CN110323442A - A kind of carbon coating Fe3O4Composite material and preparation method and application - Google Patents
A kind of carbon coating Fe3O4Composite material and preparation method and application Download PDFInfo
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Abstract
The invention belongs to new energy field, in particular to a kind of carbon coating Fe3O4Composite material and preparation method and application.A kind of carbon coating Fe3O4Composite material, the composite material, has the following structure general formula: CNT@hollow Fe3O4@C, wherein CNT is carbon nanotube, hollow Fe3O4It is Fe3O4Hollow pipe, be in hollow tubular structure, C is to be coated on hollow Fe3O4Outermost layer carbon shell, the material have layering tubular structure, outermost layer clad be carbon shell, carbon shell inner wall be Fe3O4The hollow tube of composition is carbon nanotube in innermost layer, wherein carbon nanotube and Fe3O4It is reserved with certain clearance space between pipe, forms tube-in-tube structure, which can be applied to lithium ion battery, sodium-ion battery or kalium ion battery as negative electrode material.
Description
Technical field
The invention belongs to new energy field, in particular to a kind of carbon coating Fe3O4It composite material and preparation method and answers
With.
Background technique
Lithium ion battery (LIB) becomes portable due to its high-energy density, long circulation life and good safety
The main power source of electronic equipment.For this purpose, with greater need for higher energy/power density and more preferable circulative new electrode material.
Wherein, Fe3O4Due to its low cost, environment friendly and high theoretical capacity (924mA h g-1) and be considered as a kind of having very much
The anode material of prospect.However, such as in the case where the metal oxide anode based on conversion, lithium is inserted into/extract Fe3O4Process
In volume change big (74%) cause Fe3O4The aggregation and crushing of anode typically result in the circulation of quick inducing capacity fading and difference
Stability.
In order to improve Fe3O4The lithium storge quality of anode has developed two kinds of main policies in the past few years.A kind of strategy
It is the nanometer Fe that manufacture has mesoporous or hollow structure3O4Material.This nanostructure anode can provide active sites abundant
Point, short electrons/ions diffusion path and the interstitial space for volume adjustment, to improve specific capacity and cyclical stability.
Another strategy is by Fe3O4It is combined with various carbon nanomaterials (such as carbon nanotube, graphene, mesoporous carbon and carbon coating), purport
Fe is solved at the same time3O4Electric conductivity defect and volume change.For example, Jiaping Wang et al. discovery is coated with Fe3O4Carbon receive
Mitron (CNT) shows good cyclicity, and in 0.1A g-1800mAh g is kept after lower 100 circulations-1Capacity
[Nano Lett.,13(2013)818].There is previous report to demonstrate respectively and utilizes graphene/CNT@Fe3O4On composite material
Addition carbon coating can mitigate Fe3O4Aggregation, thus extend battery cycle life [a.Chem.Eng.J., 326 (2017) 507；
b.Chem.Eur.J.,19(2013)9866；c.J.Mater.Chem.A,3(2015)18289].However, due to its volume change
Greatly, Fe3O4The problem of assembling and crushing, still can occur during charge and discharge cycles for base anode, fill so that seriously limiting it
Discharge cycles stability.
Summary of the invention
In view of the problems of the existing technology the purpose of the present invention, provides a kind of carbon coating Fe3O4Composite material and its preparation
Methods and applications.
The technical scheme is that
A kind of carbon coating Fe3O4Composite material, the composite material, has the following structure general formula: CNT@hollow
Fe3O4@C, wherein CNT is carbon nanotube, hollow Fe3O4It is Fe3O4Hollow tube, be in hollow tubular structure, C is to be coated on
hollow Fe3O4Outermost layer carbon shell, the material have layering tubular structure, outermost layer clad be carbon shell, carbon shell
Inner wall is Fe3O4The hollow tube of composition is carbon nanotube in innermost layer, wherein carbon nanotube and Fe3O4It is reserved between pipe certain
Clearance space, formed tube-in-tube structure.
