CN109638234A - One-dimensional porous antimony base functional carbon nanotubes of one kind and its preparation method and application - Google Patents
One-dimensional porous antimony base functional carbon nanotubes of one kind and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to sodium-ion battery Material Fields, disclose one-dimensional porous antimony base functional carbon nanotubes of one kind and its preparation method and application.Antimony containing compounds or dispersed nano antimony are mixed with carbon precursor polymer, pyrolyzed-polymer, organic solvent, stirring, ultrasonic treatment are uniformly dispersed, and obtain precursor solution；By gained precursor solution by electrostatic spinning, nano-composite fiber is obtained；Nano-composite fiber is obtained into one-dimensional porous antimony base functional carbon nanotubes successively through pre-oxidation and carbonization treatment under inert atmosphere or reducing atmosphere.The present invention in carbon nanotube by introducing antimony nano material, gained composite material has very high specific surface area, mutually highly cross-linked conductive network and porous structure, as anode material of lithium-ion battery using specific capacity with higher, long period good cycle and excellent high rate performance.
Description
Technical field
The invention belongs to sodium-ion battery Material Fields, and in particular to a kind of one-dimensional porous antimony base functional carbon nanotubes and
Preparation method and application.
Background technique
Currently, sodium-ion battery (SIBs) has had the potentiality as lithium ion battery low cost substitute.SIBs business
The major obstacle of change first is that can the negative electrode material that provided forthright to meet battery capacity stability and high power under high current
Energy.Development it is completely new, efficient anode material of lithium-ion battery become the task of top priority.
Antimony (Sb) has always been considered as being a kind of up-and-coming negative electrode material, in fact, a Sb atomic energy is to greatest extent
Ground reacts three Na atoms and forms Na3Sb alloy reaches theoretical 660mAh g-1High theoretical capacity.However, due to a large amount of
During sodium insertion/deintercalation, the volume change (being up to about 290%) that antimony (Sb) is very big can be caused, this will will lead to the crushing of Sb
And cathode is lost with collector and is contacted, cause chemical property to decline.Therefore, it is found and is inhibited by scientific and effective method
The method of the volume expansion of antimony base is of crucial importance the stability of antimony base sodium ion negative electrode material.
Zhu et al. is prepared for receiving with the Sb@C of typical yolk core-shell structure using nanometer Sn as template, with chemical displacement method
Rice Hollow Sphere Composites, in 1000mA g-1Current density under, 300 times circulation after reversible specific capacity be maintained at 405mAh
g-1, coulombic efficiency 99.1%, but synthesis step is cumbersome, long preparation period, low yield is unfavorable for sodium ion negative electrode material
Batch production and large-scale application.Cao et al. is prepared for Sb/C nanofiber using electrostatic spinning technique, in low current following table
Good cycle performance is showed, but wherein the content of antimony is 38%, and it is lower to result in sodium-ion battery specific capacity.
Carbon nanotube (CNFs) is the promising material for SIBs, due to their excellent electrochemistry and mechanicalness
Can, and lighter in weight can more effectively establish a conduction percolation network, can be used as active sodium ion compared with other carbon materials
Storage material or as physical support object high capacity cathode pole material such as phosphorus, tin, germanium, antimony, and the CNFs network being interweaved can
With buffer the volume expansion because of alloying process generate and mechanical stress, can effectively shorten sodium ion diffusion path.But mesh
The carbon nanotube of preceding specific morphology and the composite material of antimony base functional material and preparation method rare report.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of one-dimensional
Porous antimony base functional carbon nanotubes.
Another object of the present invention is to provide the preparation methods of above-mentioned one-dimensional porous antimony base functional carbon nanotubes.
A further object of the present invention is to provide above-mentioned one-dimensional porous antimony base functional carbon nanotubes as sodium-ion battery
The application of negative electrode material.
The object of the invention is achieved through the following technical solutions:
A kind of one-dimensional porous antimony base functional carbon nanotubes, by carbon nanotube and the metal being uniformly distributed in carbon nanotube
Antimony is constituted.
Further, the diameter of the carbon nanotube is 100nm~5 μm, the granular size of metallic antimony be 10nm~
500nm。
Further, the mass percentage of the metallic antimony is 5%~80%.
