CN104852015A - Niobium pentoxide nanosheet composite material, preparation method and application thereof - Google Patents
Niobium pentoxide nanosheet composite material, preparation method and application thereof Download PDFInfo
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- CN104852015A CN104852015A CN201510073867.4A CN201510073867A CN104852015A CN 104852015 A CN104852015 A CN 104852015A CN 201510073867 A CN201510073867 A CN 201510073867A CN 104852015 A CN104852015 A CN 104852015A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- 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
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- 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
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 invention discloses a niobium pentoxide nanosheet composite material, a preparation method and application thereof. The preparation method comprises a first step of adding soluble niobate used as a niobium source into a mixed solvent of deionized water and ethidene diamine, performing heating reaction, after finishing the heating reaction, naturally cooling, and alternately washing with water and ethyl alcohol so as to obtain an orthorhombic phase niobium pentoxide nanosheet; and a second step of performing ultrasonic mixing on the prepared niobium pentoxide and oleic acid according to weight ratio of 5:1-1:10, heating for 1-8 hours in an inert gas at 400-1200DEG C, so as to obtain the amorphous carbon wrapped niobium pentoxide nanosheet composite material. According to the method, the oleic acid adsorbs crystal face to anneal so as to form amorphous carbon, and an amorphous carbon layer wraps on the surface of the niobium pentoxide nanosheet. The method has simple steps, is fast, and is easy to operate; and the prepared amorphous carbon wrapped niobium pentoxide composite material has small size and good electrical conductivity, and has the characteristics of large capacity, good cycling stability, high rate capacity and so on when being used as the cathode of a battery.
Description
Technical field
The application relates to lithium ion battery negative material field, particularly relates to a kind of niobium pentoxide nano sheet composite material and its preparation method and application.
Background technology
Owing to having high-energy-density and high power density, lithium ion battery has key player in each electronic product.Negative material is one of critical material of lithium ion battery, the performance of serious restriction lithium ion battery.At present, the research of negative material comprises: material with carbon element, lithium titanate, metal oxide, silica-based and tin-based material.Material with carbon element and lithium titanate have comparatively low capacity; Although most metals oxide, silica-based and tin-based material capacity is higher, in charge and discharge process, material volume change greatly, shortens battery life.
Orthorhombic phase pentoxide crystal structure has effective passage of higher li Ion transfer, can effectively store lithium ion and structure remains unchanged, have higher lithium storage content and structural stability.But niobium pentaoxide has lower conductivity, restrict its charge/discharge capacity under high current density.
Summary of the invention
The object of the application is to provide a kind of new niobium pentoxide nano sheet composite material and its preparation method and application.
To achieve these goals, the application have employed following technical scheme:
The one side of the application discloses a kind of preparation method of orthorhombic phase niobium pentoxide nano sheet composite material, comprise the following steps, (1) with solubility niobium salt for niobium source, niobium source is joined in the mixed solvent of deionized water and ethylenediamine composition, heating is reacted, reaction terminates rear cooling naturally, obtains orthorhombic phase niobium pentoxide nano sheet after alternately washing with water and ethanol; (2) niobium pentaoxide prepared by step (1) is mixed according to weight ratio 5:1-1:10 with oleic acid, at 400-1200 DEG C, heat 1-8 hour in inert gas atmosphere, obtain the orthorhombic phase niobium pentoxide nano sheet composite material that agraphitic carbon is coated.In a kind of implementation of the application, at 400-1000 DEG C, heat 2 hours.
It should be noted that, the key of the application is the hydro thermal method preparing niobium pentaoxide and oleic acid to anneal and forms amorphous carbon and combine, the creationary Surface coating at niobium pentoxide nano sheet is one deck amorphous carbon at least, compared with independent niobium pentaoxide, the composite material of the application, not only further increase specific capacity, and there is good conductivity.
Also it should be noted that, the concrete operations mode that water and ethanol alternately wash, with reference to the mode of washing in conventional niobium pentaoxide production procedure, is not specifically limited at this; The key of the application forms the coated niobium pentaoxide composite material of agraphitic carbon, in follow-up application, such as prepare negative material time, its following process is determined according to concrete working condition or production object, is not specifically limited at this.
