CN107248569A - Using the methylimidazole cdicynanmide of 1 ethyl 3 antimony made from carbon source/nitrogen-doped carbon compound and its preparation method and application - Google Patents
Using the methylimidazole cdicynanmide of 1 ethyl 3 antimony made from carbon source/nitrogen-doped carbon compound and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of method that antimony/nitrogen-doped carbon compound is prepared by carbon source of the methylimidazole cdicynanmide of 1 ethyl 3, including：Trichloride antimony and the methylimidazole cdicynanmide of 1 ethyl 3 are dissolved in methanol respectively, mixed with vigorous stirring, is stood after two kinds of solution are sufficiently mixed, gel white solid is collected by centrifugation, methanol centrifuge washing is used；By products therefrom in H2It is carbonized under/Ar atmosphere, obtains antimony/nitrogen-doped carbon compound.The present invention also provides antimony obtained by this method/nitrogen-doped carbon compound and the compound as the application of anode material of lithium-ion battery.The present invention is using trichloride antimony, the methylimidazole cdicynanmide ionic liquid of 1 ethyl of ionic liquid 3 as raw material, technique is simple, raw material environmental protection, it is suitable for batch production, obtained antimony/nitrogen-doped carbon compound has excellent chemical property, the low hard carbon of reversible capacity can be replaced to be applied to sodium-ion battery as preferable anode material of lithium-ion battery.
Description
Technical field
The present invention relates to a kind of electrode material, more particularly to one kind is using 1- ethyl-3-methylimidazoles cdicynanmide as carbon source
Obtained antimony/nitrogen-doped carbon compound and preparation method thereof, and the antimony/nitrogen-doped carbon compound are used as sodium-ion battery negative pole
The application of material.
Background technology
Electrochmical power source common at present includes lead-acid battery, metal-hydrogen nickel battery, nickel-cadmium cell and lithium ion battery.
These electrochmical power sources all play the important and pivotal role in mankind nowadays life and the development of national economy.Wherein plumbic acid is electric
Pond material price is cheap, technology mature, therefore it is most widely used.But lead-acid battery energy density is low, and contain a huge sum of money
Belong to Element Lead, serious pollution is produced to environment.These limitations of lead-acid battery limit the further expansion of its application
Greatly.Developing rapidly for society proposes higher requirement to battery technology, and Development of Novel environment protection type battery has become trend.Lithium
Ion battery because its energy density is high, have extended cycle life be widely used in portable electric appts, hybrid vehicle and
Pure electric automobile field.But, the earth's crust content low (0.0065%) of lithium, geographical distribution are uneven, cost is high so that lithium ion
Battery can not meet increasingly increased extensive energy storage demand.In recent years, sodium-ion battery replacing as lithium ion battery
Dai Pin receives much attention, and this, which is primarily due to sodium-ion battery, has that cost of material is cheap, aboundresources, advantages of environment protection.
So far, people have prepared a variety of sodium-ion battery positive materials, and anode material of lithium-ion battery
Development is relatively slow.Therefore, design is with preparing the task of top priority that high performance negative material is sodium-ion battery development.Antimony has
There is higher theoretical capacity (660mAhg-1), good conductivity, this becomes a kind of promising anode material of lithium-ion battery.
However, antimony has serious Volume Changes during deintercalation sodium, easily cause antimony particle efflorescence, lose electrical contact, finally lead
Cause cyclical stability poor.
The content of the invention
Goal of the invention：Antimony/nitrogen-doped carbon is simply prepared it is an object of the invention to provide a kind of environmental protection, technique to be combined
The method of thing, and a kind of anode material of lithium-ion battery with excellent chemical property is provided.
Technical scheme：A kind of side that antimony/nitrogen-doped carbon compound is prepared by carbon source of 1- ethyl-3-methylimidazoles cdicynanmide
Method, this method comprises the following steps：
1) trichloride antimony is dissolved in methanol, forms settled solution, obtain solution A；
2) 1- ethyl-3-methylimidazole cdicynanmides are dissolved in methanol, obtain solution B；
3) solution B is poured into the solution A with vigorous stirring, stood after two kinds of solution are sufficiently mixed, from
The heart collects gel white solid, uses methanol centrifuge washing；
4) by step 3) products therefrom is in H2It is carbonized under/Ar mixed atmospheres, obtains the antimony/nitrogen-doped carbon compound.
In this method, the 1- ethyl-3-methylimidazoles cdicynanmide of addition and the mass ratio of trichloride antimony are 7: 10~9: 10.
Step 3) in, time of repose is 10~20h；It it is 3~6 times with the number of times of methanol centrifuge washing.
