CN108649191A - The preparation method and its resulting materials of a kind of antimony/nitrogen-doped graphene compound and application - Google Patents
The preparation method and its resulting materials of a kind of antimony/nitrogen-doped graphene compound and application Download PDFInfo
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- CN108649191A CN108649191A CN201810297192.5A CN201810297192A CN108649191A CN 108649191 A CN108649191 A CN 108649191A CN 201810297192 A CN201810297192 A CN 201810297192A CN 108649191 A CN108649191 A CN 108649191A
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Abstract
The present invention provides preparation method and its gained composite material and application of the composite material as anode material of lithium-ion battery of a kind of antimony/nitrogen-doped graphene compound, and the preparation method comprises the following steps：1) by graphene oxide, 1 ethyl, 3 methylimidazole cdicynanmide and antimony powder ball milling mixing；2) it mixture and is scattered in distilled water after taking out ball milling, ultrasonic disperse is uniform, freeze-drying；3) by step 2) products therefrom in H2Carbonization is to get the antimony/nitrogen-doped graphene compound under/Ar atmosphere.Compared with the existing technology, the method of the present invention is simple for process, the raw material used is environmentally protective, it is suitable for producing in batches, antimony obtained/nitrogen-doped graphene compound has excellent chemical property, it can be used as the low star antimony of ideal anode material of lithium-ion battery substitution reversible capacity and be applied to sodium-ion battery, be a kind of promising anode material of lithium-ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of antimony/nitrogen-doped graphene compound and its resulting materials and applications, belong to
Electrode material technical field.
Background technology
Lithium ion battery is as the energy-storage system being most widely used, and due to its energy density height, life cycle is long, in electricity
The power supply market of electrical automobile and portable electronic device occupies leading position.However, the scarcity of lithium resource and geographical distribution are not
Equilibrium seriously hinders large-scale application of the lithium ion battery in energy storage.Sodium-ion battery has and the comparable physics of lithium and change
Characteristic is learned, and sodium is resourceful, it is cheap, it is considered to be useful for larger scale stationary energy storage.Recently, a large amount of stratiform oxidation
Object and polyanionic compound have been found as efficient sodium-ion battery positive material.Although a variety of negative electrode of lithium ion battery materials
Material has been used for sodium-ion battery research, but most of trials are all unsatisfactory.Therefore, exploitation has height ratio capacity and suitable oxygen
The novel anode material of change reduction potential is a significant challenge in sodium-ion battery field.
Antimony is due to higher theoretical specific capacity (660mAh g-1) receive the extensive concern of researchers.Antimony and sodium
Between can form Na3Sb alloys, but in sodium with during going sodium serious volume expansion can occur for antimony sill
(~390%) causes active material to lose electrical contact with conductive additive, decays rapidly so as to cause capacity.In cyclic process
Middle antimony particle surface can form the process that thick, unstable solid electrolyte film with electronic isolation hinders reaction, drop
Low first circle coulombic efficiency so that cyclical stability is deteriorated.
Invention content
Goal of the invention：For problems of the prior art, the object of the present invention is to provide a kind of antimony/N doping graphite
The preparation method and its resulting materials of alkene compound and application, the preparation method is environmentally protective, it is simple for process, can scale,
And gained compound electrochemical performance.
Technical solution：To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows：
A kind of preparation method of antimony/nitrogen-doped graphene compound, includes the following steps：
1) by graphene oxide, 1- ethyl-3-methylimidazoles cdicynanmide and antimony powder ball milling mixing；
2) it mixture and is scattered in distilled water after taking out ball milling, ultrasonic disperse is uniform, freeze-drying；
3) by step 2) products therefrom in H2Carbonization is to get the antimony/nitrogen-doped graphene compound under/Ar atmosphere.
In the step 1), the mass ratio of the 1- ethyl-3-methylimidazoles cdicynanmide of addition, graphene oxide and antimony is 1:
2:(4~7).