Preferably, in step (1), the deionized water of mixed solvent and the volume ratio of ethylenediamine are 99:1-1:99, are more preferably 35:5-5:35.It should be noted that, the volume ratio of deionized water and ethylenediamine affects the important parameter reacted, ratio both can controlling with reference to the niobium pentaoxide hydro-thermal reaction of routine, in a kind of scheme of the application, in order to produce the niobium pentaoxide meeting the application's demand, in mixed solvent, the volume ratio of deionized water and ethylenediamine is 35:5-5:35.
Preferably, in step (1), heating the temperature of carrying out reacting is 150-250 DEG C, and the reaction time is 5-30 hour.It should be noted that, heat the temperature and time carrying out reacting to carry out with reference to the hydro thermal method of routine, in a kind of scheme of the application, in conjunction with the actual conditions of the application, setting reaction temperature is 150-250 DEG C, preferred reaction temperature is 150-240 DEG C, and the reaction time is set to 5-30 hour, preferably 24 hours.
Preferably, solubility niobium salt be acetic acid niobium, at least one of fluoridizing in niobium, niobium chloride, iodate niobium and bromination niobium.It should be noted that, the conventional solubility niobium salt preparing niobium pentaoxide for hydro thermal method may be used to the application in theory, and the application preferably adopts acetic acid niobium, fluoridizes niobium, niobium chloride, iodate niobium or bromination niobium.
Preferably, the reaction density in solubility niobium source is 0.001mol/L-0.2mol/L.
Preferably, in step (2), niobium pentaoxide mixes according to weight ratio 2:1-1:5 with oleic acid, and the mode of mixing is ultrasonic mixing.
Preferably, inert gas is nitrogen and/or argon gas.
Orthorhombic phase niobium pentoxide nano sheet composite material prepared by the preparation method that the another side of the application also discloses the application, the Surface coating of this composite material has amorphous carbon, and amorphous carbon accounts for the 1%-15% of total weight.Preferably, amorphous carbon accounts for the 5%-15% of total weight.
In addition, the application uses Shortcomings for existing niobium pentaoxide as lithium ion battery negative material and studies, therefore, the application in lithium ion battery negative material prepared by the niobium pentoxide nano sheet composite material that the application further provides the application.It should be noted that, in a kind of implementation of the application, niobium pentoxide nano sheet composite material the application prepared and conventional conductive agent, together with binding agent, are prepared into negative material for lithium ion battery.Wherein, conductive agent is preferably acetylene black, the preferred sodium cellulose glycolate of binding agent (writing a Chinese character in simplified form, CMC).
Therefore, the one side again of the application discloses a kind of negative material for lithium ion battery, the niobium pentoxide nano sheet composite material containing the application in this negative material.
Further, in a kind of implementation of the application, the negative material of the niobium pentoxide nano sheet composite material containing the application is made lithium ion battery; Therefore, the one side again of the application discloses a kind of lithium ion battery made by negative material of the niobium pentoxide nano sheet composite material containing the application.
Owing to adopting above technical scheme, the beneficial effect of the application is:
The preparation method of the application utilizes oleic acid to adsorb crystal face annealing and forms agraphitic carbon, and at niobium pentoxide nano sheet Surface coating amorphous carbon layer prepared by hydro thermal method, preparation method's step is simple, quick, easy to operate.Further, the niobium pentoxide nano sheet composite material that the agraphitic carbon prepared by the preparation method of the application is coated, uses as battery cathode and has that capacity is high, good cycling stability, rate capability high.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the niobium pentoxide nano sheet composite material that in the embodiment of the present application, agraphitic carbon is coated;
Fig. 2 is the high power transmission electron microscope picture of the niobium pentoxide nano sheet composite material that in the embodiment of the present application, agraphitic carbon is coated;
Fig. 3 adopts the niobium pentoxide nano sheet composite material of the application as the charge/discharge capacity curve of the button cell of negative material in the embodiment of the present application;
Fig. 4 adopts the niobium pentoxide nano sheet composite material of the application as the button cell of negative material at 100mAg in the embodiment of the present application
-1current density under charging cycle performance chart;
Fig. 5 adopts the niobium pentoxide nano sheet composite material of the application as the multiplying power charging performance curve chart of the button cell of negative material in the embodiment of the present application.
