CN104009215A - Vanadium dioxide-graphene compound and its use as lithium ion battery positive electrode material - Google Patents
Vanadium dioxide-graphene compound and its use as lithium ion battery positive electrode material 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
- 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
- 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
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- 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
Abstract
The invention relates to a vanadium dioxide-graphene compound and its use as a lithium ion battery positive electrode material. The compound is composed of vanadium dioxide-graphene compound bands or sheets, and the specific surface area of the compound is 20-800m<2>/g; vanadium dioxide in the compound is VO2(B),C2/m structure crystals; graphene on the compound bands or sheets has a porous structure; and when the compound is used as the lithium ion battery positive electrode material, the charge and discharge platform is 2.5V, and the specific capacity of a battery using the positive electrode material is higher than 400mAh/g and 200mAh/g after the battery is repeated charged and discharged at 1C and 200C 110 times. The compound has the advantages of high conductivity, low dimensions, super excellent high-magnification performances and good cycle stability, is an ideal lithium ion battery positive electrode material; and additionally, the compound is prepared through a technology having the advantages of high repeatability, simple process and less time consumption by using cheap raw materials, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of new vanadium dioxide-graphene complex that can be used as lithium ion electronics positive electrode.
Background technology
Along with the continuous breakthrough of electronics technology and the great attention to the energy, environmental protection in the world, the novel secondary energy is just by leaps and bounds flourish in world wide.Wherein, lithium rechargeable battery is 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 mainly consists 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 cheaply lithium rechargeable battery with the preparation of 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 when high power charging-discharging, have the poor shortcoming of chemical property.Therefore, the research in this field now concentrates in research, exploitation and the technology of preparing of high-energy, high power, long-life, low cost new positive electrode.
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, and in charge and discharge process, resistance is larger, especially produce very large polarization during high power charging-discharging, finally cause cycle performance poor.And large polarization easily causes electrolyte to decompose, cause poor safety performance.In all oxides of alum, titanium dioxide alum (VO
2) (B) there is unique edge atom and share (edge-sharing VO
6octahedra) structure, highly stable in charge and discharge process.But the cycle performance that current titanium dioxide alum is poor and limited preparation method still limit its practical application.
Summary of the invention
Technical problem to be solved by this invention is to overcome the vanadium dioxide poorly conductive of prior art and the storage poor deficiency of cyclicity during lithium, and a kind of vanadium dioxide-graphene complex that has high power capacity, high rate capability, excellent cycling performance, can be used as anode material for lithium-ion batteries is provided.
For solving above technical problem, the present invention takes following technical scheme:
A kind of vanadium dioxide-graphene complex, it is raw material that this compound be take oxide and the graphene oxide of vanadium, by hydro thermal method or solvent-thermal method, be prepared from, its by length between 1 ~ 100 μ m, width between the μ m of 20nm ~ 100, vanadium dioxide-Graphene composite band or the sheet of thickness between 1 ~ 50nm 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, this compound is when the anode material for lithium-ion batteries, specific capacity is at 1C and 200C, after 1100 repeated charge respectively higher than 400mAh/g and 200mAh/g.
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, in water heating kettle and at 100 ℃ ~ 300 ℃ of temperature, carry out hydro-thermal reaction and/or solvent thermal reaction, wherein the mass ratio that feeds intake of the oxide of alum and graphene oxide is 0.8 ~ 10:1;
(2), adopt any seasoning be selected from vacuumize, freeze drying and supercritical drying to be dried the product system of front step, obtain solid product, be vanadium dioxide-graphene complex;
This preparation method also optionally comprises step (3): step (1) afterwards, step (2) before, in the system after step (1), add reducing agent, make to occur reduction reaction.
Further: in step (1), the oxide of described alum can be the various oxides of the vanadium except vanadic oxide, for example can be for being selected from one or more in two alum of titanium dioxide alum, three oxidation two alum, oxidation two alum, four oxidations.Wherein from cost angle, consider, preferably vanadic oxide.