In the step 1), the rotating speed of ball milling and time are respectively 600~800rpm and 20~for 24 hours.
In step 2), the time of the freeze-drying is 2~4 days.
In step 3), the carbonization method is：Step 2) products therefrom is placed in tube furnace, makes tube furnace with 4~10
℃min-1Rate be warming up to 550~650 DEG C after keep 2~4h.
In step 3), the H2In/Ar atmosphere, H2Percent by volume be 5%~10%.
Antimony/nitrogen-doped graphene compound obtained by above-mentioned preparation method.
The antimony/application of the nitrogen-doped graphene compound as anode material of lithium-ion battery.
A kind of anode material of lithium-ion battery, including the antimony/nitrogen-doped graphene compound.
The method of the present invention by graphene oxide, 1- ethyl-3-methylimidazoles cdicynanmide and antimony mixing and ball milling, ultrasonic disperse,
Antimony/nitrogen-doped graphene compound, the 1- ethyl-3-methylimidazoles in carbonisation are obtained after the processing such as freeze-drying, carbonization
Cdicynanmide itself decomposes and realizes the N doping to graphene oxide.Therefore, the present invention provides a kind of antimony/nitrogen-doped graphene
Compound, the antimony/nitrogen-doped graphene compound are prepared by the above method.It is penetrated using x-ray powder diffraction instrument (XRD), X
The composition of photoelectron spectra (XPS) test gained antimony/nitrogen-doped graphene compound；Using scanning electron microscope (SEM),
Transmission electron microscope (TEM), selective electron diffraction (SAED) and high resolution transmission electron microscopy (HRTEM) analysis gained
Size, pattern and the micro-structure etc. of antimony/nitrogen-doped graphene compound.The result shows that the antimony/nitrogen-doped graphene surface light
Sliding and visible redox graphene is in accordion, there is equally distributed antimony nano particle in nitrogen-doped graphene matrix.
Have in the prior art using 1- ethyl-3-methylimidazoles cdicynanmide as antimony made from carbon source/nitrogen-doped carbon compound,
Preparation method is forms complex compound by 1- ethyl-3-methylimidazoles cdicynanmide and antimony trichloride, carbon forming rate height and with carbon after pyrolysis
The form of matrix exists；Because nitrogenous in 1- ethyl-3-methylimidazole cdicynanmides, it is N doping to lead to gained carbon base body.And
In the methods of the invention, 1- ethyl-3-methylimidazoles cdicynanmide does not form complex compound, and 1- second with antimony powder or graphene oxide
Base -3- methylimidazole cdicynanmide dosages are less, and 1- ethyl-3-methylimidazoles cdicynanmide is decomposed completely in pyrolytic process, and real
Now to the N doping of graphene oxide, exist in the form of nitrogen source during entire material preparation.
Antimony/nitrogen-doped graphene compound is carried out chemical property by the present invention as anode material of lithium-ion battery to it
Test, the results showed that, the antimony/nitrogen-doped graphene compound have excellent chemical property, first circle charge/discharge capacity
Respectively 521.9mAh g-1Left and right and 715.5mAh g-1Left and right, first circle coulombic efficiency is 72.9% or so, and high rate performance is excellent
It is different.On the other hand, the present invention provides above-mentioned antimony/application of the nitrogen-doped graphene compound as anode material of lithium-ion battery.
Technique effect：Compared with the existing technology, the method for the present invention is simple for process, and the raw material used is environmentally protective, is suitable for
Batch production, antimony obtained/nitrogen-doped graphene compound have excellent chemical property, can be used as ideal sodium ion electricity
Negative material substitution reversible capacity low star antimony in pond is applied to sodium-ion battery, is a kind of promising sodium-ion battery cathode material
Material.
