CN106848302A - A kind of preparation method of the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion battery negative material of N doping - Google Patents

A kind of preparation method of the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion battery negative material of N doping Download PDF

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CN106848302A
CN106848302A CN201710032005.6A CN201710032005A CN106848302A CN 106848302 A CN106848302 A CN 106848302A CN 201710032005 A CN201710032005 A CN 201710032005A CN 106848302 A CN106848302 A CN 106848302A
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lithium ion
graphene
preparation
graphene coated
self assembly
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曹丽云
齐慧
李嘉胤
黄剑锋
杜欣怡
马萌
李春光
陈文卓
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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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
    • 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
    • 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
    • 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 kind of preparation method of the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion battery negative material of N doping, commercially available graphene oxide is dissolved in ethylene glycol first, then by the finely dispersed suspension A of ultrasonically treated formation graphene oxide；Then by analytically pure soluble ferric iron salt and surfactant addition deionized water, stirring makes molysite fully dissolve, and is then added in suspension A, is configured to the mixed solution B of molysite and graphene oxide；Then mixed solution B is carried out into microwave reaction, obtains product C；Finally by product C and urea or melamine mixed grinding, then sealed pyrolysis are the graphene coated Fe for obtaining N doping3O4Self-assembly microspheres lithium ion battery negative material.By graphene coated, it can effectively solve Fe to the present invention3O4The problem of poorly conductive, makes battery structure more stablize, so as to improve the stable circulation performance of battery.

Description

A kind of graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of N doping The preparation method of cell negative electrode material
Technical field
The invention belongs to electrochemical technology field, and in particular to a kind of graphene coated ferroso-ferric oxide of N doping is from group The preparation method of the multistage microballoon lithium ion battery negative material of dress.
Background technology
Because lithium ion battery has energy density high, long service life, advantages of environment protection, recent years turn into Study hotspot, and it is successfully realized commercialization.Electric automobile can be applied in order to develop the next generation, the large-scale energy is deposited The more effective lithium ion battery material of storage equipment, can search out a kind of negative material with excellent chemical property is Individual key factor.Oxide (the Fe of iron2O3,Fe3O4) there is high power capacity (~1000mAh/g), low cost, wide material sources are nontoxic The advantages of, with existing graphite electrode (372mAhg-1) compare, with significant advantage.But single Fe3O4Poorly conductive, Easily there is volumetric expansion during discharge and recharge and cause activity powder to be come off from collection liquid surface, and cause electrode capacity drastically to decline, this A little shortcomings greatly limit its extensive use, it is therefore desirable to which the material for finding good conductivity is combined to improve its conduction with it Property, Xiulin Fan are by Fe3O4And carbon coated (J.Mater.Chem.A, 2014,2,14641-14648) is carried out on surface, To improve its structural stability, but because the electric conductivity of material is poor, the high rate performance of this composite construction need to be carried It is high.Jisheng Zhou (RSC Advances, 2011,1,782-791) are by by Fe3O4Graphene simple composite improves material The electric conductivity of material, but due to Fe3O4Graphenic surface is simply simply attached to, not by graphene coated, this kind of structure is being filled Still the stability of activity powder efflorescence, material can be caused further raising is also needed to during electric discharge.
The content of the invention
It is an object of the invention to provide a kind of graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium of N doping The preparation method of ion battery cathode material, with the defect for overcoming above-mentioned prior art to exist, the present invention passes through graphene coated It can effectively solve Fe3O4Poorly conductive, can suppress volumetric expansion again, while carry out N doping to Graphene can also carry significantly The reactivity site of Graphene high, makes battery structure more stablize, so as to improve the stable circulation performance of battery.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of system of the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion battery negative material of N doping Preparation Method, comprises the following steps：
1) commercially available graphene oxide is dissolved in ethylene glycol, is then disperseed by ultrasonically treated formation graphene oxide Uniform suspension A；
2) by analytically pure soluble ferric iron salt and surfactant addition deionized water, stirring makes molysite fully dissolve, It is then added in suspension A, is configured to the mixed solution B of molysite and graphene oxide, V in mixed solution BEthylene glycol：VWater=(3 ~1)：1, the concentration of molysite is 0.05~0.5mol/L, and the concentration of surfactant is 0.05~0.5g/L, graphene oxide Concentration is 0.5~2.5mg/mL；
3) mixed solution B is carried out into microwave reaction, obtains product C；
4) by product C and urea or melamine with mass ratio 1:(1~5) mixed grinding, then sealed pyrolysis are to obtain The graphene coated Fe of N doping3O4Self-assembly microspheres lithium ion battery negative material.
