CN106252653B - A kind of graphitic carbon support of N doping and cladding Fe3O4The preparation method of anode material of lithium-ion battery - Google Patents
A kind of graphitic carbon support of N doping and cladding Fe3O4The preparation method of anode material of lithium-ion battery Download PDFInfo
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- CN106252653B CN106252653B CN201610725280.1A CN201610725280A CN106252653B CN 106252653 B CN106252653 B CN 106252653B CN 201610725280 A CN201610725280 A CN 201610725280A CN 106252653 B CN106252653 B CN 106252653B
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- lithium
- ion battery
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
A kind of graphitic carbon support of N doping and carbon coating Fe3O4Source of iron, urea, carbohydrate and organic acid are add to deionized water, stir evenly, mixed solution A is made by the preparation method of anode material of lithium-ion battery；By mixed solution A ultrasound 0.5-2h, equably mixed solution B is made；After will be dry after mixed solution B freezings under an argon atmosphere, at 400-600 DEG C, then in air atmosphere heat preservation 0.5-3h at 250-400 DEG C, and keeps the temperature 0.5-4h, obtains graphitic carbon support and the carbon coating Fe of N doping3O4Anode material of lithium-ion battery.The present invention supports it that can effectively improve Fe by graphitic carbon3O4Electric conductivity, graphite carbon coating can inhibit volume expansion, while and Fe again3O4It is compound also improve to a certain extent cell reaction activity, substantially improve the high rate performance of battery.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of graphitic carbon support of N doping and carbon coating Fe3O4Sodium
The preparation method of ion battery cathode material.
Background technology
Since lithium ion battery has energy density high, service life is long, and advantages of environment protection, recent years become
Research hotspot, and it is successfully realized commercialization.But lithium resource is relatively low in the reserves of the earth, and it is expensive, this
As continue develop lithium ion battery an obstacle.Therefore there is an urgent need to find a kind of rich reserves, kin element
To replace elemental lithium.Sodium and the element that lithium is same main group, and sodium is higher and widely distributed in the reserves of the earth, therefore in recent years
Carry out a large amount of researcher and put into a large amount of energy in the research of sodium-ion battery, sodium-ion battery also achieves rapidly
Development.However, sodium element differs larger with the radius of elemental lithium, therefore volume expansion becomes restriction sodium-ion battery development
One principal element.
The oxide of iron have high power capacity, low cost, derive from a wealth of sources, it is nontoxic the advantages that, be with existing theoretical capacity
372mAhg-1Graphite electrode compare, have significant advantage.However iron oxide poorly conductive, easily occur when charge and discharge significant
Volume expansion and cause to recycle these unstable disadvantages and greatly limit its extensive use, it is therefore desirable to find good conductivity
Material with its it is compound improve its electric conductivity, and it is swollen to alleviate the volume occurred when embedded sodium ion and abjection by surface cladding
It is swollen, and then to improve battery performance.
Invention content
The present invention is directed to existing issue, and main purpose is a kind of graphitic carbon support preparing N doping of proposition and carbon coating
Fe3O4As the method for anode material of lithium-ion battery, support it that can effectively improve Fe by graphitic carbon3O4Electric conductivity, graphite
Carbon coating can inhibit volume expansion, while and Fe again3O4It is compound also improve to a certain extent cell reaction activity, significantly
Improve the high rate performance of battery.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of graphitic carbon support of N doping and carbon coating Fe3O4The preparation method of anode material of lithium-ion battery, including with
Lower step：
1) source of iron, urea, carbohydrate and organic acid are add to deionized water, are stirred evenly, it is dense that source of iron is made
Degree is 0.5-5mol/L, urea concentration 0.5-10mol/L, carbohydrate concentration 0.05-0.5mol/L, and organic acid is dense
Degree is the mixed solution A of 0.01-0.5mol/L；
2) by the mixed solution A of above-mentioned preparation at 200~500W ultrasound 0.5-2h, equably mixed solution B is made；
3) will be dry after mixed solution B freezings, obtain loose product C；
4) under an argon atmosphere by loose product C, at 400-600 DEG C, 0.5-3h is kept the temperature, product D is obtained；
5) in air atmosphere by product D, at 250-400 DEG C, and 0.5-4h is kept the temperature, obtains the graphitic carbon support of N doping
And carbon coating Fe3O4Anode material of lithium-ion battery.
