simple hydro thermal method or solvent-thermal method to prepare there is low dimension and titanium dioxide alum-Graphene composite sheet, their the favourable lithium ion of low dimension quick embedding wherein and deviating from, and in compound, vanadium dioxide is VO
2(B), the crystal of C2/m structure, highly stable in charge and discharge process; (3), when gained titanium dioxide alum-graphene complex is used as anode material for lithium-ion batteries, at about 2.5V, there is a good charge and discharge platform; (4) gained titanium dioxide alum-graphene complex is as specific capacity during anode material for lithium-ion batteries large (specific capacity is greater than 400mAh/g when 1C discharge and recharge); (5) when gained titanium dioxide alum-graphene complex is used as anode material for lithium-ion batteries, there is excellent high rate capability (when 200C discharge and recharge, capacity is greater than 200mAh/g); (6) when gained titanium dioxide alum-graphene complex is used as anode material for lithium-ion batteries, there is super good cycle performance (at 1C and 200C, respectively higher than 400mAh/g and 200mAh/g after 1400 repeated charge).
To sum up, compound of the present invention has high conductivity, there is super excellent high rate capability and good circulation stability, be ideal anode material for lithium-ion batteries, the fields such as various portable electric appts, electric automobile and Aero-Space can be widely used in; In addition, this compound can from the low raw material of price, high by repeatability, process is simple, few technique consuming time prepares, and is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the morphology characterization result of the titanium dioxide alum-Graphene composite band of embodiment 1, wherein (a) and (b) scanning electron microscope (SEM) photograph (SEM) that is different multiplying, confirm that its average length is between 1 ~ 100 μm, width is between 20-500nm; C () confirms above-mentioned width and characteristic transparent, ultra-thin under Electronic Speculum thereof for transmission electron microscope picture (TEM), a nearly step; D () high-resolution-ration transmission electric-lens figure (HRTEM), confirms its VO
2(B) in mono-crystalline structures and composite sheet, Graphene is loose structure; E () and (f) atomic force microscope (AFM) and analysis thereof, confirm that the thickness of titanium dioxide alum band is about 10nm.Specific surface area analysis is relevant with drying means, is 20 ~ 800m
2/ g (BET test);
Fig. 2 is the structural characterization result of the titanium dioxide alum-Graphene composite band of embodiment 1, and wherein (a) X-ray confirms that the titanium dioxide alum in gained titanium dioxide alum-Graphene composite band is the crystal of C2/m structure, and crystal parameter is:
(β=106.6o) (JCPDSNo.31-1438); Titanium dioxide alum (B) the crystal structure figure of crystal face projection that b () prolongs (010);
Fig. 3 is the chemical property result of vanadium dioxide-graphene complex of the present invention: the constant current charge-discharge curve of electrode under 1C and 20C multiplying power that the compound of (a) embodiment 1 is made; The b cycle performance of electrode under 1C multiplying power (30 circulations) that the compound of () embodiment 1, embodiment 3 and comparative example 1 is made; The c cycle performance of electrode under 200C multiplying power (1400 circulations) that the compound of () embodiment 1 and embodiment 3 is made, the cycle performance of electrode under 200C multiplying power (3000 circulations) that the compound of (d) embodiment 1 is made;
Fig. 4 is the titanium dioxide alum-Graphene composite band of embodiment 4 and the morphology characterization result of sheet, and wherein (a) is scanning electron microscope (SEM) photograph (SEM), and confirm that the average length of composite sheet is between 1 ~ 100 μm, width is between 1 ~ 100 μm; B () is high-resolution-ration transmission electric-lens figure (HRTEM), a nearly step confirms that its titanium dioxide alum sheet is that mono-crystalline structures and composite sheet upper part are covered by Graphene; C () electron energy loss spectroscopy (EELS) (EDX), confirms that the atomic ratio of V and O in titanium dioxide alum is 2:1.
Fig. 5 is the appearance structure characterization result of the titanium dioxide alum-Graphene composite band of embodiment 6, and wherein (a) is scanning electron microscope (SEM) photograph (SEM), and confirm that the average length of composite sheet is between 1 ~ 10 μm, width is between 200 ~ 800nm; B () electronic diffraction spectrogram, a nearly step confirms that its titanium dioxide alum band is mono-crystalline structures.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following examples.