Further, step 1) in commercially available graphene oxide is dissolved in the molten of 1~5mg/mL is configured in ethylene glycol Liquid.
Further, step 1) in ultrasonically treated power be 300W, the time is 1~3h.
Further, step 2) described in soluble ferric iron salt be iron ammonium oxalate or ammonium ferric sulfate.
Further, step 2) described in surfactant be PVP or PEG.
Further, step 2) middle stirring 10min-30min, molysite is fully dissolved.
Further, step 3) in microwave reaction be specially：Mixed solution B is poured into microwave hydrothermal reaction kettle, then Sealed reactor, is put it into microwave hydrothermal reaction, and at 100-180 DEG C, the reaction time is controlled in 10- for reaction temperature control 120min。
Further, the compactedness of microwave hydrothermal reaction kettle is 30%-80%.
Further, step 4) in sealed pyrolysis be specially：Porcelain is put into after product C and urea or melamine mixed grinding In boat, after being warming up to 400-700 DEG C with the heating rate of 3-10 DEG C/min in tube furnace, 1-5h, then furnace cooling are incubated To room temperature.
Compared with prior art, the present invention has following beneficial technique effect：
Electric conductivity to improve product of the invention, for the purpose of alleviation volumetric expansion, and then is prepared for the Graphene of N doping Cladding classification Fe3O4Porous material, wherein Graphene have offer electric conductivity, by coating the double action come rock-steady structure, greatly Improve Fe greatly3O4Chemical property, in addition the present invention realize oxygen using the coordination of organic molysite and graphene oxide Change iron in graphenic surface growth in situ, and then form the structure of graphene coated, experimental technique is simple, with low cost, it is easy to Realize, employ the ingenious combination of microwave hydrothermal and high temperature pyrolysis, the hollow Fe of graphene coated of this N doping3O4Material is special Different structure, alleviates volumetric expansion significantly, improves the electric conductivity of product, and the circulation of product and high rate performance have been obtained significantly Lifting.
Further, by controlling reaction condition, the graphene coated Fe of N doping prepared by the present invention3O4Self assembly is micro- Under the electric current of 1A/g, electric discharge first has reached 900-1350mAh/g to ball lithium ion battery negative material, by 100 circulations Afterwards, still it is maintained at 750-11200mAh/g.
Brief description of the drawings
Fig. 1 is the XRD of product prepared by embodiment 1；
Fig. 2 is the SEM figures of product prepared by embodiment 1, and multiplication factor is 10,000 times；
Fig. 3 is the SEM figures of product prepared by embodiment 1, and multiplication factor is 40,000 times；
Fig. 4 is the TEM figures of product prepared by embodiment 1, and multiplication factor is 40,000 times；
Fig. 5 is the TEM figures of product prepared by embodiment 1, and multiplication factor is 200,000 times；
Fig. 6 is the chemical property figure of product prepared by embodiment 1.