Further, the preferably 2 ~ 8:1 of mass ratio that feeds intake of the oxide of alum (for example vanadic oxide) and graphene oxide, more preferably 2 ~ 5:1, most preferably is 3 ~ 5:1.
Further, in step (1), described organic solvent, for arbitrarily the oxide of vanadium and graphene oxide are had to 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, for example ethylene glycol.
Further, when the solvent adopting in step (1) does not have reproducibility, preferred implementation step (3); When the solvent adopting in step (1) has reproducibility, can select to implement or implementation step (3) not.
According to the present invention, the reducing agent adding in step (3) can include but not limited to hydrazine hydrate, sodium borohydride, potassium borohydride, hydrogen etc. for various reducing agents common in organic chemistry, and the temperature of the reduction reaction of step (3) is generally 50 ℃ ~ 100 ℃.The consumption of reducing agent is generally the 0.01-0.1 wt% of products therefrom.
Preferably, the reaction that makes step (1) is carried out at 150 ℃ ~ 250 ℃ of temperature.More preferably, at 150 ℃ ~ 200 ℃ of temperature, carry out.The setting of reaction temperature can be by being directly heated to the design temperature in described scope or being warming up to stage by stage design temperature and at each stage constant temperature certain hour, these are not particularly limited.Reaction temperature has certain influence to the size of prepared composite band or sheet.
A concrete and preferred aspect according to the present invention, described compound by length between 1 ~ 100 μ m, width between 20nm-500nm, the vanadium dioxide-Graphene composite band of thickness between 1 ~ 50nm form, when this compound is used as anode material for lithium-ion batteries, charge and discharge platform is 2.5V, specific capacity is at 1C and 200C, after 1400 repeated charge respectively higher than 400Ah/g and 200mAh/g.
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 a kind of above-mentioned vanadium dioxide-graphene complex as the purposes of anode material for lithium-ion batteries.
According to a concrete aspect, take following steps to prepare lithium ion cell positive work electrode:
(1), titanium dioxide alum-graphene complex, binder PVDF, acetylene black are mixed in the ratio of 100:10:1, spread upon uniformly on aluminium foil or stainless steel substrates after being modulated into paste with N-2 methyl-pyrrolidones;
(2), in vacuum drying oven, at 120 ℃, be dried 8-15 hour;
(3), by scribbling the aluminium foil of titanium dioxide alum-graphene complex or stainless steel, cut into disk and make work electrode.
Method of testing to the chemical property of electrode material is as follows:
(1), simulated battery adopts is button CR2032 type system, to electrode, is wherein metal lithium sheet, the assembling of simulated battery completes in the German M. Braun Unilab of company type glove box.
(2), the reversible capacity of electrode material, coulombic efficiency, cycle performance, experiment adopts constant current charge-discharge to carry out test analysis.The system of discharging and recharging 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) to adopt alum oxidation thing and graphene oxide that price is low be raw material in the present invention; (2) utilize simple hydro thermal method or solvent-thermal method to prepare to have titanium dioxide alum-Graphene composite band and titanium dioxide alum-Graphene composite sheet of low dimension, their low dimension is favourable with quick embedding therein of lithium ion with deviate 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 as anode material for lithium-ion batteries, in 2.5V left and right, there is a good charge and discharge platform; (4) specific capacity large (specific capacity is greater than 400mAh/g when 1C discharges and recharges) when gained titanium dioxide alum-graphene complex is as anode material for lithium-ion batteries; (5) when gained titanium dioxide alum-graphene complex is as anode material for lithium-ion batteries, there is excellent high rate capability (when 200C discharges and recharges, capacity is greater than 200mAh/g); (6) gained titanium dioxide alum-graphene complex has super good cycle performance (at 1C and 200C, after 1400 repeated charge respectively higher than 400mAh/g and 200mAh/g) when the anode material for lithium-ion batteries.