Step 4) in, carbonization is by step 3) products therefrom is placed in tube furnace, makes tube furnace with 4~10 DEG C of min-1's
Speed is warming up to 2~4h of holding after 550~650 DEG C；H2In/Ar mixed atmospheres, H2Percent by volume be 5%~10%.
The inventive method is using non-volatile, non-flammable ionic liquid 1- ethyl-3-methylimidazoles cdicynanmide as carbon source, by antimony
Antimony/nitrogen-doped carbon compound is obtained after carrying out the processing such as mixed dissolution, centrifugation, carbonization with ionic liquid.Therefore, the present invention is another
Aspect provides a kind of antimony/nitrogen-doped carbon compound, and the antimony/nitrogen-doped carbon compound is prepared by the above method.Using X-ray
The composition of powder diffractometer (XRD), x-ray photoelectron power spectrum (XPS) test gained antimony/nitrogen-doped carbon compound；Utilize scanning
Electron microscope (SEM), transmission electron microscope (TEM), SEAD (SAED) and high resolution transmission electron microscopy
(HRTEM) size, pattern and micro-structural of analysis gained antimony/nitrogen-doped carbon compound etc..As a result show, the antimony/N doping
Carbon complex surface is smooth, there is equally distributed nanometer size antimony in unformed carbon substrate, and doped with nitrogen, antimony in carbon substrate
Nanocrystal is uniformly coated by nitrogen-doped carbon.
Antimony/nitrogen-doped carbon compound is used as the test that anode material of lithium-ion battery carries out chemical property to it, knot
Fruit shows that the antimony/nitrogen-doped carbon compound has excellent chemical property, and first circle charge/discharge specific capacity is 440/
720mAh g-1, after circulation 150 is enclosed ,+charge/discharge specific capacity still can 385.4/395mAh g-1, capability retention up to 87.5%/
54.8%, and high rate performance is excellent.Therefore, another aspect of the present invention provides above-mentioned antimony/nitrogen-doped carbon compound and is used as sodium ion
The application of cell negative electrode material, and a kind of anode material of lithium-ion battery is provided, the anode material of lithium-ion battery is comprising above-mentioned
Antimony/nitrogen-doped carbon compound.
Beneficial effect：The present invention's prepares the method for antimony/nitrogen-doped carbon compound with trichloride antimony, ionic liquid 1- second
Base -3- methylimidazole cdicynanmides ionic liquid is raw material, and obtaining a kind of antimony/nitrogen-doped carbon by mixing, centrifugation and pyrolysis is combined
Thing.This method technique is simple, the raw material environmental protection used, is suitable for batch production, obtained antimony/nitrogen-doped carbon compound tool
There is excellent chemical property, the low hard carbon of reversible capacity can be replaced to be applied to sodium as preferable anode material of lithium-ion battery
Ion battery, is a kind of promising anode material of lithium-ion battery.
Brief description of the drawings
Fig. 1 a are ESEM (SEM) figure of antimony/nitrogen-doped carbon compound, and the figure shows the composite surface that pyrolysis is obtained
It is smooth, show that antimony is coated by nitrogen-doped carbon；Fig. 1 b are transmission electron microscope (TEM) figure of antimony/nitrogen-doped carbon compound, and the figure shows antimony
Average-size is about 15nm in the composite, and is evenly distributed in carbon substrate；Fig. 1 c are the constituency of antimony/nitrogen-doped carbon compound
Electronic diffraction (SAED) figure, the figure, which is shown in, has the antimony of the hexagonal crystal system of some is nanocrystalline to be formed in unformed carbon substrate；Figure
1d is high-resolution-ration transmission electric-lens (HRTEM) figure of antimony/nitrogen-doped carbon compound, and the figure shows that the interplanar distance in antimony crystal grain is
0.31nm, antimony nanocrystal is uniformly coated by nitrogen-doped carbon.
Fig. 2 a are X-ray diffraction (XRD) figure of antimony/nitrogen-doped carbon compound (Sb@NC), and the figure shows the characteristic peak of antimony
(012) 28.7 ° are appeared in, the interplanar distance with 0.31nm is corresponding, this is consistent with the result that HRTEM is observed；Fig. 2 b are
The XPS figures of nitrogen-doped carbon (NC) derived from antimony/nitrogen-doped carbon compound (Sb@NC) and ionic liquid, the chart is bright, with ionic liquid
The nitrogen-doped carbon of syntaxy is compared, and N signal is it will be clear that high-resolution N 1s XPS spectrums are shown in 399.1eV
Locate the new peak occurred, this may be with SbCl3/ Emim-dca is in reducing atmosphere (H2/ Ar) pyrolysis during produce Sb-N-C keys have
Close.