Embodiment
Amorphous carbon is as a kind of special defect grapheme material, be rarely used in composite material, the creationary feature utilizing oleic acid annealing to form amorphous carbon of the application, in advance oleic acid is mixed with niobium pentaoxide, anneal again, form the niobium pentoxide nano sheet composite material that amorphous carbon is coated.Composite material prepared by the application, not only have good specific capacity, and conductivity is good; Be made into lithium ion battery negative material, have that capacity is high, good cycling stability, rate capability high.
Below by specific embodiments and the drawings, the application is described in further detail.Following examples are only further described the application, should not be construed as the restriction to the application.
Embodiment one
The niobium pentoxide nano sheet composite material and preparation method thereof of this example is as follows:
(1) take columbium pentachloride as niobium source, niobium source is joined in the mixed solvent of 40ml deionized water and ethylenediamine composition, wherein, the final concentration of columbium pentachloride is 0.001mol/L, in 40ml mixed solvent, deionized water and ethylenediamine volume ratio are 5:35, after columbium pentachloride dissolves, to be transferred in the polytetrafluoro container of 50 milliliters and to be fixed in stainless reactor, then with baking oven directly at 240 DEG C, heat 24 hours, reaction completes, naturally cool, when the temperature of question response still is reduced to 25 degree naturally, obtained reactant is washed 3 times successively with water and ethanol respectively, by the sample after washing in 60 DEG C of baking ovens dry 4 hours, obtain orthorhombic phase niobium pentoxide nano sheet,
(2) then niobium pentaoxide prepared by step (1) is mixed according to weight ratio 2:1 with oleic acid, and adopt ultrasonic mixing 24 hours, by its mixture in argon gas atmosphere 400 DEG C heating 2 hours, namely obtain the orthorhombic phase niobium pentoxide nano sheet composite material that the amorphous carbon of this example is coated.
Through measuring, in the composite material of this example, agraphitic carbon content accounts for 9.5% of agraphitic carbon coated niobium pentoxide nano sheet composite material total weight.
Adopt ESEM to observe composite material prepared by this example, as depicted in figs. 1 and 2, Fig. 1 is the scanning electron microscope (SEM) photograph of the agraphitic carbon coated niobium pentoxide nano sheet composite material of this example preparation to result, and Fig. 2 is high power transmission electron microscope picture.As shown in Figure 1, the yardstick of the agraphitic carbon coated niobium pentoxide nano sheet composite material of this example is 300-500 ran, and its nanometer sheet thickness is 5-8 nanometer; As shown in Figure 2, agraphitic carbon is about 1-2 layer.
Agraphitic carbon coated niobium pentoxide nano sheet composite material prepared by this example is made lithium ion battery negative material, and adopts button cell to test its chemical property.In the lithium ion battery negative material of this example, conductive agent adopts acetylene black, and binding agent adopts CMC, niobium pentoxide nano sheet composite material: acetylene black: CMC mixes according to the ratio of weight ratio 80wt.%: 10wt.%: 10wt.%, coats on Copper Foil.In button cell, electrolyte adopts the LiPF of 1mol/L
6/ EC-DEC-DMC (1: 1: 1, w/w).Carry out charged/discharged with 100mA/g respectively, potential range is 0 ~ 3.0V.After tested, when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 563mAh/g, and after discharge and recharge in 100 weeks, discharge capacity can reach more than 396mAh/g.Charging and discharging curve, cycle characteristics curve and multiplying power property curve that the difference that Fig. 3, Fig. 4, Fig. 5 are respectively agraphitic carbon coated niobium pentoxide nano sheet composite material circulates.
Embodiment two
This example adopts the method identical with embodiment one and condition to prepare niobium pentoxide nano sheet composite material, and unique difference is, the final concentration of columbium pentachloride is 0.05mol/L, and all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the yardstick of agraphitic carbon coated niobium pentoxide nano sheet composite material is 100-300 ran, and its nanometer sheet thickness is 4-7 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 8% of agraphitic carbon coated niobium pentoxide nano sheet composite material total weight.