Specific embodiment
The present invention is described in further detail below：
A kind of system of the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion battery negative material of N doping Preparation Method, comprises the following steps：
1) commercially available graphene oxide is dissolved in ethylene glycol the solution for being configured to 1~5mg/mL, is occurred by ultrasound Device forms the finely dispersed suspension A of graphene oxide with the 1~3h of power ultrasonic of 300W；
2) by analytically pure soluble ferric iron salt (iron ammonium oxalate or ammonium ferric sulfate), surfactant (PVP or PEG) is added to In deionized water, 10min-30min is stirred, molysite is fully dissolved, be then added in suspension A, be configured to molysite and oxygen The mixed solution B of graphite alkene, wherein solvent are the mixed solution of ethylene glycol and water, and VEthylene glycol：VWaterIt is (3~1)：1, molysite Concentration is 0.05~0.5mol/L, and surfactant concentration is 0.05~0.5g/L, the concentration of graphene oxide for 0.5~ 2.5mg/mL；
3) by the mixed solution B of above-mentioned preparation, pour into microwave hydrothermal reaction kettle, compactedness is 30%-80%, Ran Houmi Envelope reactor, is put it into microwave hydrothermal reaction, and at 100-180 DEG C, the reaction time is controlled in 10- for reaction temperature control 120min, reaction naturally cools to room temperature after terminating, and the product of gained is designated as into C；
4) by product C and urea (or melamine) with mass ratio 1:1~1:5 mixed grindings, are put into porcelain boat, in tubular type Sealed pyrolysis in stove, pyrolysis temperature is 400-700 DEG C, and pyrolysis time is 1-5h, and heating rate is 3-10 DEG C/min, is finally given The graphene coated Fe of N doping3O4Self-assembly microspheres lithium ion battery negative material.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
1) commercially available graphene oxide is dissolved in ethylene glycol organic solution the solution for being configured to 1mg/mL, by ultrasound Generator is formed the finely dispersed suspension of graphene oxide and is designated as suspension A with the power ultrasonic 1h of 300W；
2) by analytically pure soluble iron iron ammonium oxalate, surfactant PVP is added in deionized water, stirs 10min, Molysite is fully dissolved, is then added in suspension A, be configured to the mixed solution B of molysite and graphene oxide, wherein solvent It is ethylene glycol and the mixed solution (V of waterEthylene glycol：VWaterIt is 3：1), the concentration of molysite is 0.05mol/L, and PVP concentration is 0.5g/L, oxygen The concentration of graphite alkene is 0.5mg/mL；
3) by the mixed solution B of above-mentioned preparation, pour into microwave hydrothermal reaction kettle, compactedness is 50%, then seal anti- Kettle is answered, is put it into microwave hydrothermal reaction, at 100 DEG C, reaction time control is in 10min, reaction knot for reaction temperature control Room temperature is naturally cooled to after beam, the product of gained is designated as C；
4) by product C and urea with mass ratio 1:1 mixed grinding, is put into porcelain boat, the sealed pyrolysis in tube furnace, pyrolysis Temperature is 400 DEG C, and pyrolysis time is 5h, and heating rate is 5 DEG C/min, finally gives the graphene coated Fe of N doping3O4From group Dress microballoon lithium ion battery negative material.
Referring to Fig. 1, the product particles of gained are analyzed into sample, hair with Rigaku D/max2000PCX- x ray diffractometer xs Existing product is the Fe of phase3O4(JCPDS 85-1436)。
Referring to Fig. 2 and Fig. 3, the product of gained is entered with the JSM-6700F type SEM that Japanese firm produces Row observation, it can be seen that made Fe from SEM figures3O4Fe in/graphene complex3O4The size of microballoon is 600-800nm, It is dispersed in Graphene, the surface of Fe3O4 microballoons is coated by a layer graphene.
Referring to Fig. 4 and Fig. 5, the product of gained is transmitted with the FEI Tecnai G2 F20 S-TWIN that U.S. FEI is produced Electronic Speculum is observed, as can be seen from Figure 4 Fe3O4Fe in/graphene complex3O4Microballoon is in Hollow hierarchical, from Fig. 5 In it can also be seen that microballoon is by length to be the hierarchy that assembles of club shaped structure of 100nm.
The product of the gained of embodiment 1 is prepared into button-shaped lithium ion battery, specific encapsulation step is as follows：By activity Powder, conductive agent (Super P), bonding agent (carboxyl methyl cellulose) is 8 according to mass ratio:1:After 1 proportioning grinding is uniform, Be made slurry, equably slurry is applied on Copper Foil with coating device, then in vacuum drying chamber 80 DEG C dry 12h.Afterwards by electricity Pole piece is assembled into lithium ion half-cell, and constant current charge-discharge test, test voltage are carried out to battery using new prestige electrochemical workstation It is 0.01V-3.0V, test current density size is 1A/g, and test result is shown in Fig. 6, by after the circulation of 100 circles, battery is still The capacity of 1150mAh/g can be kept, it is seen that product under high current, product can still keep high power capacity and stability, This is attributed to the special construction of the graphene coated of N doping.