The preparation method of above-mentioned one-dimensional porous antimony base functional carbon nanotubes, including following preparation step:
(1) antimony containing compounds or dispersed nano antimony are mixed with carbon precursor polymer, pyrolyzed-polymer, organic solvent
It closes, stirring, ultrasonic treatment are uniformly dispersed, and obtain precursor solution；
(2) precursor solution obtained by step (1) is obtained into nano-composite fiber by electrostatic spinning；
(3) nano-composite fiber obtained by step (2) is successively pre-oxidized and is carbonized under inert atmosphere or reducing atmosphere
Processing, obtains one-dimensional porous antimony base functional carbon nanotubes.
Preferably, antimony containing compounds described in step (1) are selected from antimony trichloride, nitric acid antimony, antimony acetate, antimony trisulfide, sulfuric acid
One of antimony, antimony oxide, antimony pentoxide, potassium antimony tartrate are a variety of.
Preferably, the average grain diameter of dispersed nano antimony described in step (1) is 10~200nm.
Preferably, step (1) carbon precursor polymer be selected from polyacrylonitrile, polyvinylpyrrolidone, polycarbonate,
It is poly- sough, polystyrene, polyethylene, polypropylene, polyvinyl butyral, polyethylene terephthalate, poly terephthalic acid fourth
One of diester is a variety of；The pyrolyzed-polymer is selected from polymethyl methacrylate, polystyrene, polylactic acid, polycyclic oxygen
One of ethane is a variety of；The organic solvent is selected from hexafluoroisopropanol, pyridine, n,N-Dimethylformamide, N- methyl pyrrole
Pyrrolidone, tetrahydrofuran, chloroform, any one in chloroform.
Preferably, the mass concentration of antimony containing compounds or dispersed nano antimony is in precursor solution described in step (1)
0.1%~20%, the mass concentration of carbon precursor polymer is 3%~20%, and the mass concentration of pyrolyzed-polymer is 0.01%
~10%.
Preferably, the heating rate of step (3) described pre-oxidation be 0.5~10 DEG C/min, Pre oxidation be 100~
500 DEG C, preoxidation time is 1~4h；The heating rate of the carbonization is 0.5~10 DEG C/min, and carburizing temperature is 400~1500
DEG C, carbonization time is 2~10h.
Application of the above-mentioned one-dimensional porous antimony base functional carbon nanotubes as anode material of lithium-ion battery.
Further, the application process are as follows: mix one-dimensional porous antimony base functional carbon nanotubes with carbon black and PVDF
Slurrying is coated on copper foil, obtaining sodium-ion battery cathode.
Compared with the existing technology, the invention has the following advantages and beneficial effects:
(1) present invention has very high specific surface by introducing antimony nano material, gained composite material in carbon nanotube
Product, mutually highly cross-linked conductive network and porous structure, this special structure can effectively be buffered because of alloying process
Volume expansion generate and mechanical stress, volume expansion problem can be effectively relieved, reduce the deformation of electrode, enhance electrode
Electric conductivity；Sodium ion/electron diffusion path can be effectively shortened simultaneously, greatly improve the dynamic performance of material；
High antimony content provides guarantee for high battery specific capacity.It is as anode material of lithium-ion battery using ratio with higher
Capacity, long period good cycle and excellent high rate performance.
(2) present invention utilizes electrostatic spinning technique, and synthesis step is simple, and yield is high, with short production cycle, can satisfy big rule
Mould, high-power business flexible electronic device requirement, has broad application prospects, so that sodium-ion battery moves towards commercialization process
Further.
Detailed description of the invention
Fig. 1 is the product SEM figure in the embodiment of the present invention 3 after the pre-oxidation of nano-composite fiber obtained by electrostatic spinning.
Fig. 2 is the SEM figure of the one-dimensional porous antimony base functional carbon nanotubes of gained after being finally carbonized in the embodiment of the present invention 3.
Fig. 3 is the one-dimensional porous antimony base functional carbon nanotubes partial enlargement of gained after being finally carbonized in the embodiment of the present invention 3
SEM figure.