Fig. 3 a are the charge/discharge curve figure of antimony/nitrogen-doped carbon compound (Sb@NC), and the figure is shown, first circle charge/discharge capacity
Respectively 440 and 720mAhg-1, coulombic efficiency is 61% or so；The big irreversible capacity loss of first circle (39%) be typically by
Form what solid electrolyte film was caused in the electrolyte decomposition in first circle discharge process and in composite surface；Fig. 3 b are antimony/nitrogen
Doping carbon complex (Sb NC), nitrogen-doped carbon (NC) and nanocrystalline (Sb) cycle performance figure of antimony, Fig. 3 c are high content-antimony/nitrogen
Carbon complex (H-Sb NC) and low content-antimony/nitrogen-doped carbon compound (L-Sb NC) cycle performance figure adulterate (based on TGA knots
Really, the height of the Sb contents obtained is named as high and low content antimony/nitrogen-doped carbon compound), antimony/sucrose pyrolysis carbon complex
(Sb SC), antimony/polyacrylonitrile pyrolysis carbon complex (Sb PNC) cycle performance figure, cycle performance figure (Fig. 3 b, 3c) is in voltage
Scope is 0.01-2Vvs Na/Na+, current density is 100mAg-1Under conditions of, the cycle performance of 7 kinds of materials, antimony/N doping
Carbon complex first circle discharge capacity 720mAhg-1, reversible capacity is respectively 395mAhg after circulation 100 is enclosed-1, higher than it
The capacity of his six kinds of materials；Fig. 3 d be antimony/nitrogen-doped carbon compound (Sb NC), antimony/sucrose pyrolysis carbon complex (Sb SC),
Antimony/polyacrylonitrile pyrolysis carbon complex (Sb PNC) high rate performance figure, high rate performance figure (Fig. 3 d) shows that antimony/nitrogen-doped carbon is combined
Thing (Sb NC) though at higher current densities, such as 2 or 5Ag-1, its capability retention may remain in 63.9 or 53.1%, right
Should be in 285 or 237mAhg-1Capacity.
Embodiment
Embodiment 1
(1) preparation of antimony/nitrogen-doped carbon compound
Weigh 400mg trichloride antimonies to be dissolved in 5mL methanol to form settled solution, the settled solution is named as solution
A.500mg 1- ethyl-3-methylimidazole cdicynanmide ion liquid dissolvings are obtained into solution B in 5mL methanol.It is being stirred vigorously
It is lower to pour into solution B in solution A, obtain terminating stirring after homogeneous solution.Stand after 12h, by the way that white solid is collected by centrifugation,
White solid is washed and centrifuged 5 times with methanol.Then, products therefrom is placed in porcelain boat and is transferred in tube furnace, in H2/
600 DEG C are warming up to 5 DEG C/min heating rate under Ar (5: 95v/v) atmosphere, then 2h is kept at 600 DEG C, obtains black
Antimony/N doping carbon complex (Sb@NC).
(2) sign of antimony/nitrogen-doped carbon compound
Utilize size, pattern and the micro- knot of antimony/nitrogen-doped carbon compound obtained by SEM, TEM, SAED and HRTEM map analysis
Structure.Fig. 1 a are ESEM (SEM) figure of antimony/nitrogen-doped carbon compound, and the figure shows that the composite surface that pyrolysis is obtained is smooth,
Show that antimony is coated by nitrogen-doped carbon.Fig. 1 b are transmission electron microscope (TEM) figure of antimony/nitrogen-doped carbon compound, and antimony is can be seen that by the figure
Antimony particle average-size is about 15nm in the composite, and is evenly distributed in carbon substrate.Fig. 1 c are antimony/nitrogen-doped carbon compound
SEAD (SAED) figure, have the antimony nanometer crystalline form of the hexagonal crystal system of some in the bright unformed carbon substrate of the chart
Into.Fig. 1 d are high-resolution-ration transmission electric-lens (HRTEM) figure of antimony/nitrogen-doped carbon compound, and the figure shows the interplanar in antimony crystal grain
Away from for 0.31nm, larger interplanar distance is conducive to Na+Insertion and alloying.