Further, the carbon nanotube is selected from multi-walled carbon nanotube, single-walled carbon nanotube, single-walled carbon nanotube and restrains it
One of；
Further, the single-walled carbon nanotube is restrained, the caliber of multi-walled carbon nanotube is selected from 5-50nm；
Further, the single-walled carbon nanotube is restrained, the caliber of multi-walled carbon nanotube is selected from 20-50nm；
Further, the carbon nanotube and Fe3O4Certain clearance space volume is reserved between pipe to be greater than or equal to
Fe3O4Fe in hollow pipe3O4The 74% of mass volume；
Further, described to be coated on hollow Fe3O4The thickness of surface carbon shell is selected from 1-15nm, preferably 3-6nm；
Further, the carbon nanotube, Fe3O4Preferably be selected from 15.6wt% respectively with the content of C, 68.6wt% and
15.8wt%；
The caliber of the composite material is 60nm-450nm, length 50nm-10um；
The caliber of the composite material is 100-200nm, length 500nm-3um；
The pore volume of the composite material is 0.27cm3/g；
The Fe3O4Object phase is consistent with object on JCPDS No.19-0629 standard card；
The Fe3O4In nanometer strip, each strip Fe3O4It is crosslinked together, form porous Fe3O4Hollow tube.
A kind of carbon coating Fe3O4The application of composite material is applied to lithium ion battery, sodium-ion battery as negative electrode material
Or kalium ion battery.
One kind includes the carbon coating Fe3O4The secondary cell of composite material, the secondary cell include lithium-ion electric
Pond, sodium-ion battery or kalium ion battery, the lithium ion battery, sodium-ion battery or kalium ion battery include positive, negative
Pole and electrolyte；The cathode includes: collector and the negative electrode material that is supported on the collector；Wherein, the negative electrode material
Contain the composite material.
A kind of carbon coating Fe3O4The preparation method of composite material, comprising the following steps:
1) preparation of carboxylic carbon nano-tube: after carbon nanotube is placed in concentrated nitric acid the 1-6h that flows back, cold filtration is used in combination
Deionized water is washed to neutrality, drying for standby；The carbon nanotube is selected from multi-walled carbon nanotube or single-walled carbon nanotube wherein
One of；The caliber of the multi-walled carbon nanotube is selected from 5-50nm.
2) preparation of CNT@C composite nano materials: carboxylic carbon nano-tube, lauryl sodium sulfate and glucose are dispersed
In deionized water, mixture solution A is obtained after ultrasonic disperse is uniform；The carboxylic carbon nano-tube, dodecyl sulphate
The mass ratio of sodium and glucose is 20:2:(400~800).Mixture solution A is transferred in stainless steel cauldron liner and is carried out
Hydro-thermal reaction keeps 3h~48h or more at 160~200 DEG C.After reaction kettle cooled to room temperature, brown product is collected,
It is washed repeatedly several times with deionized water and ethyl alcohol, obtains CNT C composite nano materials after dry.
The structure of the CNT@C is one layer of carbon-coating of carbon nanotube outer cladding.
The temperature and time of the reaction of the hydro-thermal, 180-190 DEG C of further preferred temperature, 12~15h of time；
3) preparation of CNT@C@FeOOH composite material: CNT@C is dissolved in ethyl alcohol and the mixed solution of deionized water, ultrasound
After being uniformly dispersed, ferric salt and urea is added, continues ultrasonic disperse, obtains mixed solution B.By mixed solution B at 60-80 DEG C
Heating stirring for 24 hours more than.CNT@C@FeOOH composite material is obtained after filtration, washing and drying.The CNT@C@FeOOH is multiple
The structure of condensation material is CNT@C external sheath FeOOH；The volume ratio of the second alcohol and water is 32:5.3；The FeOOH is
Nanoparticle, particle size 3-10nm.The CNT@C@FeOOH material has multilayer coating structure, and most kernel axle center is
Carbon nanotube, carbon nano tube surface coat one layer of carbon-coating, coat one layer of FeOOH outside carbon-coating again.
4)CNT@hollow Fe2O3Preparation: CNT@C@FeOOH is placed in calcination in air, calcination to selective removal
Fall the intermediate carbon-coating in whole CNT C FeOOH, finally obtains CNT hollow Fe2O3Composite material；Calcination temperature in air
Selected from 230-550 DEG C, the time is selected from 0.5-12h；It is preferred that being warming up to 400 DEG C in air with the rate of 1-20 DEG C/min, and protect
Hold 2h.