Description of the drawings
Fig. 1：Wherein, a is that the SEM of antimony/nitrogen-doped graphene compound (Sb/N-rGO) schemes, which shows what pyrolysis obtained
Composite surface is smooth, shows antimony by graphene coated；B is that the TEM of antimony/nitrogen-doped graphene compound schemes, which shows multiple
The average-size for closing antimony in object is about 100nm, and is evenly distributed in carbon substrate；C is antimony/nitrogen-doped graphene compound
SAED schemes, which shows antimony nano particle category hexagonal crystal system；D is that the HRTEM of antimony/nitrogen-doped graphene compound schemes, further
Prove that antimony nano particle is coated by nitrogen-doped graphene.
Fig. 2：Wherein, a is the XRD diagram of Sb/N-rGO compounds, which shows that the characteristic peak (012) of antimony appears in 28.7o,
Corresponding with the interplanar distance of 0.31nm, this is consistent with the result that HRTEM figures are observed；B is Sb/N-rGO compounds and nitrogen
Raman (Raman) figure of doped graphene (N-rGO), two characteristic peaks of amorphous carbon occur in the Raman figures of Sb/N-rGO
In 1351cm-1And 1585cm-1Place.The peak intensity of D bands and G bands ratio (I in Sb/N-rGO samplesD/IG=1.25) it is more than antimony/graphite
Alkene (Sb/rGO) (ID/IG=1.23), this may further enhance its disordered structure due to N doping；C is Sb/N-rGO compounds
And the N 1s XPS figures of N-rGO, there are three peaks N 1s positioned at 397.9e V, 399.2e V and 400.8e V after fitting, this
A little peaks correspond respectively to pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen.Compared with N-rGO, pyridine nitrogen position is by 399.2eV in Sb/N-rGO
Become 399.8eV, i.e., can deviate this to high combination shows that there is relatively strong between antimony and the pyridine nitrogen of/N doping graphene oxide
Interaction, this may be related with Sb-N-C keys are generated during three kinds of raw materials are pyrolyzed.
Fig. 3：Wherein, a is Sb/N-rGO composite electrodes in 0.01-2.0V (vs.Na/Na+) voltage range, sweep speed
For 0.1mV s-1The cyclic voltammetry curve of Shi Qiansi circles；B is the charge/discharge curve figure of Sb/N-rGO compounds.It can therefrom see
Go out first circle charging and discharging curve slope occur in 0.98V or so be because form SEI films；At 0.55V for discharge platform and
0.78V or so is the insertion and abjection that charging platform corresponds to sodium ion respectively.This is phase with the peak what is observed in CV curves
Consistent；C be Sb, Sb/rGO compound, Sb/N-rGO compounds voltage range be 0.01-2V vs Na/Na+, electric current is close
Degree is 0.1Ag-1Under conditions of, the cycle performance figure of 3 kinds of materials, the figure is shown, the charging of the first circles of Sb/N-rGO electrode materials and
Specific discharge capacity is respectively 521.9 and 715.7mAh g-1, corresponding first circle coulombic efficiency is 72.9%, first lap charge and discharge
Electric process specific volume amount loss rate is about 27.1%, it may be possible to by the formation of solid electrolyte film (SEI), the decomposition of electrolyte and sodium
Ion is irreversibly embedded in caused.Capacity is followed successively by 16.6,323.5 and 472.4mAh g after three kinds of electrode cycles 150 enclose-1, capacity retention ratio is respectively 3.14%, 61.9 and 90.5%.It is clear that the cyclical stability of Sb and Sb/rGO compounds is remote
Far lag behind Sb/N-rGO compounds；D is the high rate performance figure of Sb, Sb/rGO, Sb/N-rGO.Even if Sb/N-rGO is in high current
Under density, such as 2 or 5A g-1, capacity may remain in 403 or 360mAh g-1Capacity.
Specific implementation mode
The present invention is further described below with reference to specific embodiment.