Embodiment 1
A kind of vanadium dioxide-graphene complex, it prepares as follows:
(1), by vanadic oxide 1800mg and graphene oxide 400mg (the two mass ratio is 4.5:1) mix, be distributed in 200mL water, be then sealed in water heating kettle, at 180 ± 5 DEG C, react 12 hours;
(2), in the system through step (1) add 2-10mL (35wt%) hydrazine hydrate, at 80 ± 2 DEG C, carry out reduction reaction, react 5 hours;
(3), at-40 DEG C of temperature freeze drying obtain solid product, be vanadium dioxide-graphene complex.
Characterize the pattern etc. of gained vanadium dioxide-graphene complex, result is see Fig. 1.Vanadium dioxide-graphene complex is by average length between 1 ~ 100 μm, and width is at 20 ~ 500nm, and the vanadium dioxide of thickness between 1 ~ 50nm-Graphene composite band composition, specific area is 420m
2/ g.
Characterize the structure of vanadium dioxide-graphene complex, result, see Fig. 2, shows in compound, and titanium dioxide alum is VO
2(B), the crystal of C2/m structure, crystal parameter is:
(β=106.6o) (JCPDSNo.31-1438); In composite band, Graphene closely covers on titanium dioxide alum, is loose structure.
Vanadium dioxide-graphene complex is made work electrode according to method provided by the present invention and carries out corresponding electrochemical property test, result is as follows: coulombic efficiency is more than 90% first, and when 1C discharge and recharge, stabilization ratio capacity is 441mAh/g; When 20C discharge and recharge, stabilization ratio capacity is 328mAh/g; When 200C discharge and recharge, stabilization ratio capacity is 210mAh/g; Under above-mentioned multiplying power during discharge and recharge, after 1400 repeated charge, capacity all can keep more than 90% of initial capacity.
Embodiment 2
Embodiment 2 provides a kind of vanadium dioxide-graphene complex, its preparation method substantially with embodiment 1, unlike, the mass ratio that feeds intake of its material oxidation vanadium and graphene oxide is 3:1.Vanadium dioxide-graphene complex is made work electrode according to method provided by the present invention and carries out corresponding electrochemical property test, result is as follows: coulombic efficiency is more than 90% first, and when 1C discharge and recharge, stabilization ratio capacity is 390mAh/g; When 20C discharge and recharge, stabilization ratio capacity is 295mAh/g; When 200C discharge and recharge, stabilization ratio capacity is 204mAh/g; Under above-mentioned multiplying power during discharge and recharge, after 1400 repeated charge, capacity all can keep more than 90% of initial capacity.
Embodiment 3
This example provides a kind of vanadium dioxide-graphene complex, its preparation method substantially with embodiment 1, unlike, the mass ratio that feeds intake of its material oxidation vanadium and graphene oxide is 2:1.
Vanadium dioxide-graphene complex is made work electrode according to method provided by the present invention and carries out corresponding electric performance test, result is as follows: coulombic efficiency is 92% first, and when 1C discharge and recharge, stabilization ratio capacity is 370mAh/g; When 20C discharge and recharge, stabilization ratio capacity is 284mAh/g; When 200C discharge and recharge, stabilization ratio capacity is 194mAh/g; And under above-mentioned multiplying power during discharge and recharge, after 1400 repeated charge, capacity all can keep more than 92% of initial capacity.
Embodiment 4
This example provides a kind of vanadium dioxide-graphene complex, and it prepares as follows:
(1), by vanadic oxide 1800mg and graphene oxide 400g (the two mass ratio is 4.5:1) mix, be distributed in 200mL water, be then sealed in water heating kettle, at 210 ± 5 DEG C, react 20 hours;
(2), in the system through step (1) add 2-10mL (35wt%) hydrazine hydrate, at 90 ± 2 DEG C, carry out reduction reaction, react 5 hours;
(3), supercritical drying obtains solid product, is vanadium dioxide-graphene complex.