The composition of gained antimony/nitrogen-doped carbon compound is tested using XRD (JCPDS card No.35-0732).Fig. 2 a are
X-ray diffraction (XRD) figure of antimony/nitrogen-doped carbon compound (Sb@NC), the figure shows that the characteristic peak (012) of antimony is appeared in
28.7 °, the interplanar distance with 0.31nm is corresponding, and this is consistent with the result that HRTEM is observed, it was demonstrated that compound obtained by pyrolysis
Antimony is nanocrystal in thing.Fig. 2 b are nitrogen-doped carbon (NC) derived from antimony/nitrogen-doped carbon compound (Sb@NC) and ionic liquid
XPS schemes, and the figure is shown, compared with nitrogen-doped carbon derived from ionic liquid, and N signal is it will be clear that high-resolution N
1s XPS spectrums are shown in the new peak occurred at 399.1eV, and this may be with SbCl3/ Emim-dca is in reducing atmosphere (H2/ Ar)
Sb-N-C keys are produced during pyrolysis relevant, XPS figure (Fig. 2 b) analysis shows are likely to form Sb- in antimony/nitrogen-doped carbon compound
N-C keys, are conducive to improving its storage sodium performance.
(3) electrochemical property test
Using deionized water as solvent, by antimony made from the present embodiment/nitrogen-doped carbon compound (Sb@NC) and carbon black, carboxylic
Sodium carboxymethylcellulose pyce is more uniform than ground and mixed with 7: 2: 1 quality, by the even slurry of gained be applied on Cu paper tinsels and by its
12h is dried in vacuo at 40 DEG C, it is 0.8-1.2mg cm that load capacity, which is made,-2Electrode slice.Use 1mol L-1NaClO4Ethylene
Alkene ester/propene carbonate/fluoro carbon ethylene carbonate (volume ratio is 1: 1: 0.1) solution is used as sodium-ion battery electrolyte, glass
Glass fiber and pure sodium metal foil are respectively as sodium-ion battery barrier film and to electrode.The test of chemical property is using CR2032 electricity
Pond.All operations about battery are carried out all in the glove box full of argon gas atmosphere.
The constant current charge-discharge test of battery at room temperature, with blue electricity CT2001A multi-channel battery test systems,
0.01-2Vvs Na/Na+Carried out in the range 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 then arrives in frequency range in 100kHz
10mHz, amplitude is progress under 10.0mV sine wave.Specific performance is shown in Fig. 3.Fig. 3 a are antimony/nitrogen-doped carbon compound (Sb@
NC charge/discharge curve figure), the figure shows that first circle charge/discharge capacity is respectively 440 and 720mAhg-1, coulombic efficiency is
61% or so；The big irreversible capacity loss of first circle (39%) is due to the electrolyte decomposition and compound in first circle discharge process
Thing surface forms what solid electrolyte film was caused.Fig. 3 b are antimony/nitrogen-doped carbon compound (Sb@NC) cycle performance figures, and antimony/nitrogen is mixed
Miscellaneous carbon complex first circle discharge capacity 720mAhg-1, reversible capacity is respectively 395mAhg after circulation 100 is enclosed-1.Fig. 3 d
It is antimony/nitrogen-doped carbon compound (Sb NC), antimony/sucrose pyrolysis carbon complex (Sb SC), antimony/polyacrylonitrile pyrolysis carbon complex
(Sb@PNC) high rate performance figure, high rate performance figure (Fig. 3 d) shows that antimony/nitrogen-doped carbon compound (Sb@NC) is close even in high current
Under degree, such as in 2 or 5Ag-1, its capability retention may remain in 63.9 or 53.1%, corresponding to 285 or 237mAhg-1
Capacity.
Comparative example 1
(1) preparation of the carbon complex (H-Sb@NC) of high content-antimony/N doping
Weigh 500mg trichloride antimonies to be dissolved in 5mL methanol to form settled solution, be named as solution A.By 500mg 1-
Ethyl-3-methylimidazole cdicynanmide ion liquid dissolving obtains solution B in 5mL methanol.Solution B is poured into vigorous stirring
In solution A, obtain terminating stirring after homogeneous solution.Stand after 12h, by the way that white solid is collected by centrifugation, with methanol by white
Solid is washed and centrifuged 5 times.Then, products therefrom is transferred in porcelain boat and is transferred in tube furnace, in H2/Ar(5∶95v/v)
600 DEG C are warming up to 5 DEG C/min heating rate under atmosphere, then 2h is kept at 600 DEG C, black high content-antimony/nitrogen is obtained
The carbon complex (H-Sb@NC) of doping.