Embodiment 1
(1) preparation of Sb/N-rGO compounds
Graphene oxide dispersion (the 10mg mL that 10mL is prepared by Hummers methods-1), 300mg purchase business
Antimony powder and 50mg 1- ethyl-3-methylimidazole cdicynanmides are added in ball grinder, and ball milling is for 24 hours at 800 rpm.To point after ball milling
In dispersion liquid plus 10mL water is diluted, and takes out the mixture after dilution and the ultrasound 5min in numerical control ultrasonic cleaner, is formed
Uniform dispersion.Acquired solution is quickly freezed with liquid nitrogen and is freeze-dried 2 days, gained powder is placed in single temperature zone tube furnace,
In Ar/H2(wherein H under atmosphere2Percent by volume is 5%), with 5 DEG C of min-1Speed be heated to 600 DEG C, and in the temperature
2h is kept, Sb/N-rGO compounds are obtained.
(2) characterization of antimony/nitrogen-doped graphene compound
Utilize size, pattern and the micro-structure of Sb/N-rGO compounds obtained by SEM, TEM, SAED and HRTEM map analysis.
Fig. 1 a are that the SEM of Sb/N-rGO compounds schemes, which shows that the composite surface that pyrolysis obtains is smooth, show antimony by nitrogen-doped carbon
Cladding.Fig. 1 b are that the TEM of Sb/N-rGO compounds schemes, and can be seen that average-size is about 100nm to antimony in the composite by the figure, and
It is evenly distributed in nitrogen-doped graphene matrix.Fig. 1 c are that the SAED of Sb/N-rGO compounds schemes, the bright antimony nano particle of the chart
Belong to hexagonal crystal system.Fig. 1 d are that the HRTEM of Sb/N-rGO compounds schemes, and this view further illustrates nitrogen-doped graphenes to antimony nanometer
The cladding of particle.
Fig. 2 a are the XRD diagram of Sb/N-rGO compounds, which shows that (012) characteristic peak of antimony appears in 28.7o, with
The interplanar distance of 0.31nm is corresponding, this is consistent with the result that HRTEM is observed.Fig. 2 b are Sb/N-rGO compounds and N-
The Raman of rGO schemes, and two characteristic peaks of amorphous carbon appear in 1351cm in the Raman figures of Sb/N-rGO-1And 1585cm-1
Place.The peak intensity of D bands and G bands ratio (I in Sb/N-rGO samplesD/IG=1.25) it is more than Sb/rGO (ID/IG=1.23), this may
Since N doping further enhances its disordered structure.Fig. 2 c are Sb/N-rGO compounds and the N 1s XPS figures of N-rGO, through fitting
There are three peaks N 1s positioned at 397.9e V, 399.2e V and 400.8e V afterwards, these peaks correspond respectively to pyridine nitrogen, pyrroles's nitrogen
With graphite nitrogen.Compared with N-rGO, pyridine nitrogen position becomes 399.8eV from 399.2eV in Sb/N-rGO, i.e., being combined to height can be partially
It moves this and shows that there is stronger interactions between antimony and the pyridine nitrogen of/N doping graphene oxide, this may be with three kinds of originals
It is related that Sb-N-C keys are generated during material pyrolysis.
(3) electrochemical property test
Using deionized water as solvent, by Sb/N-rGO compounds made from the present embodiment and carbon black, carboxymethyl cellulose
Sodium is with 7:2:1 quality is more uniform than ground and mixed, the even slurry of gained is applied on Cu foils and by it at 40 DEG C vacuum
Dry 12h, it is 0.8-1.2mg cm that load capacity, which is made,-2Electrode slice.Use 1mol L-1NaClO4Propene carbonate/fluoro
Ethylene carbonate (volume ratio 1:0.05) solution is made respectively as sodium-ion battery electrolyte, glass fibre and pure sodium metal foil
For sodium-ion battery diaphragm and to electrode.The test of chemical property uses CR2032 batteries.Battery pack, which is mounted in, is full of argon gas gas
It is carried out in the glove box of atmosphere.