Embodiment 2
1) commercially available graphene oxide is dissolved in ethylene glycol organic solution the solution for being configured to 5mg/mL, by ultrasound Generator is formed the finely dispersed suspension of graphene oxide and is designated as suspension A with the power ultrasonic 2h of 300W；
2) by analytically pure soluble ferric iron salt ammonium ferric sulfate, Surfactant PEG is added in deionized water, stirring 20min, molysite is fully dissolved, and is then added in suspension A, is configured to the mixed solution B of molysite and graphene oxide, its Middle solvent is mixed solution (the V ethylene glycol of ethylene glycol and water：V water is 2：1), the concentration of molysite is 0.2mol/L, and PEG concentration is 0.5g/L, the concentration of graphene oxide is 2.5mg/mL；
3) by the mixed solution B of above-mentioned preparation, pour into microwave hydrothermal reaction kettle, compactedness is 60%, then seal anti- Kettle is answered, is put it into microwave hydrothermal reaction, at 160 DEG C, reaction time control is in 20min, reaction knot for reaction temperature control Room temperature is naturally cooled to after beam, the product of gained is designated as C；
4) by product C and melamine with mass ratio 1:2 mixed grindings, are put into porcelain boat, the sealed pyrolysis in tube furnace, Pyrolysis temperature is 600 DEG C, and pyrolysis time is 1h, and heating rate is 10 DEG C/min, finally gives the graphene coated of N doping Fe3O4Self-assembly microspheres lithium ion battery negative material.
Embodiment 3
1) commercially available graphene oxide is dissolved in ethylene glycol organic solution the solution for being configured to 3mg/mL, by ultrasound Generator is formed the finely dispersed suspension of graphene oxide and is designated as suspension A with the power ultrasonic 1h of 300W；
2) by analytically pure soluble ferric iron salt iron ammonium oxalate, surfactant PVP is added in deionized water, stirring 20min, molysite is fully dissolved, and is then added in suspension A, is configured to the mixed solution B of molysite and graphene oxide, its Middle solvent is mixed solution (the V ethylene glycol of ethylene glycol and water：V water is 1：1), the concentration of molysite is 0.1mol/L, and PVP concentration is 0.2g/L, the concentration 1.5mg/mL of graphene oxide；
3) by the mixed solution B of above-mentioned preparation, pour into microwave hydrothermal reaction kettle, compactedness is 50%, then seal anti- Kettle is answered, is put it into microwave hydrothermal reaction, at 120 DEG C, reaction time control is in 120min, reaction knot for reaction temperature control Room temperature is naturally cooled to after beam, the product of gained is designated as C；
4) by product C and urea with mass ratio 1:5 mixed grindings, are put into porcelain boat, the sealed pyrolysis in tube furnace, pyrolysis Temperature is 500 DEG C, and pyrolysis time is 2h, and heating rate is 3 DEG C/min, finally gives the graphene coated Fe of N doping3O4From group Dress microballoon lithium ion battery negative material.
Embodiment 4
1) commercially available graphene oxide is dissolved in ethylene glycol organic solution the solution for being configured to 1mg/mL, by ultrasound Generator is formed the finely dispersed suspension of graphene oxide and is designated as suspension A with the power ultrasonic 3h of 300W；
2) by analytically pure soluble ferric iron salt ammonium ferric sulfate, Surfactant PEG is added in deionized water, stirring 30min, molysite is fully dissolved, and is then added in suspension A, is configured to the mixed solution B of molysite and graphene oxide, its Middle solvent is mixed solution (the V ethylene glycol of ethylene glycol and water：V water is 1:1), the concentration of molysite is 0.5mol/L, and PEG concentration is 0.05g/L, the concentration of graphene oxide is 1.5mg/mL；
3) by the mixed solution B of above-mentioned preparation, pour into microwave hydrothermal reaction kettle, compactedness is 80%, then seal anti- Kettle is answered, is put it into microwave hydrothermal reaction, at 180 DEG C, reaction time control is in 20min, reaction knot for reaction temperature control Room temperature is naturally cooled to after beam, the product of gained is designated as C；
4) by product C and urea with mass ratio 1:3 mixed grindings, are put into porcelain boat, the sealed pyrolysis in tube furnace, pyrolysis Temperature is 700 DEG C, and pyrolysis time is 3h, and heating rate is 8 DEG C/min, finally gives the graphene coated Fe of N doping3O4From group Dress microballoon lithium ion battery negative material.

