CN106159225B - A method of producing carbon complex amorphous vanadium oxide powder - Google Patents
A method of producing carbon complex amorphous vanadium oxide powder Download PDFInfo
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- CN106159225B CN106159225B CN201610592630.1A CN201610592630A CN106159225B CN 106159225 B CN106159225 B CN 106159225B CN 201610592630 A CN201610592630 A CN 201610592630A CN 106159225 B CN106159225 B CN 106159225B
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/58—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
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- 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
Abstract
The present invention relates to a kind of methods producing carbon complex amorphous vanadium oxide nanopowders end, belong to new energy field.Technical process is：Use vanadium source, fuel, adjuvant and carbon source for raw material, according to a certain percentage wiring solution-forming；Solution is heated under certain atmosphere, after volatilizing, concentrating and to form gel combustion synthesis reaction occurs for solution.The heat that combustion reaction is released can make reaction from maintenance, finally obtain carbon complex amorphous vanadium oxide powder.Bulk gas is generated in reaction process, can not only powder product be effectively prevent to reunite, and can also form meso-hole structure.And due to using liquid phase mixing, it can be achieved that the tiny amorphous vanadium particle of granularity and carbon combine closely with it is evenly dispersed.Raw material of the present invention is easy to get, and simple process and low cost is easy to industrialization, when the carbon complex amorphous vanadium oxide powder being prepared is as lithium cell negative pole material, has both high power capacity and excellent cyclical stability.
Description
Technical field
The invention belongs to new energy field, it is related to a kind of carbon complex amorphous vanadium oxide of one-step synthesis as lithium cell negative pole
The method of material.
Background technology
New and renewable energy technology is one of 21 century most important new high-tech industry, wherein electrochemical energy storage
The developing direction of system is large capacity, high power and long-life.And lithium ion battery is light-weight with its, energy density is big, without note
The advantages that recalling effect, long lifespan is widely used in the fields such as mobile phone, video camera, laptop, electric vehicle.Currently, quotient
Lithium ion battery negative material is mainly carbons negative material, its theoretical capacity is only 372mAh/g, is not adapted to
The widespread demand of the miniaturization of portable electronic device and electric vehicle team large-capacity high-power electrochmical power source at present.Cause
This, it is very urgent for the lithium ion battery demand of high-energy-density, long circulation life, fast charging and discharging.Currently, a large amount of research
It has shifted towards and finds novel negative material, wherein vanadium oxide is since it is with typical layer structure, high theoretical specific capacity, valence
Lattice are cheap and easy acquisition, become ideal candidate material.Although the vanadium oxide capacity of crystalline state is high, it is possible to provide a large amount of lattice storage
Lithium ion is deposited, but after storing, lattice is easily converted to stable phase, therefore lithium ion is pricked by solid in lattice, irreversible.
In addition, the poorly conductive of vanadium oxide, resistance is high.These two aspects all limits its application in terms of lithium electricity.
Research shows that there are two types of the lithium electrical properties that measure can improve vanadium oxide：When can by the compound method of carbon into
Row improves, this is because carbon material has, conductivity height, large specific surface area, flexibility are good, are imitated with metal oxide with cooperateing with
The advantages that answering can improve the electric conductivity and cyclical stability of composite material.Second is that by vanadium oxide amorphous material, this is because nothing
The vanadium oxide of amorphous configuration can not only alleviate bulk effect, and a large amount of defects in structure are also used as lithium in charge and discharge process
The storage point of ion is conducive to improve capacity.(Niu C, et al.Nanoresearch, 2015.) is by inclined vanadium for example, Niu etc.
Sour ammonium, citric acid and ethylene glycol wiring solution-forming, solution is positioned in reactor, is heated at 180 DEG C, then heavy by what is obtained
Starch is washed, is dried, and is finally calcined to obtain amorphous vanadium/carbosphere in a nitrogen atmosphere, which is used for
When lithium ion battery, high efficiency, high stability, the excellent chemical property such as long lifespan are presented.Therefore, how simply, just
Just, the carbon complex amorphous vanadium oxide material of preparing of high efficiency and low cost has weight to application of the promotion vanadium oxide in lithium electricity
Want meaning.
Invention content
The present invention provides a kind of method preparing carbon complex amorphous vanadium oxide powder.The present invention using vanadate as vanadium source,
Water soluble organic substance is carbon source, and it is adjuvant or fuel to add suitable amine organic matter, using synthetic method of solution burning, one
Step obtains carbon and amorphous state vanadium oxide composite powder.This method is simple, efficiently, low cost, and can realize tiny amorphous
Vanadium oxide particle is uniformly compound with carbon.