The constant current charge-discharge test of battery at room temperature, with blue electricity CT2001A multi-channel battery test systems,
0.01-2V vs Na/Na+It is carried out within the scope of fixed voltage.Cyclic voltammetric (CV) and electrochemical impedance spectroscopy (EIS) use PARSTAT
4000 electrochemical workstations are tested.CV is in 0.1mV s-1Sweep and carried out under speed, EIS is then arrived in frequency range in 100kHz
10mHz, amplitude be 10.0mV sine wave under carry out.Specific performance is shown in Fig. 3.Fig. 3 a are that Sb/N-rGO composite electrodes exist
0.01-2.0V(vs.Na/Na+) voltage range, sweep speed is 0.1mV s-1The cyclic voltammetry curve of Shi Qiansi circles.Fig. 3 b are
The charge/discharge curve figure of Sb/N-rGO compounds.It can be seen that there is slope in 0.98V or so in first circle charging and discharging curve
It is because foring SEI films；Charging platform corresponds to the insertion and abjection of sodium ion respectively at discharge platform and 0.78V at 0.55V.
This is consistent with the peak showed on CV curves.Fig. 3 c are Sb, Sb/rGO compound, Sb/N-rGO compounds in voltage range
For 0.01-2V vs Na/Na+, current density 0.1Ag-1Under conditions of, the cycle performance figure of 3 kinds of materials, the figure is shown, Sb/
It is respectively 521.9 and 715.7mAh g that the first circle of N-rGO electrode materials, which is charged and discharged specific capacity,-1, corresponding first circle library
Human relations efficiency is 72.9%, and first lap charge and discharge process specific volume amount loss rate is about 27.1%, it may be possible to by solid electrolyte film
(SEI) formation, irreversibly insertion causes for the reduction decomposition and sodium ion of electrolyte.Capacity after three kinds of electrode cycles 150 enclose
It is followed successively by 16.6,323.5 and 472.4mAh g-1, capacity retention ratio is respectively 3.14%, 61.9 and 90.5%.It is clear that Sb
Lag far behind Sb/N-rGO compounds with the cyclical stability of Sb/rGO compounds.Fig. 3 d are Sb, Sb/rGO, Sb/N-rGO
High rate performance figure.Even if Sb/N-rGO is at higher current densities, such as 2 or 5Ag-1, capacity may remain in 403 or 360mAh
g-1Capacity.
Comparative example 1
(1) business antimony powder is bought
(2) electrochemical property test
Antimony powder is with carbon black, sodium carboxymethylcellulose with 7:2:Ground and mixed is uniform in water for 1 mass ratio, by the equal of gained
Homogenate body is applied on Cu foils and it is dried in vacuo 12h at 40 DEG C, and it is 0.8-1.2mg cm that load capacity, which is made,-2Electrode
Piece.Use 1mol L-1NaClO4Propene carbonate/fluoro carbon ethylene carbonate (volume ratio 1:0.05) solution as sodium from
Sub- battery electrolyte, glass fibre and pure sodium metal foil are respectively as sodium-ion battery diaphragm and to electrode.Chemical property
Test uses CR2032 batteries.Battery pack is mounted in the glove box full of argon gas atmosphere and carries out.
Sodium-ion battery performance test is carried out to star antimony, detailed process and conditional parameter are same as Example 1, specific to survey
Test result is shown in Fig. 3.As shown in figure 3, cycle performance figure (Fig. 3 c) shows the first circle charge/discharge capacity 527.4/ of the material
700.4mAh g-1；Discharge capacity is down to 16.6mAh g after 150 circle of cycle-1, capacity retention ratio 3.14%, hence it is evident that be less than
The cycle performance of Sb/N-rGO.