The present invention, which further improves, to be, source of iron is ammonium ferric oxalate or ferric citrate in step 1).
The present invention, which further improves, to be, organic acid is acetic acid or ethanedioic acid in step 1).
The present invention, which further improves, to be, carbohydrate is fructose, sucrose or cellulose in step 1).
The present invention, which further improves, to be, the time stirred in step 1) is 10-30min.
The present invention, which further improves, to be, the temperature freezed in step 3) is -30 DEG C, time 2-5h.
The present invention, which further improves, to be, dry in step 3) is specifically the dry 24- in vacuum freeze drier
48h。
The present invention, which further improves, to be, the flow of argon gas is 50~500sccm in step 4).
The present invention, which further improves, to be, with the rate of 5-15 DEG C/min from room temperature to 400-600 in step 4)
℃。
The present invention, which further improves, to be, with the rate of 5-10 DEG C/min from room temperature to 250-400 in step 5)
℃。
Compared with prior art, the device have the advantages that：
1) present invention carries out N doping, the cost of material of the method using urea using carbohydrate as carbon source to carbon source
Cheap, method is simple.
2) present invention prepared by product be graphite alkylene after carbon support and carbon coating Fe3O4, graphited structure can be big
The big electric conductivity for promoting product, this point are graphited carbon for the carbon of raising, this can greatly improve the electric conductivity of product,
Chemical property for improving product has very great help, especially high rate performance.
3) electrochemical performance of the product prepared by the present invention, under the electric current of 0.1A/g, the capacity of battery is up to
470 mAh/g, when current density increases to 8A/g, battery can still keep the capacity of 260mAh/g, it is seen that product
Under high current, high power capacity and stability can be still kept.
4) the product graphite carbon coating Fe prepared by the present invention3O4, wherein having carried out N doping to graphitic carbon, substantially increase
The reactivity of clad graphitic carbon.
Description of the drawings
Fig. 1 is the XRD diagram that the present invention implements 1.
Fig. 2 is the low power TEM figures that the present invention implements 1.
Fig. 3 is the high power TEM figures that the present invention implements 1.
Fig. 4 is to implement 1 electric performance test figure.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
1) analytically pure ammonium ferric oxalate, urea, fructose and ethanedioic acid are add to deionized water, stir 20min,
It is a concentration of that a concentration of 1mol/L of ammonium ferric oxalate, urea concentration 2mol/L, fructose concentration 0.1mol/L, ethanedioic acid is made
The mixed solution A of 0.1 mol/L；
2) by the mixed solution A of above-mentioned preparation at 200W ultrasound 2h, equably mixed solution B is made；
3) mixed solution B is freezed into 2h at -30 DEG C, then drying for 24 hours, obtains loose production in vacuum freeze drier
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, argon flow amount 100sccm, with 10 DEG C/min's
Rate keeps the temperature 2h from room temperature to 600 DEG C, obtains product D；
5) product D is placed in Muffle furnace, in air atmosphere, 300 DEG C is warming up to the rate of 5 DEG C/min from room temperature,
And 0.5h is kept the temperature, obtain graphitic carbon support and the carbon coating Fe of N doping3O4Anode material of lithium-ion battery.
Product is analyzed using Rigaku D/max2000PCX- x ray diffractometer xs, the XRD of products therefrom is shown in Fig. 1.From Fig. 1
In it can be seen that product be Fe3O4。
Referring to Fig. 2 and Fig. 3, the FEI Tecnai G2F20S-TWIN transmission electron microscopes that sample U.S. FEI is produced into
Row observation, as can be seen that product is in the carbon-coated structure of graphite from Fig. 2 and Fig. 3, graphitization clear-cut texture is visible.