(2) electrochemical property test
Using deionized water as solvent, by the carbon complex (H-Sb@NC) of high content-antimony/N doping made from step (1)
It is more uniform than ground and mixed with 7: 2: 1 quality with carbon black, sodium carboxymethylcellulose, the even slurry of gained is applied on Cu paper tinsels
And it is dried in vacuo 12h at 40 DEG C, it is 0.8-1.2mg cm that load capacity, which is made,-2Electrode slice.Use 1mol L-1NaClO4
Ethylene carbonate/propylene carbonate/fluoro carbon ethylene carbonate (volume ratio is 1: 1: 0.1) solution be used as sodium-ion battery electricity
Liquid is solved, glass fibre and pure sodium metal foil are respectively as sodium-ion battery barrier film and to electrode.The test of chemical property is used
CR2032 batteries.All operations about battery are carried out all in the glove box full of argon gas atmosphere.
Sodium-ion battery performance test is carried out to the carbon complex (H-Sb@NC) of gained high content-antimony/N doping, specifically
Process and conditional parameter are same as Example 1, and specific test result is shown in Fig. 3.As shown in figure 3, cycle performance figure (Fig. 3 c) table
The first circle charge/discharge capacity 407/624mAh g of the bright material-1；Charge/discharge capacity is down to 285/292mAh after the circle of circulation 100
g-1, capability retention is 70.0%/46.8%, hence it is evident that less than antimony/nitrogen-doped carbon compound (Sb@NC) cycle performance.
Comparative example 2
(1) preparation of the carbon complex (L-Sb@NC) of low content-black antimony/N doping
Weigh 320mg trichloride antimonies to be dissolved in 5mL methanol to form settled solution, be named as solution A.By 500mg 1-
Ethyl-3-methylimidazole cdicynanmide ion liquid dissolving obtains solution B in 5mL methanol.Solution B is fallen with vigorous stirring
Enter in solution A, obtain terminating stirring after homogeneous dispersion liquid.12h is stood, will be white with methanol by the way that white solid is collected by centrifugation
Color solid is washed and centrifuged 5 times.Then, products therefrom is placed in porcelain boat and is transferred in tube furnace, in H2/Ar(5∶95v/
V) 600 DEG C are warming up to 5 DEG C/min heating rate under atmosphere, then keep 2h at 600 DEG C, obtain low content-black antimony/
The carbon complex (L-Sb@NC) of N doping.
(2) electrochemical property test
Using deionized water as solvent, by the carbon complex (L- of low content made from step (1)-black antimony/N doping
Sb NC) it is more uniform than ground and mixed with 7: 2: 1 quality with carbon black, sodium carboxymethylcellulose, the even slurry of gained is applied to
12h is dried in vacuo on Cu paper tinsels and by it at 40 DEG C, it is 0.8-1.2mg cm that load capacity, which is made,-2Electrode slice.Use 1mol L-1NaClO4Ethylene carbonate/propylene carbonate/fluoro carbon ethylene carbonate (volume ratio is 1: 1: 0.1) solution as sodium from
Sub- battery electrolyte, glass fibre and pure sodium metal foil are respectively as sodium-ion battery barrier film and to electrode.Chemical property
Test uses CR2032 batteries.All operations about battery are carried out all in the glove box full of argon gas atmosphere.
As shown in figure 3, cycle performance figure (Fig. 3 c) shows the first circle charge/discharge capacity 374/584mAh g of the material-1；Follow
Capacity is down to 314/319mAh g after ring 100 is enclosed-1, capability retention is 91.5%/54.6%, although capability retention is not
It is low, but capacity is significantly lower than the cycle performance of antimony/nitrogen-doped carbon compound (Sb@NC).
Comparative example 3
(1) preparation of antimony/sucrose pyrolysis carbon complex (Sb SC)
Weigh 400mg trichloride antimonies to be dissolved in 5mL methanol to form settled solution, be named as solution A.By 500mg sugarcanes
Sugar is dissolved in 5mL methanol and obtains solution B.Solution B is poured into solution A with vigorous stirring, obtained after homogeneous dispersion liquid
Terminate stirring.Stand after 12h, by the way that white solid is collected by centrifugation, the white solid is washed and centrifuged 5 times with methanol.Then,
Products therefrom is placed in porcelain boat and is transferred in tube furnace, in H2With 5 DEG C/min heating speed under/Ar (5: 95v/v) atmosphere
Rate is warming up to 600 DEG C, is then kept for 2 hours at 600 DEG C, obtains black antimony/sucrose pyrolysis carbon complex (Sb SC).