Comparative example 2
(1) preparation of Sb/rGO
Graphene oxide dispersion (the 10mg mL that 10mL is prepared by Hummers methods-1) with 300mg purchase quotient
Industry antimony powder is added in ball grinder, and ball milling is for 24 hours at 800 rpm.Into the dispersion liquid after ball milling plus 10mL water is diluted, and is taken out
Mixture after dilution and the ultrasound 5min in numerical control ultrasonic cleaner form uniform dispersion.By acquired solution liquid nitrogen
It quickly freezes and is freeze-dried 2 days, gained powder is placed in single temperature zone tube furnace, in Ar/H2(wherein H under atmosphere2Volume basis
Than for 5%), with 5 DEG C of min-1Speed be heated to 600 DEG C, and keep 2h in the temperature, obtain Sb/rGO compounds.
(2) electrochemical property test
Using deionized water as solvent, by step (1) Sb/rGO compounds and carbon black, sodium carboxymethylcellulose with 7:2:1
Quality it is more uniform than ground and mixed, the even slurry of gained is applied on Cu foils and it is dried in vacuo 12h at 40 DEG C, make
It is 0.8-1.2mg cm to obtain load capacity-2Electrode slice.Use 1mol L-1NaClO4Propene carbonate/fluoro carbon ethylene carbonate
Ester (volume ratio 1:0.05) solution is as sodium-ion battery electrolyte, and glass fibre and pure sodium metal foil are respectively as sodium ion
Battery diaphragm and to electrode.The test of chemical property uses CR2032 batteries.All operations in relation to battery are all full of argon
It is carried out in the glove box of gas atmosphere.
As shown in figure 3, cycle performance figure (Fig. 3 c) shows the first circle charge/discharge capacity 503.4/681.7mAh of the material
g-1；Specific discharge capacity is down to 323.5mAh g after 150 circle of cycle-1, capacity retention ratio 64.2%.Although capacity retention ratio
It is not low, but it is significantly lower than Sb/N-rGO compounds.
Embodiment 2
Graphene oxide dispersion (the 10mg mL that 10mL is prepared by Hummers methods-1), 250mg purchase business
Antimony powder and 50mg1- ethyl-3-methylimidazole cdicynanmides are added in ball grinder, and ball milling is for 24 hours at 800 rpm.To point after ball milling
In dispersion liquid plus 10mL water is diluted, and takes out the mixture after dilution and the ultrasound 5min in numerical control ultrasonic cleaner, is formed
Uniform dispersion.Acquired solution is quickly freezed with liquid nitrogen and is freeze-dried 2 days, gained powder is placed in single temperature zone tube furnace,
In Ar/H2(wherein H under atmosphere2Percent by volume is 5%), with 4 DEG C of min-1Speed be heated to 600 DEG C, and in the temperature
2h is kept, Sb/N-rGO-2 compounds are obtained.
Structural characterization and electrochemistry are carried out to obtained Sb/N-rGO-2 compounds in the same manner as shown in Example 1
Performance test, it is as a result substantially the same manner as Example 1.
Embodiment 3
Graphene oxide dispersion (the 10mg mL that 10mL is prepared by Hummers methods-1), 350mg purchase business
Antimony powder and 50mg1- ethyl-3-methylimidazole cdicynanmides are added in ball grinder, and ball milling is for 24 hours at 800 rpm.To point after ball milling
In dispersion liquid plus 10mL water is diluted, and takes out the mixture after dilution and the ultrasound 5min in numerical control ultrasonic cleaner, is formed
Uniform dispersion.Acquired solution is quickly freezed with liquid nitrogen and is freeze-dried 2 days, gained powder is placed in single temperature zone tube furnace,
In Ar/H2(wherein H under atmosphere2Percent by volume is 10%), with 5 DEG C of min-1Speed be heated to 600 DEG C, and in the temperature
3h is kept, Sb/N-rGO-3 compounds are obtained.
Structural characterization and electrochemistry are carried out to obtained Sb/N-rGO compounds in the same manner as shown in Example 1
It can test, it is as a result substantially the same manner as Example 1.