Fig. 4 is the one-dimensional porous antimony base functional carbon nanotubes partial enlargement of gained after being finally carbonized in the embodiment of the present invention 3
TEM figure.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) antimony trichloride 0.02g, polyacrylonitrile 1.5g, polymethyl methacrylate 0.05g, N, N- dimethyl formyl are taken
Amine 8.0mL is placed in sealing container, by 6 hours stirrings, 6 hours ultrasounds, obtains high degree of dispersion, stable electrostatic spinning forerunner
Liquid solution.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) under 95vt.% nitrogen+5vt.% hydrogen mixed gas atmosphere according to
It is secondary through pre-oxidation and carbonization treatment.The heating rate of pre-oxidation is 0.5 DEG C/min, and Pre oxidation is 250 DEG C, preoxidation time
It is 2 hours, carbonization heating rate is 0.5 DEG C/min, and carburizing temperature is 600 DEG C, and carbonization time is 6 hours, be can be obtained one-dimensional
Porous antimony base functional carbon nanotubes.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
Embodiment 2
(1) nitric acid antimony 0.4g, polyvinylpyrrolidone 0.9g, polystyrene 0.2g, N-Methyl pyrrolidone 11.0mL are taken
It is placed in sealing container, by 10 hours stirrings, 6 hours ultrasounds, it is molten to obtain high degree of dispersion, stable electrostatic spinning presoma
Liquid.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) under 97vt.% nitrogen+3vt.% hydrogen mixed gas atmosphere according to
It is secondary through pre-oxidation and carbonization treatment.The heating rate of pre-oxidation is 0.5 DEG C/min, and Pre oxidation is 200 DEG C, preoxidation time
It is 1 hour, carbonization heating rate is 0.5 DEG C/min, and carburizing temperature is 500 DEG C, and carbonization time is 3 hours, be can be obtained one-dimensional
Porous antimony base functional carbon nanotubes.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
Embodiment 3
(1) it takes antimony acetate 1.3g, poly- carbonic acid vinegar 0.65g, polystyrene 0.08g, tetrahydrofuran 15.0mL to be placed in sealing to hold
In device, by 9 hours stirrings, 8 hours ultrasounds, high degree of dispersion, stable electrostatic spinning precursor solution are obtained.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) under 90%vt. nitrogen+10vt.% hydrogen mixed gas atmosphere according to
It is secondary through pre-oxidation and carbonization treatment.The heating rate of pre-oxidation is 1 DEG C/min, and Pre oxidation is 250 DEG C, and preoxidation time is
2 hours, carbonization heating rate was 1 DEG C/min, and carburizing temperature is 700 DEG C, and carbonization time is 4 hours, be can be obtained one-dimensional porous
Antimony base functional carbon nanotubes.
Product SEM figure of the present embodiment after electrostatic spinning gained nano-composite fiber pre-oxidation is as shown in Figure 1.Final carbon
The SEM figure of the one-dimensional porous antimony base functional carbon nanotubes of gained is as shown in Figure 2 after change.The one-dimensional porous antimony base of gained after final carbonization
The SEM figure of functional carbon nanotubes partial enlargement is as shown in Figure 3.The one-dimensional porous antimony base Functional carbon nanometer of gained after final carbonization
The TEM figure of pipe partial enlargement is as shown in Figure 4.It can be seen that the fibre of the one-dimensional porous antimony base functional carbon nanotubes of gained by result above
Dimension diameter is 265nm, and metallic antimony particle is uniformly distributed in carbon nanotube.In fibrous inside like a certain number of " antimony island " quilts
" the carbon sea " of surrounding surrounds, and granular size is 10_nm~500_nm.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
Embodiment 4
(1) antimony sulfate 0.2g, polyethylene 1.2g, polylactic acid 0.12g, hexafluoroisopropanol 10.4mL is taken to be placed in sealing container
In, by 7 hours stirrings, 9 hours ultrasounds, obtain high degree of dispersion, stable electrostatic spinning precursor solution.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) in a nitrogen atmosphere successively through pre-oxidation and carbonization treatment.Pre-oxidation
Heating rate be 2 DEG C/min, Pre oxidation be 250 DEG C, preoxidation time be 3 hours, carbonization heating rate be 1.5 DEG C/
Min, carburizing temperature are 750 DEG C, and carbonization time is 5 hours, and one-dimensional porous antimony base functional carbon nanotubes can be obtained.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
Embodiment 5