This example adopts the identical method of embodiment one to prepare negative material, and its chemical property tested by the same button cell that adopts, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 550mAh/g, and after discharge and recharge in 100 weeks, discharge capacity can reach more than 390mAh/g.
Embodiment three
This example adopts the method identical with embodiment one and condition to prepare niobium pentoxide nano sheet composite material, difference is, the final concentration of columbium pentachloride is 0.2mol/L, and, niobium pentaoxide prepared by step (1) mixes according to weight ratio 1:1 with oleic acid, and all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the yardstick of agraphitic carbon coated niobium pentoxide nano sheet composite material is 150-400 ran, and its nanometer sheet thickness is 5-8 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 5.3% of agraphitic carbon coated niobium pentoxide nano sheet composite material total weight.
This example adopts the identical method of embodiment one to prepare negative material, and its chemical property tested by the same button cell that adopts, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 555mAh/g, and after discharge and recharge in 100 weeks, discharge capacity can reach more than 386mAh/g.
Embodiment four
This example adopts the method identical with embodiment one and condition to prepare niobium pentoxide nano sheet composite material, difference is, (1) final concentration of columbium pentachloride is 0.05mol/L, (2) in the 40ml mixed solvent of step (1), deionized water and ethylenediamine volume ratio are 20:20, (3) with baking oven directly at 150 DEG C, heat 24 hours, (4) niobium pentaoxide that prepared by step (1) mixes according to weight ratio 1:5 with oleic acid, (5) by mixture in argon gas atmosphere 1000 DEG C heating 2 hours, except above 5 differences, all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the yardstick of agraphitic carbon coated niobium pentoxide nano sheet composite material is 100-300 ran, and its nanometer sheet thickness is 7-10 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 14.8% of agraphitic carbon coated niobium pentoxide nano sheet composite material total weight.
This example adopts the identical method of embodiment one to prepare negative material, and its chemical property tested by the same button cell that adopts, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 560mAh/g, and after discharge and recharge in 100 weeks, discharge capacity can reach more than 386mAh/g.
Embodiment five
This example adopts the method identical with embodiment one and condition to prepare niobium pentoxide nano sheet composite material, difference is, (1) final concentration of columbium pentachloride is 0.05mol/L, (2) in the 40ml mixed solvent of step (1), deionized water and ethylenediamine volume ratio are 20:20, (3) with baking oven directly at 150 DEG C, heat 24 hours, (4) niobium pentaoxide that prepared by step (1) mixes according to weight ratio 1:2.5 with oleic acid, (5) by mixture in argon gas atmosphere 1000 DEG C heating 2 hours, except above 5 differences, all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the yardstick of agraphitic carbon coated niobium pentoxide nano sheet composite material is 100-300 ran, and its nanometer sheet thickness is 7-11 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 12.3% of agraphitic carbon coated niobium pentoxide nano sheet composite material total weight.
This example adopts the identical method of embodiment one to prepare negative material, and its chemical property tested by the same button cell that adopts, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 551mAh/g, and after discharge and recharge in 100 weeks, discharge capacity can reach more than 370mAh/g.
Embodiment six
This example adopts the method identical with embodiment one and condition to prepare niobium pentoxide nano sheet composite material, difference is, (1) final concentration of columbium pentachloride is 0.05mol/L, (2) in the 40ml mixed solvent of step (1), deionized water and ethylenediamine volume ratio are 35:5, (3) with baking oven directly at 200 DEG C, heat 24 hours, (4) niobium pentaoxide that prepared by step (1) mixes according to weight ratio 1:2.5 with oleic acid, (5) by mixture in argon gas atmosphere 700 DEG C heating 2 hours, except above 5 differences, all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the yardstick of agraphitic carbon coated niobium pentoxide nano sheet composite material is 100-300 ran, and its nanometer sheet thickness is 6-9 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 12.1% of agraphitic carbon coated niobium pentoxide nano sheet composite material total weight.
This example adopts the identical method of embodiment one to prepare negative material, and its chemical property tested by the same button cell that adopts, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 545mAh/g, and after discharge and recharge in 100 weeks, discharge capacity can reach more than 369mAh/g.