Embodiment 4
Graphene oxide dispersion (the 10mg mL that 10mL is prepared by Hummers methods-1), 300mg purchase business
Antimony powder and 50mg1- ethyl-3-methylimidazole cdicynanmides are added in ball grinder, and ball milling is for 24 hours at 600 rpm.To point after ball milling
In dispersion liquid plus 10mL water is diluted, and takes out the mixture after dilution and the ultrasound 5min in numerical control ultrasonic cleaner, is formed
Uniform dispersion.Acquired solution is quickly freezed with liquid nitrogen and is freeze-dried 2 days, gained powder is placed in single temperature zone tube furnace,
In Ar/H2(wherein H under atmosphere2Percent by volume is 10%), with 5 DEG C of min-1Speed be heated to 650 DEG C, and in the temperature
3h is kept, Sb/N-rGO-4 compounds are obtained.
Structural characterization and electrochemistry are carried out to obtained Sb/N-rGO-4 compounds in the same manner as shown in Example 1
Performance test, it is as a result substantially the same manner as Example 1.
Embodiment 5
Graphene oxide dispersion (the 10mg mL that 10mL is prepared by Hummers methods-1), 300mg purchase business
Antimony powder and 50mg1- ethyl-3-methylimidazole cdicynanmides are added in ball grinder, at 600 rpm ball milling 20h.To point after ball milling
In dispersion liquid plus 10mL water is diluted, and takes out the mixture after dilution and the ultrasound 5min in numerical control ultrasonic cleaner, is formed
Uniform dispersion.Acquired solution is quickly freezed with liquid nitrogen and is freeze-dried 4 days, gained powder is placed in single temperature zone tube furnace,
In Ar/H2(wherein H under atmosphere2Percent by volume is 10%), with 10 DEG C of min-1Speed be heated to 550 DEG C, and in the temperature
Upper holding 4h, obtains Sb/N-rGO-4 compounds.
Structural characterization and electrochemistry are carried out to obtained Sb/N-rGO-4 compounds in the same manner as shown in Example 1
Performance test, it is as a result substantially the same manner as Example 1.
Claims (9)
1. a kind of preparation method of antimony/nitrogen-doped graphene compound, which is characterized in that include the following steps：
1) by graphene oxide, 1- ethyl-3-methylimidazoles cdicynanmide and antimony powder ball milling mixing；
2) it mixture and is scattered in distilled water after taking out ball milling, ultrasonic disperse is uniform, freeze-drying；
3) by step 2) products therefrom in H2Carbonization is to get the antimony/nitrogen-doped graphene compound under/Ar atmosphere.
2. the preparation method of antimony according to claim 1/nitrogen-doped graphene compound, which is characterized in that the step
1) in, the mass ratio of the 1- ethyl-3-methylimidazoles cdicynanmide of addition, graphene oxide and antimony is 1:2:(4~7).
3. the preparation method of antimony according to claim 1/nitrogen-doped graphene compound, which is characterized in that the step
1) in, the rotating speed of ball milling and time are respectively 600~800rpm and 20~for 24 hours.
4. the preparation method of antimony according to claim 1/nitrogen-doped graphene compound, which is characterized in that in step 2),
The time of the freeze-drying is 2~4 days.
5. the preparation method of antimony according to claim 1/nitrogen-doped graphene compound, which is characterized in that in step 3),
The carbonization method is：Step 2) products therefrom is placed in tube furnace, makes tube furnace with 4~10 DEG C of min-1Rate be warming up to
2~4h is kept after 550~650 DEG C.
6. the preparation method of antimony according to claim 1/nitrogen-doped graphene compound, which is characterized in that in step 3),
The H2In/Ar atmosphere, H2Percent by volume be 5%~10%.
7. antimony/nitrogen-doped graphene compound obtained by any one of claim 1~6 preparation method.
8. antimony/application of the nitrogen-doped graphene compound as anode material of lithium-ion battery described in claim 7.
9. a kind of anode material of lithium-ion battery, which is characterized in that the anode material of lithium-ion battery includes described in claim 7
Antimony/nitrogen-doped graphene compound.
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