(1) antimony oxide 1.67g, polyvinyl butyral 0.3g, Pluronic F-127 0.02g, pyridine 7.3mL is taken to be placed in
In sealing container, by 10 hours stirrings, 12 hours ultrasounds, high degree of dispersion, stable electrostatic spinning precursor solution are obtained.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) under 96vt.% helium+4vt.% hydrogen mixed gas atmosphere according to
It is secondary through pre-oxidation and carbonization treatment.The heating rate of pre-oxidation is 3 DEG C/min, and Pre oxidation is 280 DEG C, and preoxidation time is
2 hours, carbonization heating rate was 2 DEG C/min, and carburizing temperature is 800 DEG C, and carbonization time is 4 hours, be can be obtained one-dimensional porous
Antimony base functional carbon nanotubes.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
Embodiment 6
(1) antimony oxide 2.1g, polyvinyl butyral 1.6g, Pluronic F-127 0.26g, chloroform 20.0mL are taken
It is placed in sealing container, by 10 hours stirrings, 12 hours ultrasounds, it is molten to obtain high degree of dispersion, stable electrostatic spinning presoma
Liquid.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) under helium atmosphere successively through pre-oxidation and carbonization treatment.Pre-oxidation
Heating rate be 2.5 DEG C/min, Pre oxidation be 300 DEG C, preoxidation time be 3 hours, carbonization heating rate be 3 DEG C/
Min, carburizing temperature are 900 DEG C, and carbonization time is 5 hours, and one-dimensional porous antimony base functional carbon nanotubes can be obtained.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
Embodiment 7
(1) potassium antimony tartrate 0.125g, polyethylene terephthalate 0.253g, Pluronic F-127 0.345g, chloroform are taken
3.5mL is placed in sealing container, by 9 hours stirrings, 12 hours ultrasounds, obtains high degree of dispersion, stable electrostatic spinning forerunner
Liquid solution.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) under an argon atmosphere successively through pre-oxidation and carbonization treatment.Pre-oxidation
Heating rate be 1.5 DEG C/min, Pre oxidation be 350 DEG C, preoxidation time be 2.5 hours, carbonization heating rate be 3
DEG C/min, carburizing temperature is 1200 DEG C, and carbonization time is 7 hours, and one-dimensional porous antimony base functional carbon nanotubes can be obtained.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
Embodiment 8
(1) antimony trisulfide 0.4g, polybutylene terephthalate 2.8g, polystyrene 0.036g, N-Methyl pyrrolidone are taken
20.3mL is placed in sealing container, by 5 hours stirrings, 7 hours ultrasounds, obtains high degree of dispersion, stable electrostatic spinning forerunner
Liquid solution.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) under 95vt.% argon gas+5vt.% hydrogen mixed gas atmosphere according to
It is secondary through pre-oxidation and carbonization treatment.The heating rate of pre-oxidation is 2 DEG C/min, and Pre oxidation is 350 DEG C, and preoxidation time is
2.5 hours, carbonization heating rate was 4 DEG C/min, and carburizing temperature is 900 DEG C, and carbonization time is 3 hours, be can be obtained one-dimensional more
Hole antimony base functional carbon nanotubes.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
Embodiment 9
(1) antimony trichloride 1.56g, Acrylic Fiber Wastes 4.23g, polystyrene 0.67g, N-Methyl pyrrolidone are taken
50.0mL is placed in sealing container, by 15 hours stirrings, 9 hours ultrasounds, obtains high degree of dispersion, stable electrostatic spinning forerunner
Liquid solution.
(2) the electrostatic spinning precursor solution of preparation is fitted into electrostatic spinning syringe, aluminium foil is fixed on receiver board
On, by high pressure spinneret, drying is collected, obtains nano-composite fiber.
(3) by nano-composite fiber obtained by step (2) in a nitrogen atmosphere successively through pre-oxidation and carbonization treatment.Pre-oxidation
Heating rate be 2 DEG C/min, Pre oxidation be 300 DEG C, preoxidation time be 2.5 hours, carbonization heating rate be 3 DEG C/
Min, carburizing temperature are 700 DEG C, and carbonization time is 6 hours, and one-dimensional porous antimony base functional carbon nanotubes can be obtained.
Turn after taking one-dimensional porous antimony base functional carbon nanotubes obtained by the present embodiment and PVDF and carbon black mixed grinding
Enter in vial, NMP is added, material is coated on copper foil and electrode is made by magnetic agitation 1h, is used as using metallic sodium to electricity
Pole is assembled into CR2016 type button cell in glove box, carries out electrochemical property test.