(2) electrochemical property test
Using deionized water as solvent, antimony made from step (1)/sucrose is pyrolyzed carbon complex (Sb SC) and carbon black, carboxylic
Sodium carboxymethylcellulose pyce is more uniform than ground and mixed with 7: 2: 1 quality, by the even slurry of gained be applied on Cu paper tinsels and by its
12h is dried in vacuo at 40 DEG C, it is 0.8-1.2mg cm that load capacity, which is made,-2Electrode slice.Use 1mol L-1NaClO4Ethylene
Alkene ester/propene carbonate/fluoro carbon ethylene carbonate (volume ratio is 1: 1: 0.1) solution is used as sodium-ion battery electrolyte, glass
Glass fiber and pure sodium metal foil are respectively as sodium-ion battery barrier film and to electrode.The test of chemical property is using CR2032 electricity
Pond.All operations about battery are carried out all in the glove box full of argon gas atmosphere.
As shown in figure 3, cycle performance figure (Fig. 3 c) shows that the first circle charge/discharge specific capacity of the material is 281/501mAh
g-1；After the circle of circulation 100, charge/discharge specific capacity is 215/219mAh g-1, capability retention is 76.8%/43.6%, is less than
The cycle performance of antimony/nitrogen-doped carbon compound.High rate performance figure (Fig. 3 d) shows the material in 5Ag-1Under current density, capacity is
200mAh g-1, high rate performance of the high rate performance significantly lower than antimony/nitrogen-doped carbon compound (Sb@NC).
Comparative example 4
(1) preparation of antimony/polyacrylonitrile pyrolysis carbon complex (Sb PNC)
Weigh 400mg trichloride antimonies to be dissolved in 5mLN, dinethylformamide to form settled solution, be named as solution
A.500mg polyacrylonitrile is dissolved in 5mL DMFs and obtains solution B.Solution B is fallen with vigorous stirring
Enter in solution A, obtain terminating stirring after homogeneous dispersion liquid.After 12 hours, by the way that white solid is collected by centrifugation.Will be white with methanol
Color solid is washed and centrifuged 5 times.Then, products therefrom is placed in porcelain boat and is transferred in tube furnace, in H2/Ar(5∶95v/
V) 600 DEG C are warming up to 5 DEG C/min heating rate under atmosphere, are then kept for 2 hours at 600 DEG C, obtain black antimony/poly- third
Alkene nitrile is pyrolyzed carbon complex.
(2) electrochemical property test
Using deionized water as solvent, antimony made from step (1)/polyacrylonitrile is pyrolyzed carbon complex (Sb PNC) and charcoal
Black, sodium carboxymethylcellulose is more uniform than ground and mixed with 7: 2: 1 quality, and the even slurry of gained is applied on Cu paper tinsels and incited somebody to action
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 slice.Use 1mol L-1NaClO4Carbon
Vinyl acetate/propene carbonate/fluoro carbon ethylene carbonate (volume ratio is 1: 1: 0.1) solution is electrolysed as sodium-ion battery
Liquid, glass fibre and pure sodium metal foil are respectively as sodium-ion battery barrier film and to electrode.The test of chemical property is used
CR2032 batteries.All operations about battery are carried out all in the glove box full of argon gas atmosphere.
As shown in figure 3, cycle performance figure (Fig. 3 c) shows that the first circle charge/discharge specific capacity of the material is 217/376mAh
g-1；After the circle of circulation 100, charge/discharge specific capacity is 167/168mAh g-1, capability retention is 76.7%/44.5%, is less than
The cycle performance of antimony/nitrogen-doped carbon compound.High rate performance figure (Fig. 3 d) shows the material in 5A g-1Under current density, capacity
For 110mAh g-1, high rate performance of the high rate performance significantly lower than antimony/nitrogen-doped carbon compound (Sb@NC).
Comparative example 5
(1) preparation of nitrogen-doped carbon compound (NC)
1.0mL 1- ethyl-3-methylimidazole cdicynanmides are put into porcelain boat and are transferred in tube furnace, in H2/Ar(5∶
600 DEG C 95v/v) are warming up to 5 DEG C/min heating rate under atmosphere, then 2h is kept at 600 DEG C, black N doping is obtained
Carbon compound (NC).
(2) electrochemical property test
Using deionized water as solvent, by nitrogen-doped carbon compound (NC) made from step (1) and carbon black, carboxymethyl cellulose
Plain sodium is more uniform than ground and mixed with 7: 2: 1 quality, by the even slurry of gained be applied on Cu paper tinsels and by its at 40 DEG C it is true
Sky dries 12h, and it is 0.8-1.2mg cm that load capacity, which is made,-2Electrode slice.Use 1mol L-1NaClO4Ethylene carbonate/carbon
Acid propylene ester/fluoro carbon ethylene carbonate (volume ratio is 1: 1: 0.1) solution as sodium-ion battery electrolyte, glass fibre and
Pure sodium metal foil is respectively as sodium-ion battery barrier film and to electrode.The test of chemical property uses CR2032 batteries.It is all
Operation about battery is carried out all in the glove box full of argon gas atmosphere.