To sum up, compound of the present invention has high conductivity, having super excellent high rate capability and good circulation stability, is ideal anode material for lithium-ion batteries, can be widely used in the fields such as various portable electric appts, electric automobile and Aero-Space; In addition, this compound can be 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 titanium dioxide alum-Graphene composite band of embodiment 1, and wherein (a) and (b) be the scanning electron microscope (SEM) photograph (SEM) of different multiplying, confirms that its average length is between 1～100 μ m, and width is between 20-500nm; (c) be transmission electron microscope picture (TEM), a nearly step confirms above-mentioned width and transparent, ultra-thin characteristic under Electronic Speculum; (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 analyzing, confirms 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 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) (JCPDS No.31-1438); (b) prolong titanium dioxide alum (B) the crystal structure figure of (010) crystal face projection;
Fig. 3 is the chemical property result of vanadium dioxide-graphene complex of the present invention: the constant current charge-discharge curve of the electrode that (a) compound of embodiment 1 is made under 1C and 20C multiplying power; (b) cycle performance (30 circulation) of the electrode that the compound of embodiment 1, embodiment 3 and comparative example 1 is made under 1C multiplying power; (c) cycle performance (1400 circulation) of the electrode that the compound of embodiment 1 and embodiment 3 is made under 200C multiplying power, the cycle performance (3000 circulation) of the electrode that (d) compound of embodiment 1 is made under 200C multiplying power;
Fig. 4 is 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), confirms that the average length of composite sheet is between 1～100 μ m, and width is between 1～100 μ m; (b) be high-resolution-ration transmission electric-lens figure (HRTEM), a nearly step confirms that its titanium dioxide alum sheet is that in mono-crystalline structures and composite sheet, part is covered by Graphene; (c) electron energy loss spectroscopy (EELS) (EDX), in confirmation titanium dioxide alum, the atomic ratio of V and O is 2:1.
Fig. 5 is the appearance structure characterization result of titanium dioxide alum-Graphene composite band of embodiment 6, and wherein (a) is scanning electron microscope (SEM) photograph (SEM), confirms that the average length of composite sheet is between 1～10 μ m, and 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
Vanadium dioxide-graphene complex, it prepares as follows:
(1), by vanadic oxide 1800mg and the two mass ratio of graphene oxide 400mg(, be 4.5:1) mix, be distributed in 200mL water, be then sealed in water heating kettle, at 180 ± 5 ℃, react about 12 hours;
(2), to through step (1) system in add 2-10mL (35wt%) hydrazine hydrate, at 80 ± 2 ℃, carry out reduction reaction, react about 5 hours;
(3), freeze drying obtains solid product at-40 ° of C temperature, is vanadium dioxide-graphene complex.
Pattern of gained vanadium dioxide-graphene complex etc. is characterized, and result is referring to Fig. 1.Vanadium dioxide-graphene complex is by average length between 1～100 μ m, and width is at 20 ~ 500nm, and the vanadium dioxide-Graphene composite band of thickness between 1 ~ 50nm forms, and specific area is 420m
2/ g.
Structure to vanadium dioxide-graphene complex characterizes, and result, referring to 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) (JCPDS No.31-1438); In composite band, Graphene closely covers on titanium dioxide alum, is loose structure.
Vanadium dioxide-graphene complex is made to work electrode and carried out corresponding electrochemical property test according to method provided by the present invention, and result is as follows: coulomb efficiency is more than 90% first, and when 1C discharges and recharges, stabilization ratio capacity is 441mAh/g; When 20C discharges and recharges, stabilization ratio capacity is 328mAh/g; When 200C discharges and recharges, stabilization ratio capacity is 210mAh/g; While discharging and recharging under above-mentioned multiplying power, after 1400 repeated charge, capacity all can keep the more than 90% of initial capacity.
Embodiment 2
Embodiment 2 provides a kind of vanadium dioxide-graphene complex, and its preparation method is substantially with embodiment 1, different, and the mass ratio that feeds intake of its raw material vanadium oxide and graphene oxide is 3:1.Vanadium dioxide-graphene complex is made to work electrode and carried out corresponding electrochemical property test according to method provided by the present invention, and result is as follows: coulomb efficiency is more than 90% first, and when 1C discharges and recharges, stabilization ratio capacity is 390mAh/g; When 20C discharges and recharges, stabilization ratio capacity is 295mAh/g; When 200C discharges and recharges, stabilization ratio capacity is 204mAh/g; While discharging and recharging under above-mentioned multiplying power, after 1400 repeated charge, capacity all can keep the more than 90% of initial capacity.