Embodiment seven
This example adopts the method identical with embodiment one and condition to prepare niobium pentoxide nano sheet composite material, difference is, (1) final concentration of columbium pentachloride is 0.05mol/L, (2) in the 40ml mixed solvent of step (1), deionized water and ethylenediamine volume ratio are 35:5, (3) with baking oven directly at 200 DEG C, heat 24 hours, (4) niobium pentaoxide that prepared by step (1) mixes according to weight ratio 1:2.5 with oleic acid, (5) by mixture in argon gas atmosphere 1200 DEG C heating 2 hours, except above 5 differences, all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the yardstick of agraphitic carbon coated niobium pentoxide nano sheet composite material is 140-360 ran, and its nanometer sheet thickness is 5-9 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 12% of agraphitic carbon coated niobium pentoxide nano sheet composite material total weight.
This example adopts the identical method of embodiment one to prepare negative material, and its chemical property tested by the same button cell that adopts, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 565mAh/g, and after discharge and recharge in 100 weeks, discharge capacity can reach more than 383mAh/g.
Visible according to above embodiment, preparation method's step of the agraphitic carbon coated niobium pentoxide nano sheet composite material of the application is simple, little, the good conductivity of agraphitic carbon coated niobium pentoxide nano sheet composite material yardstick of preparation, has as lithium ion battery negative that capacity is high, good cycling stability, rate capability high.On the basis of above embodiment, the application also tests the atmosphere of oleic acid annealing, and found that, process can adopt beyond argon gas, and other inert gas, such as nitrogen also may be used for the application.In addition, solubility niobium salt, except columbium pentachloride, can also adopt acetic acid niobium, fluoridize niobium, iodate niobium and bromination niobium etc.
Above content is the further description done the application in conjunction with concrete execution mode, can not assert that the concrete enforcement of the application is confined to these explanations.For the application person of an ordinary skill in the technical field, under the prerequisite not departing from the application's design, some simple deduction or replace can also be made, all should be considered as the protection range belonging to the application.
Claims (10)
1. a preparation method for orthorhombic phase niobium pentoxide nano sheet composite material, is characterized in that: described preparation method comprises the following steps,
(1) with solubility niobium salt for niobium source, joined in niobium source in the mixed solvent of deionized water and ethylenediamine composition, heating is reacted, and reaction terminates naturally to cool afterwards, obtains orthorhombic phase niobium pentoxide nano sheet after alternately washing with water and ethanol;
(2) niobium pentaoxide prepared by step (1) is mixed according to weight ratio 5:1-1:10 with oleic acid, at 400-1200 DEG C, heat 1-8 hour in inert gas atmosphere, obtain the orthorhombic phase niobium pentoxide nano sheet composite material that agraphitic carbon is coated.
2. preparation method according to claim 1, is characterized in that: in described step (1), and the deionized water of mixed solvent and the volume ratio of ethylenediamine are 99:1-1:99, is preferably 35:5-5:35.
3. preparation method according to claim 1, is characterized in that: in described step (1), and heating the temperature of carrying out reacting is 150-250 DEG C, and the reaction time is 5-30 hour.
4. preparation method according to claim 1, is characterized in that: described solubility niobium salt is acetic acid niobium, at least one of fluoridizing in niobium, niobium chloride, iodate niobium and bromination niobium.
5. preparation method according to claim 1, is characterized in that: the reaction density in described solubility niobium source is 0.001mol/L-0.2mol/L.
6. preparation method according to claim 1, is characterized in that: in described step (2), niobium pentaoxide mixes according to weight ratio 2:1-1:5 with oleic acid, and the mode of described mixing is ultrasonic mixing.
7. preparation method according to claim 1, is characterized in that: described inert gas is nitrogen and/or argon gas.
8. orthorhombic phase niobium pentoxide nano sheet composite material prepared by the preparation method according to any one of claim 1-7, it is characterized in that: the Surface coating of described composite material has amorphous carbon, described amorphous carbon accounts for the 1%-15% of total weight.
9. for a negative material for lithium ion battery, it is characterized in that: containing the orthorhombic phase niobium pentoxide nano sheet composite material described in claim 7 or 8 in described negative material.