The product of gained is prepared into button-shaped sodium-ion battery, specific encapsulation step is as follows：By activity powder, conductive agent
(Super P), bonding agent (carboxyl methyl cellulose) are 7 according to mass ratio:2:After 1 proportioning grinding uniformly, slurry is made,
Equably slurry is applied on copper foil with coating device, then in 80 DEG C of dry 12h of vacuum drying chamber.Electrode slice is assembled into later
Sodium ion half-cell carries out constant current charge-discharge test, test voltage 0.01V- using new prestige electrochemical workstation to battery
3.0V, test current density size is respectively 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 4A/g and 8A/g.Test result
See Fig. 4, as can be seen from the figure under the electric current of 0.1A/g, the capacity of battery is up to 470mAh/g, as current density increases,
Capacity slowly smoothly reduces, and when current density increases to 8A/g, battery can still keep the capacity of 260mAh/g, it is seen that
Product under high current, can still keep high power capacity and stability.
Embodiment 2
1) analytically pure ferric citrate, urea, sucrose and ethanedioic acid are add to deionized water, stir 20min, system
It is a concentration of at a concentration of 2mol/L of ammonium ferric oxalate, urea concentration 5mol/L, concentration of glucose 0.2mol/L, ethanedioic acid
The mixed solution A of 0.2mol/L；
2) by the mixed solution A of above-mentioned preparation at 500W ultrasound 1h, equably mixed solution B is made；
3) mixed solution B is freezed into 3h at -30 DEG C, then the dry 30h in vacuum freeze drier, obtains loose production
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, argon flow amount 200sccm, with 10 DEG C/min's
Rate keeps the temperature 2h from room temperature to 500 DEG C, obtains product D；
5) product D is placed in Muffle furnace, in air atmosphere, with the rate of 10 DEG C/min from room temperature to 400 DEG C,
And 0.5h is kept the temperature, obtain graphitic carbon support and the carbon coating Fe of N doping3O4Anode material of lithium-ion battery.
Embodiment 3
1) analytically pure ammonium ferric oxalate, urea, cellulose and acetic acid are add to deionized water, stir 10min,
A concentration of 0.5mol/L of ammonium ferric oxalate, urea concentration 0.5mol/L, fructose concentration 0.4mol/L, ethanedioic acid concentration is made
For the mixed solution A of 0.4mol/L；
2) by the mixed solution A of above-mentioned preparation at 300W ultrasound 0.5h, equably mixed solution B is made；
3) mixed solution B is freezed into 2h at -30 DEG C, then the dry 48h in vacuum freeze drier, obtains loose production
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, argon flow amount 50sccm, with the speed of 5 DEG C/min
Rate keeps the temperature 0.5h from room temperature to 400 DEG C, obtains product D；
5) product D is placed in Muffle furnace, in air atmosphere, with the rate of 6 DEG C/min from room temperature to 250 DEG C,
And 4h is kept the temperature, obtain graphitic carbon support and the carbon coating Fe of N doping3O4Anode material of lithium-ion battery.
Embodiment 4
1) analytically pure ferric citrate, urea, fructose and acetic acid are add to deionized water, stir 30min, is made
A concentration of 5mol/L of ammonium ferric oxalate, urea concentration 7mol/L, concentration of glucose 0.05mol/L, ethanedioic acid are a concentration of
The mixed solution A of 0.5mol/L；
2) by the mixed solution A of above-mentioned preparation at 400W ultrasound 1.5h, equably mixed solution B is made；
3) mixed solution B is freezed into 4h at -30 DEG C, then the dry 40h in vacuum freeze drier, obtains loose production
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, argon flow amount 350sccm, with 15 DEG C/min's
Rate keeps the temperature 1.5h from room temperature to 450 DEG C, obtains product D；
5) product D is placed in Muffle furnace, in air atmosphere, with the rate of 7 DEG C/min from room temperature to 350 DEG C,
And 2h is kept the temperature, obtain graphitic carbon support and the carbon coating Fe of N doping3O4Anode material of lithium-ion battery.