It is characteristic of the invention that by solution combustion synthesis application in preparing carbon complex amorphous vanadium oxide powder.Solution combustion
Synthesis is a kind of combustion reaction betided in solution between oxidant and fuel, and therefore, it has the advantages of wet chemical method,
Can ensure in the liquid phase each component mixing uniformity, ingredient is accurate, easily-controllable, and with conventional wet chemical method such as sol-gel
Method, precipitation method etc. compare, and this method has the advantages that uniqueness again：The heat released in reaction process can make reaction from dimension
It holds, is not necessarily to extra power, low energy consumption；A large amount of gas is released in reaction process makes combustion product be in fluffy foam-like, can be with
It effectively prevent reuniting, forms the nano-powder of high-specific surface area；Combustion velocity is fast, can complete in a few minutes, technique letter
Just, fast；Furthermore, it is possible to by adjusting the factors control such as amount of the proportioning of fuel and oxidant, the rate of heat addition and combustible substance
Combustion process processed, and then control synthetic powder ingredient, object phase, pattern and performance.
After vanadium source and carbon source are dissolved in water in the present invention, in aqueous solution by vanadium source and carbon source in atom, lewis' acid
Uniformly mixing is not necessarily to external heat source by the control conditions such as fuel and oxidant proportioning, combustion atmosphere, raw material proportioning in level,
The heat released using combustion reaction makes reaction from maintenance, and vanadium source in solution is made to be converted into the tiny amorphous state oxidation of granularity
Vanadium particle, uniform " inlaying " is distributed in carbon source and is pyrolyzed in the carbon base body to be formed, to realize tiny amorphous vanadium particle
It is uniformly compound with carbon.High power capacity and excellent cyclical stability are had both with the electrode of the material preparation, it is close in the electric current of 0.1A/g
Under degree, the capacity after 100 cycles is no less than 700mAh/g.
The invention is characterised in that including the following steps：
1, the raw materials such as vanadium source, fuel, adjuvant and carbon source are weighed according to a certain percentage, are carried out with a certain amount of water uniform
Stirring is uniformly mixed and is made into precursor solution.Proportioning between wherein each raw material is：The molar ratio in fuel and vanadium source is 0.5-10,
The molar ratio in adjuvant and vanadium source is 2-15, and the molar ratio in carbon source and vanadium source is 0.01-1；
2, the precursor solution obtained in step 1 is positioned on heating furnace, the solution is added under certain atmosphere
Heat, solution occur combustion synthesis reaction, finally obtain carbon complex amorphous vanadium oxide powder after boiling, evaporating and to form gel
End；
Vanadium source described in step 1 is selected from one or more of ammonium metavanadate, ammonium poly-vanadate；Fuel be selected from urea,
One or more of glycine；Adjuvant is selected from one or more of nitric acid, ammonium nitrate, citric acid；Carbon source
Selected from one or more of sucrose, glucose, fructose, maltose, inosite, soluble starch, glycogen, xylose；One
It is one or more of air, argon gas, nitrogen to determine atmosphere.
It is an advantage of the invention that：
1, carbon complex amorphous vanadium oxide powder, technique are prepared using one step of combustion reaction between each raw material in liquid phase
It is easy, quick, it is efficient, it is at low cost.
2, the heat that combustion reaction is released can make reaction from maintenance, and low energy consumption；
3, the bulk gas released in reaction process can not only effectively prevent powder product to reunite, but also can form a large amount of Jie
Pore structure is conducive to the raising of lithium electrical property.
4, can be achieved the tiny amorphous vanadium particle of granularity and carbon combine closely with it is evenly dispersed；
5, can by adjusting the factor controllings products such as the atmosphere of proportioning, reaction between raw material and heating parameters phase,
Pattern and carbon content, and then control the performance of synthetic powder.
6, when the carbon complex amorphous vanadium oxide powder being prepared is as lithium cell negative pole material, high power capacity and excellent is had both
Cyclical stability.
Description of the drawings
Fig. 1 is the X-ray diffractogram of example 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of example 1.
Fig. 3 is the nitrogen adsorption desorption curve graph of example 1.
Fig. 4 is lithium electricity cycle performance figure of the example 1 under 0.1A/g current densities.
Specific implementation mode
Embodiment 1
Weigh 0.1 mole of ammonium metavanadate, 0.8 mole of ammonium nitrate, 0.3 mole of citric acid, 0.08 mole of glycine, glucose
0.02 mole is configured to solution, in the solution uniformly mixes vanadic acid radical ion and carbon source molecule.Solution is placed on heating furnace,
It is heated under air.Solution occurs combustion synthesis reaction, it is compound to finally obtain carbon after boiling, evaporating and to form gel
Amorphous vanadium powder.
Embodiment 2
Weigh 0.1 mole of ammonium metavanadate, 0.8 mole of ammonium nitrate, 0.3 mole of citric acid, 0.08 mole of glycine, glucose
0.03 mole is configured to solution, and solution is placed on heating furnace, is heated under air.Solution is formed by boiling, evaporation
After gel, combustion synthesis reaction occurs, obtains carbon complex amorphous vanadium oxide powder.
Embodiment 3
Weigh 0.06 mole of ammonium metavanadate, 0.8 mole of ammonium nitrate, 0.3 mole of citric acid, 0.08 mole of glycine, grape
0.01 mole of sugar is configured to solution, and solution is placed on heating furnace, is heated under air.Solution is by boiling, evaporation shape
After gel, combustion synthesis reaction occurs, obtains carbon complex amorphous vanadium oxide powder.