5)CNT@hollow Fe3O4The preparation of@C: by CNT@hollow Fe2O3It is ultrasonically formed in dispersion deionized water
Cetyl trimethylammonium bromide (CTAB) and ammonium hydroxide is added in even solution, and continuation ultrasonic disperse is uniform, and resorcinol and first is added
Aldehyde solution obtains mixed solution C, and continues to stir 16h or more.Filtering several times with water and ethanol washing is dried to obtain CNT@
hollow Fe2O3@RF composite material.By CNT@hollow Fe2O3@RF is placed in tube furnace, under an inert atmosphere pyrocarbon
Change, cooled to room temperature to get arrive CNT@hollow Fe3O4@C composite.
The RF is phenolic resin, the CNT@hollow Fe2O3@RF composite material is CNT@hollow Fe2O3
One layer of novolac resin layer of external sheath, the CNT@hollow Fe3O4The structure of@C is the Fe in hollow tubular structure3O4,
It covers in CNT outer layer, Fe3O4Clearance space is remained between hollow tube wall and CNT outer layer, and in Fe3O4Outsourcing is overlying on one layer of carbon
Layer.The temperature of the high temperature cabonization is selected from 450-600 DEG C, retention time 1-5h.The Fe3O4In nanometer strip, each strip
Fe3O4It is crosslinked together, form porous hollow tube.
Compared with prior art, carbon coating Fe provided by the invention3O4Composite material has layering tubular structure, outermost layer
Clad is carbon shell, and carbon shell inner wall is Fe3O4The molecular middle empty nanotube of nanoparticle is carbon nanotube in innermost layer, wherein
Carbon nanotube and Fe3O4It is reserved with certain clearance space between nanotube, forms tube-in-tube structure.The material of this structure is made
Carbon nanotube presence for lithium ion battery, sodium-ion battery or kalium ion battery negative electrode material, innermost layer can substantially improve
The electric conductivity of material, carbon nanotube and Fe3O4The space reserved between nanotube is conducive to caused by buffer battery intermediate ion deintercalation
The variation of volume, while external carbon-coating being capable of buffers active material volume variation broken ring integrally-built to material and group
Poly-, crushing phenomenon, to improve the structural stability of electrode material and then promote battery charging and discharging cyclical stability.In addition, this
A structure more innovation is active constituent Fe3O4It is tubular structure, not only ensure that reserved active material volume variation
Space, and active constituent Fe3O4It can also directly be contacted with outermost layer carbon-coating, be more advantageous to shorten Ion transfer path in this way, from
And improve the high rate performance of battery.
Carbon coating Fe provided by the invention3O4The technical essential of the preparation method of composite material:
In the preparation of step 2) CNT@C composite nano materials, by adjusting the usage ratio of glucose and adjusting hydro-thermal
Reaction temperature and time can effectively control C layers of thickness, thus Effective Regulation carbon nanotube and Fe3O4It is reserved between nanotube
Spatial volume, optimal reserved space volume may be implemented.The temperature and time of hydro-thermal, which directly affects, is coated on carbon nanotube
The thickness of outer layer carbon-coating, temperature is too high or the time is too long, and to will cause carbon layers having thicknesses blocked up, causes to form Fe in subsequent step3O4It is empty
Clearance space between heart tube wall and CNT outer layer is too big, to influence the battery performance of final product.
The innovation of step 4) is that accurately controlling the temperature of air calcination and calcination process guarantees in CNT@C-material
C layers are got rid of, and CNT is retained.It is preferred that being warming up to 400 DEG C in air with the rate of 1-20 DEG C/min, and keep 2h.
The innovation of step 5) is to accurately control the amount of RF and carbonization temperature the thickness, it can be achieved that outermost cladding carbon-coating
Degree, the thickness of carbon-coating will have a direct impact on the battery performance of electrode material, and carbon-coating is too thick to slow down ion transportation, carbon-coating too Bao Rong
Carbon-coating is easily caused to be destroyed in active material volume change procedure.So the thickness of carbon-coating is selected from 1-15nm, preferably 3-6nm.