Characterize the pattern etc. of gained vanadium dioxide-graphene complex, result is see Fig. 4.Vanadium dioxide-graphene complex forms with sheet jointly by being with, wherein with size with embodiment 1, the average length of sheet is between 1 ~ 100 μm, and width is at 1 ~ 100 μm, and thickness is between 1 ~ 50nm, and specific area is 620m
2/ g.
Characterize the structure of vanadium dioxide-graphene film, result, see Fig. 4, shows in composite sheet, and the atomic ratio of V and O in titanium dioxide alum is 2:1, and crystal is with VO in embodiment 1
2(B) ribbon, the crystal of C2/m structure.
Embodiment 5
This example provides a kind of vanadium dioxide-graphene complex, its preparation method substantially with embodiment 1, unlike, its raw material vanadic oxide vanadium trioxide replaces.Vanadium dioxide-graphene complex is made work electrode according to method provided by the present invention and carries out corresponding electrochemical property test, result is as follows: coulombic efficiency is more than 91% first, and when 1C discharge and recharge, stabilization ratio capacity is 420mAh/g; When 20C discharge and recharge, stabilization ratio capacity is 305mAh/g; When 200C discharge and recharge, stabilization ratio capacity is 290mAh/g; Under above-mentioned multiplying power during discharge and recharge, after 1400 repeated charge, capacity all can keep more than 90% of initial capacity.
Embodiment 6
A kind of vanadium dioxide-graphene complex, it prepares as follows:
(1), by vanadic oxide 1800mg and graphene oxide 400mg (the two mass ratio is 4.5:1) mix, be distributed in 200mL ethylene glycol, be then sealed in water heating kettle, at 180 ± 2 DEG C, react 20 hours;
(2), at-40 DEG C of temperature freeze drying obtain solid product, be vanadium dioxide-graphene complex.
Characterize the pattern etc. of gained vanadium dioxide-graphene complex, result is see Fig. 5.Vanadium dioxide-graphene complex is by average length between 1 ~ 10 μm, and width is at 200 ~ 800nm, and the vanadium dioxide of thickness between 1 ~ 50nm-Graphene composite band composition, specific area is 610m
2/ g.
Characterize the structure of vanadium dioxide-graphene complex, result, see Fig. 5, shows in compound, and titanium dioxide alum is VO
2(B), the mono-crystalline structures of C2/m structure, with embodiment 1 gained composite band.
Comparative example 1
This example provides a kind of vanadium dioxide-graphene complex, its preparation method substantially with embodiment 1, unlike, the mass ratio that feeds intake of its material oxidation vanadium and graphene oxide is 9.5:1.After making electrode slice, record its first coulombic efficiency be 85%, when 1C discharge and recharge, specific capacity is 580mAh/g first; When 20C discharge and recharge, stabilization ratio capacity is 320mAh/g; When 200C discharge and recharge, stabilization ratio capacity is less than 100mAh/g; And under above-mentioned multiplying power during discharge and recharge, after 30 repeated charge, capacity is all lower than 80% of initial capacity.
Deficiency when the present invention is directed to titanium dioxide alum poorly conductive and store up lithium existing for cycle performance difference, by the control of preparation method and preparation condition, finally obtain the power lithium-ion battery positive electrode with ultra-high capacity, ultra-high magnifications performance and super good cycle performance.This has very important significance to the development of promotion high power lithium ion cell and solution energy shortage etc.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1.
a kind of vanadium dioxide-graphene complex, it is characterized in that: this compound with the oxide of vanadium and graphene oxide for raw material, be prepared from by hydro thermal method or solvent-thermal method, its by length between 1 ~ 100 μm, width between 20nm ~ 100 μm, the thickness vanadium dioxide between 1 ~ 50nm-Graphene composite band or sheet form, the specific area of described compound is 20 ~ 800m 2 / g; In compound, vanadium dioxide is VO 2 (B), the crystal of C2/m structure, crystal parameter is:
a=12.03,
b=3.693,
c=6.42,
β=106.6
o ; On composite band or sheet, Graphene is loose structure; This compound be used as anode material for lithium-ion batteries time, charge and discharge platform is 2.5V, specific capacity at 1C and 200C, respectively higher than 400mAh/g and 200mAh/g after 1400 repeated charge.