Embodiment 3
This example provides a kind of vanadium dioxide-graphene complex, and its preparation method is substantially with embodiment 1, different, and the mass ratio that feeds intake of its raw material vanadium oxide and graphene oxide is 2:1.
Vanadium dioxide-graphene complex is made to work electrode and carried out corresponding electric performance test according to method provided by the present invention, and result is as follows: coulomb efficiency is 92% first, and when 1C discharges and recharges, stabilization ratio capacity is 370mAh/g; When 20C discharges and recharges, stabilization ratio capacity is 284mAh/g; When 200C discharges and recharges, stabilization ratio capacity is 194mAh/g; And while discharging and recharging under above-mentioned multiplying power, after 1400 repeated charge, capacity all can keep the 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 the two mass ratio of graphene oxide 400g(, be 4.5:1) mix, be distributed in 200mL water, be then sealed in water heating kettle, at 210 ± 5 ℃, react about 20 hours;
(2), to through step (1) system in add 2-10mL (35wt%) hydrazine hydrate, at 90 ± 2 ℃, carry out reduction reaction, react about 5 hours;
(3), supercritical drying obtains solid product, is vanadium dioxide-graphene complex.
Pattern of gained vanadium dioxide-graphene complex etc. is characterized, and result is referring to Fig. 4.Vanadium dioxide-graphene complex forms jointly by being with sheet, and wherein the size of band is with embodiment 1, and the average length of sheet is between 1～100 μ m, and width is at 1～100 μ m, and thickness is between 1 ~ 50nm, and specific area is 620m
2/ g.
Structure to vanadium dioxide-graphene film characterizes, and result, referring to Fig. 4, shows in composite sheet, and the V in titanium dioxide alum and the atomic ratio of O are 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, and its preparation method is substantially with embodiment 1, different, and its raw material vanadic oxide replaces with vanadium trioxide.Vanadium dioxide-graphene complex is made to work electrode and carried out corresponding electrochemical property test according to method provided by the present invention, and result is as follows: coulomb efficiency is more than 91% first, and when 1C discharges and recharges, stabilization ratio capacity is 420mAh/g; When 20C discharges and recharges, stabilization ratio capacity is 305mAh/g; When 200C discharges and recharges, stabilization ratio capacity is 290mAh/g; While discharging and recharging under above-mentioned multiplying power, after 1400 repeated charge, capacity all can keep the more than 90% of initial capacity.
Embodiment 6
Vanadium dioxide-graphene complex, it prepares as follows:
(1), by vanadic oxide 1800mg and the two mass ratio of graphene oxide 400mg(, be 4.5:1) mix, be distributed in 200mL ethylene glycol, be then sealed in water heating kettle, at 180 ± 2 ℃, react about 20 hours;
(2), freeze drying obtains solid product at-40 ° of C temperature, is vanadium dioxide-graphene complex.
Pattern of gained vanadium dioxide-graphene complex etc. is characterized, and result is referring to Fig. 5.Vanadium dioxide-graphene complex is by average length between 1～10 μ m, and width is at 200～800nm, and the vanadium dioxide-Graphene composite band of thickness between 1 ~ 50nm forms, and specific area is 610m
2/ g.
Structure to vanadium dioxide-graphene complex characterizes, and result, referring to 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, and its preparation method is substantially with embodiment 1, different, and the mass ratio that feeds intake of its raw material vanadium oxide and graphene oxide is 9.5:1.Make after electrode slice, record its first coulomb efficiency be 85%, when 1C discharges and recharges, specific capacity is 580mAh/g first; When 20C discharges and recharges, stabilization ratio capacity is 320mAh/g; When 200C discharges and recharges, stabilization ratio capacity is less than 100mAh/g; And while discharging and recharging under above-mentioned multiplying power, after 30 repeated charge, capacity is all lower than 80% of initial capacity.