Test result
Using carbon complex amorphous vanadium oxide material obtained in above-mentioned 3 embodiments as active material, with conductive charcoal
Black (Super P), polyvinylidene fluoride (PVDF) is according to mass ratio 60：30：10 make the negative material of lithium electricity.By mixture point
It is scattered in nmp solution and slurry is made, then equably slurry is coated onto on copper foil with blade, 120 DEG C of dryings in vacuum drying chamber
After 12h, in 200kg m-2Pressure under be pressed into disk.In vacuum glove box by electrode assembling be CR2023 type button cells
Carry out electro-chemical test, the EC/DMC (1 containing 1M LiPF6:1wt%) it is used as electrolyte.Metal lithium sheet is used as to electrode.Envelope
After the button cell installed stands 12h, the constant current charge-discharge test of button cell, voltage model are carried out in LAND test systems
It encloses for 0.01-3V (vs Li+/ Li), current density 0.1A/g, test environment temperature is maintained at 25 DEG C or so.As a result it counts such as
Table 1：
Comparative example 1：
0.1 mole of ammonium metavanadate, 0.8 mole of ammonium nitrate, 0.32 mole of citric acid are weighed, 0.08 mole of glycine will be each
Kind raw material is soluble in water, is configured to solution.Solution is placed on heating furnace, is heated under a nitrogen.Solution by boiling,
After evaporation forms gel, combustion synthesis reaction occurs, finally obtains the V of crystalline state2O3Powder.Using identical with embodiment 1,2,3
Method is prepared into lithium ion battery as negative material using the material and carries out electro-chemical test.Under the current density of 0.1A/g, 100
Capacity after secondary cycle is 320mAh/g.
In conclusion the present invention prepares carbon complex amorphous vanadium oxide powder using one step of solution combustion synthetic method,
The vanadium oxide particle of middle amorphous state uniform " inlaying " is distributed in carbon source and is pyrolyzed in the carbon base body to be formed.The oxygen of the impalpable structure
The bulk effect in charge and discharge process can not only be alleviated by changing vanadium, and a large amount of defects in structure are also used as in charge and discharge process
The storage point of lithium ion；And carbon base body is with conductivity height, large specific surface area, flexibility are good, with metal oxide with cooperateing with
The advantages that effect, can improve the electric conductivity and cyclical stability of entire composite material.Therefore, carbon complex amorphous of the invention
Vanadium oxide powder has higher capacity as the negative material of lithium ion battery compared to the vanadium oxide of crystalline state, and outstanding follows
Ring stability.
Claims (2)
1. a kind of method producing carbon complex amorphous vanadium oxide powder, it is characterised in that include the following steps：
A, vanadium source, fuel, adjuvant and carbon source raw material are weighed according to a certain percentage, and uniform stirring is carried out with a certain amount of water,
It is uniformly mixed and is made into precursor solution；Proportioning between wherein each raw material is：The molar ratio in fuel and vanadium source is 0.5-10, adjuvant
It is 2-15 with the molar ratio in vanadium source, the molar ratio in carbon source and vanadium source is 0.01-1；
B, the precursor solution obtained in step a is positioned on heating furnace, the solution is heated under certain atmosphere, it is molten
Liquid occurs combustion synthesis reaction, finally obtains carbon complex amorphous vanadium oxide powder after boiling, evaporating and to form gel；
Wherein, the uniform patchiness of the vanadium oxide particle of amorphous state is pyrolyzed in carbon source in the carbon base body to be formed；
Vanadium source described in a steps is one or both of ammonium metavanadate, ammonium poly-vanadate；
Fuel described in a steps is one or both of urea, glycine；
Adjuvant described in a steps is one or more of nitric acid, ammonium nitrate, citric acid；
Carbon source described in a steps is in sucrose, glucose, fructose, maltose, inosite, soluble starch, glycogen, xylose
One or more.
2. the method for production carbon complex amorphous vanadium oxide powder according to claim 1, it is characterised in that institute in b step
The certain atmosphere stated is one or more of air, argon gas, nitrogen.
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| CN106829923A (en) * | 2017-03-16 | 2017-06-13 | 石河子大学 | A kind of biomass carbon material and preparation method |
| CN107892329B (en) * | 2017-11-23 | 2020-07-17 | 北京科技大学 | Preparation device and preparation method for synthesizing powder material through high-flux combustion |
| CN113161522B (en) * | 2021-03-12 | 2022-07-19 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
| CN113782726A (en) * | 2021-09-13 | 2021-12-10 | 厦门理工学院 | Preparation method of zinc ion battery positive electrode material, zinc ion battery positive electrode material and zinc ion battery |
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| CN103035882A (en) * | 2011-10-10 | 2013-04-10 | 成都理工大学 | Method for synthesizing Li3V2(PO4)3/C by using glycine-nitrate combustion method |
| KR101708363B1 (en) * | 2013-02-15 | 2017-02-20 | 삼성에스디아이 주식회사 | Negative active material, and negative electrode and lithium battery containing the material |
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