Claims (9)

1. the preparation of the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion battery negative material of a kind of N doping Method, it is characterised in that comprise the following steps：
1) commercially available graphene oxide is dissolved in ethylene glycol, is then uniformly dispersed by ultrasonically treated formation graphene oxide Suspension A；
2) by analytically pure soluble ferric iron salt and surfactant addition deionized water, stirring makes molysite fully dissolve, then It is added in suspension A, is configured to the mixed solution B of molysite and graphene oxide, V in mixed solution BEthylene glycol：VWater=(3~1)： 1, the concentration of molysite is 0.05~0.5mol/L, and the concentration of surfactant is 0.05~0.5g/L, the concentration of graphene oxide It is 0.5~2.5mg/mL；
3) mixed solution B is carried out into microwave reaction, obtains product C；
4) by product C and urea or melamine with mass ratio 1:(1~5) mixed grinding, then sealed pyrolysis are to obtain nitrogen to mix Miscellaneous graphene coated Fe3O4Self-assembly microspheres lithium ion battery negative material.
2. the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of a kind of N doping according to claim 1 The preparation method of cell negative electrode material, it is characterised in that step 1) in commercially available graphene oxide be dissolved in ethylene glycol match somebody with somebody It is set to the solution of 1~5mg/mL.
3. the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of a kind of N doping according to claim 1 The preparation method of cell negative electrode material, it is characterised in that step 1) in ultrasonically treated power be 300W, the time is 1~3h.
4. the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of a kind of N doping according to claim 1 The preparation method of cell negative electrode material, it is characterised in that step 2) described in soluble ferric iron salt be iron ammonium oxalate or ferric sulfate Ammonium.
5. the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of a kind of N doping according to claim 1 The preparation method of cell negative electrode material, it is characterised in that step 2) described in surfactant be PVP or PEG.
6. the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of a kind of N doping according to claim 1 The preparation method of cell negative electrode material, it is characterised in that step 2) middle stirring 10min-30min, molysite is fully dissolved.
7. the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of a kind of N doping according to claim 1 The preparation method of cell negative electrode material, it is characterised in that step 3) in microwave reaction be specially：Mixed solution B is poured into microwave In hydrothermal reaction kettle, then sealed reactor, is put it into microwave hydrothermal reaction, and reaction temperature is controlled at 100-180 DEG C, Reaction time is controlled in 10-120min.
8. the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of a kind of N doping according to claim 7 The preparation method of cell negative electrode material, it is characterised in that the compactedness of microwave hydrothermal reaction kettle is 30%-80%.
9. the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion of a kind of N doping according to claim 1 The preparation method of cell negative electrode material, it is characterised in that step 4) in sealed pyrolysis be specially：Product C and urea or melamine It is put into porcelain boat after amine mixed grinding, after being warming up to 400-700 DEG C with the heating rate of 3-10 DEG C/min in tube furnace, insulation 1-5h, then cools to room temperature with the furnace.
CN201710032005.6A 2017-01-17 2017-01-17 A kind of preparation method of the graphene coated ferroso-ferric oxide self assembly multistage microballoon lithium ion battery negative material of N doping Pending CN106848302A (en)

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CN110492079A (en) * 2019-08-26 2019-11-22 东北大学 A kind of preparation method and application of sheet ferroso-ferric oxide negative electrode material
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CN111403701A (en) * 2020-03-09 2020-07-10 南京邮电大学 Preparation method of iron-based compound composite nitrogen-doped graphene sodium-ion negative electrode battery material

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CN110492079A (en) * 2019-08-26 2019-11-22 东北大学 A kind of preparation method and application of sheet ferroso-ferric oxide negative electrode material
CN111403701A (en) * 2020-03-09 2020-07-10 南京邮电大学 Preparation method of iron-based compound composite nitrogen-doped graphene sodium-ion negative electrode battery material
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