The results are shown in Table 1 for above embodiments electrochemical property test:
Each embodiment parameter of table 1 and corresponding chemical property
By result above as can be seen that the present invention is using antimony containing compounds or dispersed nano antimony, carbon matrix precursor polymerization
One-dimensional porous antimony base functional carbon nanotubes prepared by object, pyrolyzed-polymer have preferable electricity as sodium-ion battery cathode
Chemical property, can be in 20~5000mA of current density g-1120-486mAh g is kept after lower 50~2000 circle of circulation-1Can
Inverse capacity.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of one-dimensional porous antimony base functional carbon nanotubes, it is characterised in that: the one-dimensional porous antimony base Functional carbon nanometer
Pipe is made of carbon nanotube and the metallic antimony being uniformly distributed in carbon nanotube.
2. the one-dimensional porous antimony base functional carbon nanotubes of one kind according to claim 1, it is characterised in that: the carbon nanometer
The diameter of pipe is 100nm~5 μm, and the granular size of metallic antimony is 10nm~500nm.
3. the one-dimensional porous antimony base functional carbon nanotubes of one kind according to claim 1, it is characterised in that: the metallic antimony
Mass percentage be 5%~80%.
4. the preparation method of the one-dimensional porous antimony base functional carbon nanotubes of the described in any item one kind of claims 1 to 3, feature
It is to include following preparation step:
(1) antimony containing compounds or dispersed nano antimony are mixed with carbon precursor polymer, pyrolyzed-polymer, organic solvent, is stirred
It mixes, be ultrasonically treated and be uniformly dispersed, obtain precursor solution；
(2) precursor solution obtained by step (1) is obtained into nano-composite fiber by electrostatic spinning；
(3) by nano-composite fiber obtained by step (2) under inert atmosphere or reducing atmosphere successively through pre-oxidation and carbonization treatment,
Obtain one-dimensional porous antimony base functional carbon nanotubes.
5. according to right want 4 described in the one-dimensional porous antimony base functional carbon nanotubes of one kind preparation method, it is characterised in that: step
Suddenly antimony containing compounds described in (1) are selected from antimony trichloride, nitric acid antimony, antimony acetate, antimony trisulfide, antimony sulfate, antimony oxide, five oxygen
Change one of two antimony, potassium antimony tartrate or a variety of；The average grain diameter of the dispersed nano antimony is 10~200nm.
6. according to right want 4 described in the one-dimensional porous antimony base functional carbon nanotubes of one kind preparation method, it is characterised in that: step
Suddenly (1) described carbon precursor polymer is selected from polyacrylonitrile, polyvinylpyrrolidone, polycarbonate, gathers and sough, polystyrene, gather
One of ethylene, polypropylene, polyvinyl butyral, polyethylene terephthalate, polybutylene terephthalate are more
Kind；The pyrolyzed-polymer is selected from one of polymethyl methacrylate, polystyrene, polylactic acid, polyethylene oxide or more
Kind；The organic solvent be selected from hexafluoroisopropanol, pyridine, n,N-Dimethylformamide, N-Methyl pyrrolidone, tetrahydrofuran,
Any one in chloroform, chloroform.
7. according to right want 4 described in the one-dimensional porous antimony base functional carbon nanotubes of one kind preparation method, it is characterised in that: step
Suddenly the mass concentration of antimony containing compounds or dispersed nano antimony is 0.1%~20% in precursor solution described in (1), carbon forerunner
The mass concentration of body polymer is 3%~20%, and the mass concentration of pyrolyzed-polymer is 0.01%~10%.
8. according to right want 4 described in the one-dimensional porous antimony base functional carbon nanotubes of one kind preparation method, it is characterised in that: step
Suddenly the heating rate of (3) described pre-oxidation is 0.5~10 DEG C/min, and Pre oxidation is 100~500 DEG C, preoxidation time 1
~4h；The heating rate of the carbonization be 0.5~10 DEG C/min, carburizing temperature be 400~1500 DEG C, carbonization time be 2~
10h。
9. the one-dimensional porous antimony base functional carbon nanotubes of the described in any item one kind of claims 1 to 3 are negative as sodium-ion battery
The application of pole material.
10. the one-dimensional porous antimony base functional carbon nanotubes of one kind according to claim 9 are as sodium-ion battery cathode material
The application of material, it is characterised in that the application process are as follows: mix one-dimensional porous antimony base functional carbon nanotubes with carbon black and PVDF
Slurrying is closed, is coated on copper foil, obtaining sodium-ion battery cathode.
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