As shown in figure 3, cycle performance figure (Fig. 3 b) shows that the first circle charge/discharge specific capacity of the material is 90/302mAh g-1；After the circle of circulation 100, charge/discharge specific capacity is 116/117mAh g-1, capability retention is 77.3%/38.8%, is less than
The cycle performance of antimony/nitrogen-doped carbon compound (Sb@NC).
Comparative example 6
(1) preparation of antimony nanocrystal (Sb)
Under argon gas protection, 0.45g NaBH4 are dissolved in containing 13mLN, in the single-necked flask of dinethylformamide,
And it is heated to 60 DEG C.Then, by syringe, into the single-necked flask, injection is dissolved with 0.68g SbCl immediately32mLN, N-
Dimethyl formamide solution.The rapid blackening of reactant in single-necked flask, is quickly cooled down using ice-water bath.It is cooled to after room temperature,
By the way that the antimony nanocrystal (Sb) of generation is collected by centrifugation, it is washed with deionized for several times, is dried overnight at 40 DEG C.
(2) electrochemical property test
Using deionized water as solvent, by antimony nanocrystal (Sb) made from step (1) and carbon black, sodium carboxymethylcellulose
It is more uniform than ground and mixed with 7: 2: 1 quality, the even slurry of gained is applied on Cu paper tinsels and vacuum is done at 40 DEG C by it
Dry 12h, it is 0.8-1.2mg cm that load capacity, which is made,-2Electrode slice.Use 1mol L-1NaClO4Ethylene carbonate/carbonic acid third
Alkene ester/fluoro carbon ethylene carbonate (volume ratio is 1: 1: 0.1) solution is used as sodium-ion battery electrolyte, glass fibre and pure sodium
Metal foil is respectively as sodium-ion battery barrier film and to electrode.The test of chemical property uses CR2032 batteries.It is all relevant
The operation of battery is carried out all in the glove box full of argon gas atmosphere.
As shown in figure 3, cycle performance figure (Fig. 3 b) shows that the first circle charge/discharge specific capacity of the material is 390/592mAh
g-1；After the circle of circulation 100, charge/discharge specific capacity is 40/42mAh g-1, capability retention be 10.3%/7.0%, less than antimony/
The cycle performance of nitrogen-doped carbon compound (Sb@NC).
Embodiment 2
Weigh 400mg trichloride antimonies to be dissolved in 5mL methanol to form settled solution, be named as solution A.By 500mg 1-
Ethyl-3-methylimidazole cdicynanmide ion liquid dissolving obtains solution B in 5mL methanol.Solution B is fallen with vigorous stirring
Enter in solution A, obtain terminating stirring after homogeneous dispersion liquid.Stand after 12h, will with methanol by the way that white solid is collected by centrifugation
White solid is washed and centrifuged 5 times.Then, products therefrom is transferred in porcelain boat and is transferred in tube furnace, in H2/Ar(10∶
600 DEG C 90v/v) are warming up to 5 DEG C/min heating rate under atmosphere, then 4h is kept at 600 DEG C, black antimony/nitrogen is obtained
The carbon complex of doping.
Structural characterization and electricity are carried out to the carbon complex of obtained antimony/N doping according to method same as Example 1
Chemical property is tested, as a result substantially the same manner as Example 1.
Embodiment 3
Weigh 450mg trichloride antimonies to be dissolved in 5mL methanol to form settled solution, be named as solution A.By 500mg 1-
Ethyl-3-methylimidazole cdicynanmide ion liquid dissolving obtains solution B in 5mL methanol.Solution B is poured into vigorous stirring
In solution A, obtain terminating stirring after homogeneous dispersion liquid.Stand after 15h, should with methanol by the way that white solid is collected by centrifugation
White solid is washed and centrifuged 5 times.Then, products therefrom is placed in porcelain boat and is transferred in tube furnace, in H2/Ar(5∶
600 DEG C 95v/v) are warming up to 5 DEG C/min heating rate under atmosphere, then 2h is kept at 600 DEG C, black antimony/nitrogen is obtained
The carbon complex of doping.
Structural characterization and electricity are carried out to the carbon complex of obtained antimony/N doping according to method same as Example 1
Chemical property is tested, as a result substantially the same manner as Example 1.