The poor existing deficiency of cycle performance while the present invention is directed to titanium dioxide alum poorly conductive and storage lithium, by the control of preparation method and preparation condition, the final power lithium-ion battery positive electrode with ultra-high capacity, ultra-high magnifications performance and super good cycle performance that obtains.This has very important significance to the development of promotion high power lithium ion cell and solution energy shortage etc.
Above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that Spirit Essence is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. a vanadium dioxide-graphene complex, it is characterized in that: it is raw material that this compound be take oxide and the graphene oxide of vanadium, by hydro thermal method or solvent-thermal method, be prepared from, its by length between 1 ~ 100 μ m, width between the μ m of 20nm ~ 100, vanadium dioxide-Graphene composite band or the sheet of thickness between 1 ~ 50nm 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 is when the anode material for lithium-ion batteries, and charge and discharge platform is 2.5V, and specific capacity is at 1C and 200C, after 1100 repeated charge respectively higher than 400mAh/g and 200mAh/g.
2. vanadium dioxide-graphene complex according to claim 1, is characterized in that: the preparation method of described compound comprises the steps:
(1), the oxide of alum is mixed is distributed in water and/or organic solvent with graphene oxide, then be sealed in water heating kettle, at 100 ℃ ~ 300 ℃ of temperature, carry out hydro-thermal reaction and/or solvent thermal reaction, wherein the mass ratio that feeds intake of the oxide of alum and graphene oxide is 0.8 ~ 10:1;
(2), adopt any seasoning be selected from vacuumize, freeze drying and supercritical drying to be dried the product system of front step, obtain solid product, be described vanadium dioxide-graphene complex;
Described preparation method also optionally comprises step (3): step (1) afterwards, step (2) before, in the system after step (1), add reducing agent, make to occur reduction reaction.
3. vanadium dioxide-graphene complex according to claim 2, is characterized in that: in step (1), the oxide of described alum is to be selected from one or more in vanadium pentoxide, three oxidation two alum, oxidation two alum, four oxidation two alum.
4. according to the vanadium dioxide-graphene complex described in claim 2 or 3, it is characterized in that: the mass ratio that feeds intake of the oxide of described alum and graphene oxide is 3 ~ 5:1.
5. vanadium dioxide-graphene complex according to claim 2, is characterized in that: in step (1), described organic solvent is one or more the combination in ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, methyl pyrrolidone.
6. according to the vanadium dioxide-graphene complex described in claim 2 or 5, it is characterized in that: when the solvent adopting does not have reproducibility, implement described step (3) in step (1); When the solvent adopting has reproducibility, implement or do not implement described step (3) in step (1).
7. vanadium dioxide-graphene complex according to claim 2, is characterized in that: described reducing agent is to be selected from one or more in hydrazine hydrate, sodium borohydride, potassium borohydride, hydrogen, and the temperature of the reduction reaction of step (3) is 50 ℃ ~ 100 ℃.
8. vanadium dioxide-graphene complex according to claim 2, is characterized in that: the reaction that makes step (1) is carried out at 150 ℃ ~ 250 ℃ of temperature.
9. vanadium dioxide-graphene complex according to claim 1 and 2, it is characterized in that: described compound by length between 1 ~ 100 μ m, width between 20nm-500nm, the vanadium dioxide-Graphene composite band of thickness between 1 ~ 50nm form, when this compound is used as anode material for lithium-ion batteries, charge and discharge platform is 2.5V, specific capacity is at 1C and 200C, after 1400 repeated charge respectively higher than 400Ah/g and 200mAh/g.
10. vanadium dioxide-the graphene complex as described in any one claim in claim 1 ~ 9 is 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 |
| 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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| 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 |
| WO2022237151A1 (en) * | 2021-05-12 | 2022-11-17 | 郑州大学 | Method for preparing ferromagnetic vo2 using supercritical fluid technology |
| 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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