10. one kind adopts the lithium ion battery of negative material according to claim 9.
Priority Applications (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252592A (en) * | 2016-08-12 | 2016-12-21 | 合肥国轩高科动力能源有限公司 | The carbon in lithium ion battery of a kind of micro-nano structure is combined the preparation method of niobium pentaoxide material |
| CN106340400A (en) * | 2016-09-09 | 2017-01-18 | 华中科技大学 | Carbon-coating orthorhombic system nanometer rod shape Nb2O5 material and manufacturing method thereof |
| CN107055613A (en) * | 2017-02-27 | 2017-08-18 | 湖南工业大学 | One kind is without substrate niobium pentoxide nano chip arrays negative material and its preparation method and application |
| CN109817967A (en) * | 2019-01-22 | 2019-05-28 | 南京大学 | A kind of preparation method of high capacity aluminium ion cell positive material |
| CN111785955A (en) * | 2020-01-09 | 2020-10-16 | 郑州轻工业大学 | High-capacity VNb9O25Nano-sheet lithium ion battery cathode material and preparation method thereof |
| CN114890474A (en) * | 2022-04-06 | 2022-08-12 | 华东理工大学 | Superfine niobium-based nanocrystal/carbon nanosheet composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402463A (en) * | 2008-11-10 | 2009-04-08 | 华东师范大学 | Process for producing transition metal oxide nano-slice |
| CN101944590A (en) * | 2010-08-19 | 2011-01-12 | 东莞新能源科技有限公司 | Preparation method of carbon-coated lithium titanate |
| CN102593441A (en) * | 2012-02-27 | 2012-07-18 | 中信国安盟固利电源技术有限公司 | Synthesizing method of modified columbic anhydride for lithium ion battery |
-
2015
- 2015-02-11 CN CN201510073867.4A patent/CN104852015A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402463A (en) * | 2008-11-10 | 2009-04-08 | 华东师范大学 | Process for producing transition metal oxide nano-slice |
| CN101944590A (en) * | 2010-08-19 | 2011-01-12 | 东莞新能源科技有限公司 | Preparation method of carbon-coated lithium titanate |
| CN102593441A (en) * | 2012-02-27 | 2012-07-18 | 中信国安盟固利电源技术有限公司 | Synthesizing method of modified columbic anhydride for lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| HAIYAN LUO ET AL: ""Synthesis of Nb2O5 nanosheets and its electroc hemical measurements"", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Cited By (9)
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| CN106252592A (en) * | 2016-08-12 | 2016-12-21 | 合肥国轩高科动力能源有限公司 | The carbon in lithium ion battery of a kind of micro-nano structure is combined the preparation method of niobium pentaoxide material |
| CN106340400A (en) * | 2016-09-09 | 2017-01-18 | 华中科技大学 | Carbon-coating orthorhombic system nanometer rod shape Nb2O5 material and manufacturing method thereof |
| CN106340400B (en) * | 2016-09-09 | 2018-02-23 | 华中科技大学 | A kind of carbon coating rhombic system nano bar-shape Nb2O5Material and preparation method thereof |
| CN107055613A (en) * | 2017-02-27 | 2017-08-18 | 湖南工业大学 | One kind is without substrate niobium pentoxide nano chip arrays negative material and its preparation method and application |
| CN109817967A (en) * | 2019-01-22 | 2019-05-28 | 南京大学 | A kind of preparation method of high capacity aluminium ion cell positive material |
| CN109817967B (en) * | 2019-01-22 | 2021-11-05 | 南京大学 | Preparation method of high-capacity aluminum ion battery positive electrode material |
| CN111785955A (en) * | 2020-01-09 | 2020-10-16 | 郑州轻工业大学 | High-capacity VNb9O25Nano-sheet lithium ion battery cathode material and preparation method thereof |
| CN111785955B (en) * | 2020-01-09 | 2022-05-20 | 郑州轻工业大学 | High-capacity VNb9O25Nano-sheet lithium ion battery cathode material and preparation method thereof |
| CN114890474A (en) * | 2022-04-06 | 2022-08-12 | 华东理工大学 | Superfine niobium-based nanocrystal/carbon nanosheet composite material and preparation method and application thereof |
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