Embodiment 5
1) analytically pure ferric citrate, urea, cellulose and ethanedioic acid are add to deionized water, stir 15min,
A concentration of 3mol/L of ammonium ferric oxalate, urea concentration 10mol/L, concentration of glucose 0.5mol/L, ethanedioic acid concentration is made
For the mixed solution A of 0.01mol/L；
2) by the mixed solution A of above-mentioned preparation at 200W ultrasound 2h, equably mixed solution B is made；
3) mixed solution B is freezed into 5h at -30 DEG C, then the dry 30h in vacuum freeze drier, obtains loose production
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, argon flow amount 150sccm, with 12 DEG C/min's
Rate keeps the temperature 3h from room temperature to 550 DEG C, obtains product D；
5) product D is placed in Muffle furnace, in air atmosphere, with the rate of 8 DEG C/min from room temperature to 400 DEG C,
And 1h is kept the temperature, obtain graphitic carbon support and the carbon coating Fe of N doping3O4Anode material of lithium-ion battery.
Claims (8)
1. a kind of graphitic carbon of N doping supports and cladding Fe3O4The preparation method of anode material of lithium-ion battery, feature exist
In including the following steps：
1) source of iron, urea, carbohydrate and organic acid are add to deionized water, are stirred evenly, it is a concentration of that source of iron is made
0.5-5mol/L, urea concentration 0.5-10mol/L, carbohydrate concentration 0.05-0.5mol/L, organic acid concentration are
The mixed solution A of 0.01-0.5mol/L；
2) by the mixed solution A of above-mentioned preparation at 200~500W ultrasound 0.5-2h, uniform mixed solution B is made；
3) will be dry after mixed solution B freezings, obtain loose product C；
4) it under an argon atmosphere by loose product C, with the rate of 5-15 DEG C/min from room temperature to 400-600 DEG C, and keeps the temperature
0.5-3h obtains product D；
5) in air atmosphere by product D, with the rate of 5-10 DEG C/min from room temperature to 250-400 DEG C, and 0.5- is kept the temperature
4h obtains graphitic carbon support and the carbon coating Fe of N doping3O4Anode material of lithium-ion battery.
2. a kind of graphitic carbon of N doping according to claim 1 supports and cladding Fe3O4Anode material of lithium-ion battery
Preparation method, which is characterized in that source of iron is ammonium ferric oxalate or ferric citrate in step 1).
3. a kind of graphitic carbon of N doping according to claim 1 supports and cladding Fe3O4Anode material of lithium-ion battery
Preparation method, which is characterized in that organic acid is acetic acid or ethanedioic acid in step 1).
4. a kind of graphitic carbon of N doping according to claim 1 supports and cladding Fe3O4Anode material of lithium-ion battery
Preparation method, which is characterized in that carbohydrate is fructose, sucrose or cellulose in step 1).
5. a kind of graphitic carbon of N doping according to claim 1 supports and cladding Fe3O4Anode material of lithium-ion battery
Preparation method, which is characterized in that the time stirred in step 1) is 10-30min.
6. a kind of graphitic carbon of N doping according to claim 1 supports and cladding Fe3O4Anode material of lithium-ion battery
Preparation method, which is characterized in that the temperature freezed in step 3) is -30 DEG C, time 2-5h.
7. a kind of graphitic carbon of N doping according to claim 1 supports and cladding Fe3O4Anode material of lithium-ion battery
Preparation method, which is characterized in that dry in step 3) is specifically the dry 24-48h in vacuum freeze drier.
8. a kind of graphitic carbon of N doping according to claim 1 supports and cladding Fe3O4Anode material of lithium-ion battery
Preparation method, which is characterized in that the flow of argon gas is 50~500sccm in step 4).
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| CN108306001B (en) * | 2018-01-08 | 2021-04-16 | 北京科技大学 | Lithium ion battery cathode material Fe3O4Preparation method of/N-C |
| CN109192938B (en) * | 2018-07-27 | 2021-04-20 | 华南师范大学 | Flexible material and preparation method and application thereof |
| CN109280934A (en) * | 2018-09-28 | 2019-01-29 | 陕西科技大学 | A kind of carbon-coated vanadium nitride elctro-catalyst, preparation method and application |
| CN110961136B (en) * | 2019-12-18 | 2022-06-03 | 西安工业大学 | Fe with three-dimensional continuous structure3N-coated FeNCN compound and preparation method thereof |
| CN112047334A (en) * | 2020-08-19 | 2020-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nitrogen-doped lithium battery graphite cathode |
| CN113912023B (en) * | 2021-10-08 | 2023-05-23 | 常熟理工学院 | Preparation method of negative electrode material of sodium ion battery |
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