Embodiment 4
Weigh 350mg trichloride antimonies to be dissolved in 5mL methanol to form settled solution, be named as solution A.By 500mg 1-
Ethyl-3-methylimidazole cdicynanmide ion liquid dissolving obtains solution B in 5mL methanol.Solution B is poured into vigorous stirring
In solution A, obtain terminating stirring after homogeneous dispersion liquid.Stand after 10h, should with methanol by the way that white solid is collected by centrifugation
White solid is washed and centrifuged 6 times.Then, products therefrom is placed in porcelain boat and is transferred in tube furnace, in H2/Ar(5∶
550 DEG C 95v/v) are warming up to 4 DEG C/min heating rate under atmosphere, then 4h is kept at 550 DEG C, black antimony/nitrogen is obtained
The carbon complex of doping.
Structural characterization and electricity are carried out to the carbon complex of obtained antimony/N doping according to method same as Example 1
Chemical property is tested, as a result substantially the same manner as Example 1.
Embodiment 5
Weigh 450mg trichloride antimonies to be dissolved in 5mL methanol to form settled solution, be named as solution A.By 500mg 1-
Ethyl-3-methylimidazole cdicynanmide ion liquid dissolving obtains solution B in 5mL methanol.Solution B is poured into vigorous stirring
In solution A, obtain terminating stirring after homogeneous dispersion liquid.Stand after 20h, should with methanol by the way that white solid is collected by centrifugation
White solid is washed and centrifuged 3 times.Then, products therefrom is placed in porcelain boat and is transferred in tube furnace, in H2/Ar(5∶
650 DEG C 95v/v) are warming up to 10 DEG C/min heating rate under atmosphere, then 3h is kept at 650 DEG C, black antimony/nitrogen is obtained
The carbon complex of doping.
Structural characterization and electricity are carried out to the carbon complex of obtained antimony/N doping according to method same as Example 1
Chemical property is tested, as a result substantially the same manner as Example 1.
Claims (9)
1. a kind of method that antimony/nitrogen-doped carbon compound is prepared by carbon source of 1- ethyl-3-methylimidazoles cdicynanmide, its feature exists
In this method comprises the following steps：
1) trichloride antimony is dissolved in methanol, forms settled solution, obtain solution A；
2) 1- ethyl-3-methylimidazole cdicynanmides are dissolved in methanol, obtain solution B；
3) solution B is poured into the solution A with vigorous stirring, stood after two kinds of solution are sufficiently mixed, centrifugation is received
Collect gel white solid, use methanol centrifuge washing；
4) by step 3) products therefrom is in H2It is carbonized under/Ar mixed atmospheres, obtains the antimony/nitrogen-doped carbon compound.
2. according to the method described in claim 1, it is characterised in that the 1- ethyl-3-methylimidazole dicyan added in this method
The mass ratio of amine and trichloride antimony is 7: 10~9: 10.
3. according to the method described in claim 1, it is characterised in that step 3), the time of repose is 10~20h.
4. according to the method described in claim 1, it is characterised in that step 3), the number of times of the use methanol centrifuge washing is 3
~6 times.
5. according to the method described in claim 1, it is characterised in that step 4), the carbonization is by step 3) products therefrom
It is placed in tube furnace, makes tube furnace with 4~10 DEG C of min-1Speed be warming up to after 550~650 DEG C 2~4h of holding.
6. according to the method described in claim 1, it is characterised in that step 4), the H2In/Ar mixed atmospheres, H2Volume
Percentage is 5%~10%.
7. a kind of antimony/nitrogen-doped carbon compound, it is characterised in that the antimony/nitrogen-doped carbon compound in claim 1~6 by appointing
Method described in meaning one is prepared.
8. antimony/nitrogen-doped carbon compound described in claim 7 is used as the application of anode material of lithium-ion battery.
9. a kind of anode material of lithium-ion battery, it is characterised in that the anode material of lithium-ion battery is comprising described in claim 7
Antimony/nitrogen-doped carbon compound.
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| CN108649191A (en) * | 2018-03-30 | 2018-10-12 | 南京师范大学 | The preparation method and its resulting materials of a kind of antimony/nitrogen-doped graphene compound and application |
| CN109378473A (en) * | 2018-08-20 | 2019-02-22 | 中国科学院兰州化学物理研究所 | The modified carbon-supported copper catalyst of nitrogen and its application in terms of cell positive material |
| CN110265652A (en) * | 2019-07-19 | 2019-09-20 | 河南师范大学 | A kind of preparation method for lithium ion/sodium-ion battery cathode nano-sheet Sb/C composite material |
| CN110993904A (en) * | 2019-11-14 | 2020-04-10 | 江苏大学 | Preparation method of nitrogen-doped antimony-carbon composite material and application of nitrogen-doped antimony-carbon composite material to sodium ion battery electrode |
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| CN112768646A (en) * | 2020-12-04 | 2021-05-07 | 杭州电子科技大学 | Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application |
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