2.
vanadium dioxide-graphene complex according to claim 1, is characterized in that: the preparation method of described compound comprises the steps:
(1), making the oxide of alum mix with graphene oxide is distributed in water and/or organic solvent, then be sealed in water heating kettle, at temperature 100 DEG C ~ 300 DEG C, carry out hydro-thermal reaction and/or solvent thermal reaction, wherein the oxide of alum and the mass ratio that feeds intake of graphene oxide are 0.8 ~ 10:1;
(2), adopt any one seasoning be selected from vacuumize, freeze drying and supercritical drying to carry out drying to the product system of front step, obtain solid product, be described vanadium dioxide-graphene complex;
described preparation method also optionally comprises step (3): after step (1), before step (2), add reducing agent, make generation reduction reaction in the system after step (1).
3.
vanadium dioxide-graphene complex according to claim 2, is characterized in that: in step (1), the oxide of described alum be selected from vanadium pentoxide, three oxidation two alum, one oxidation two alum, four oxidation two alum in one or more.
4.
vanadium dioxide-graphene complex according to Claims 2 or 3, is characterized in that: the oxide of described alum and the mass ratio that feeds intake of graphene oxide are 3 ~ 5:1.
5.
vanadium dioxide-graphene complex according to claim 2, is characterized in that: in step (1), and described organic solvent is one or more the combination in ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, methyl pyrrolidone.
6.
vanadium dioxide-graphene complex according to claim 2 or 5, is characterized in that: when the solvent adopted in step (1) does not have reproducibility, implement described step (3); When the solvent adopted in step (1) has reproducibility, implement or do not implement described step (3).
7.
vanadium dioxide-graphene complex according to claim 2, is characterized in that: described reducing agent be selected from hydrazine hydrate, sodium borohydride, potassium borohydride, hydrogen one or more, the temperature of the reduction reaction of step (3) is 50 DEG C ~ 100 DEG C.
8.
vanadium dioxide-graphene complex according to claim 2, is characterized in that: the reaction of step (1) is carried out at temperature 150 DEG C ~ 250 DEG C.
9.
vanadium dioxide-graphene complex according to claim 1 and 2, it is characterized in that: described compound by length between 1 ~ 100 μm, width between 20nm-500nm, the thickness vanadium dioxide between 1 ~ 50nm-Graphene composite band forms, when this compound is used as anode material for lithium-ion batteries, charge and discharge platform is 2.5V, specific capacity at 1C and 200C, respectively higher than 400mAh/g and 200mAh/g after 1400 repeated charge.
10.
a kind of vanadium dioxide-graphene complex any one of claim 1 ~ 9 as described in claim is used as the purposes of anode material for lithium-ion batteries.
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| CN110627055A (en) * | 2019-10-25 | 2019-12-31 | 天津大学 | Vanadium dioxide and graphene composite film structure and preparation method and application thereof |
| CN112018348A (en) * | 2020-08-10 | 2020-12-01 | 五邑大学 | VO (volatile organic compound)2/MXene composite material and preparation method and application thereof |
| CN112242512A (en) * | 2020-10-16 | 2021-01-19 | 成都先进金属材料产业技术研究院有限公司 | Preparation method of vanadium dioxide and graphene oxide composite material |
| CN113066973A (en) * | 2021-03-15 | 2021-07-02 | 武汉理工大学 | Self-supporting vanadium graphene interface zinc storage material and preparation method and application thereof |
| CN113087019B (en) * | 2021-05-12 | 2022-09-13 | 郑州大学 | Preparation of ferromagnetic VO by supercritical fluid technology 2 Preparation method of (1) |
| CN113511679A (en) * | 2021-06-30 | 2021-10-19 | 南京邮电大学 | Method for preparing carbon-coated vanadium dioxide positive electrode material |
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| CN102208631A (en) * | 2011-04-27 | 2011-10-05 | 北京化工大学 | Ultra-long single crystal V2O5 nano wire/graphene anode material and preparation method |
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| CN101900607A (en) * | 2010-06-24 | 2010-12-01 | 电子科技大学 | Vanadium oxide film for infrared detector and manufacturing method thereof |
| CN102208631A (en) * | 2011-04-27 | 2011-10-05 | 北京化工大学 | Ultra-long single crystal V2O5 nano wire/graphene anode material and preparation method |
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