Carbon coating Fe provided by the invention3O4Composite material shows height ratio capacity as ion cathode material lithium, excellent
High rate performance and outstanding cyclical stability.In 0.2 and 4A g-1Current density under show 859 and 428mA h respectively
g-1Height ratio capacity, in 0.2A g-1758mA h g is still kept after lower 500 circulations-1Specific capacity in addition, in 1.5Ag-1Height
After lower 1000 circulations of rate, there is 409mA h g-1Specific capacity, with the long-life cycle performance.
Detailed description of the invention
Fig. 1 is preparation carbon coating Fe3O4The flow diagram of composite material, process 1 indicate to coat in carbon nanotube outer surface
One layer of carbon-coating, the expression of process 2 coat one layer of FeOOH again on the carbon-coating of cladding, and the expression of process 3 completely removes intermediate carbon-coating, together
When FeOOH be converted to Fe2O3, process 4 indicates to coat one layer of carbon-coating, while Fe in outermost layer2O3It is higher to be converted to capacity density
Fe3O4。
Fig. 2 is MWNT@C (a, b, c), MWNT@C@FeOOH (d, e, f), MWNT@hollow Fe prepared by embodiment 12O3
The representative stereoscan photograph and transmission electron microscope photo of (g, h, i) composite material.
Fig. 3 is carbon coating Fe manufactured in the present embodiment3O4The stereoscan photograph (a, b) and transmission electron microscope of composite material shine
Piece (c, d).
Fig. 4 is carbon coating Fe manufactured in the present embodiment3O4The x-ray diffractogram of powder (XRD) of composite material.
Fig. 5 is MWNT@hollow Fe manufactured in the present embodiment2O3Composite material and MWNT@hollow Fe3O4The heat of@C
Multigraph.
Fig. 6 is the thermal multigraph of MWNT@C composite manufactured in the present embodiment.
Fig. 7 is the XRD spectrum of MWNT@C@FeOOH composite material manufactured in the present embodiment.
Fig. 8 is MWNT@hollow Fe manufactured in the present embodiment2O3The XRD spectrum of composite material.
Fig. 9 is MWNT@hollow Fe manufactured in the present embodiment3O4The isothermal nitrogen adsorption desorption curve of@C composite.
Figure 10,11 are MWNT@hollow Fe manufactured in the present embodiment3O4When being used as ion battery cathode of@C composite
Charge-discharge performance figure.
Figure 12 is the lithium ion battery that comparative example is used and 1 same method of embodiment assembles and the test of identical test method
Business preparation Fe3O4And Fe2O3Charge-discharge performance figure.
Specific embodiment
Embodiment 1:
1) multi-walled carbon nanotube (MWNTs) of the selection having a size of 5-50nm first uses concentrated nitric acid before the use
(65wt%) reflux 6h under the oil bath at 140 DEG C carries out carboxylated.After being cooled to room temperature, filtration washing is until neutral, drying
It is spare.
2) carboxylated MWNTs, lauryl sodium sulfate and glucose are dispersed in deionized water, after ultrasonic disperse is uniform
Obtain mixture solution A.The specific mass ratio of carboxylated MWNTs, lauryl sodium sulfate and glucose is 20mg:2mg:
400~800mg.
3) mixture solution A is transferred in 25ml stainless steel cauldron liner, is sealed, keep 15h to carry out at 190 DEG C
Hydro-thermal reaction.After reaction kettle cooled to room temperature, brown product is collected, is washed repeatedly several times with deionized water and ethyl alcohol,
Finally dry 12h obtains MWNT@C composite nano materials at 80 DEG C.
4) 160mg MWNT C be dissolved in ethyl alcohol and the mixed solution of deionized water (volume ratio of second alcohol and water be 32ml:
5.3ml), after ultrasonic disperse is uniform, 540mg FeCl is added3·6H2O and 1.2g urea continue ultrasonic disperse, obtain mixing molten
Liquid B.
5) mixed solution B is transferred in 50ml flask.The mixture solution is placed in heating stirring 60h under 60 DEG C of oil baths.
MWNT@C@FeOOH is obtained after filtration, washing and drying.
6) it MWNT@C@FeOOH will be obtained is placed in Muffle furnace to be warming up to 400 DEG C in air with the rate of 1 DEG C/min, protect
Hold 2h.MWNT@hollow Fe is obtained after room temperature when cooling2O3Composite material.
7) by MWNT@hollow Fe2O3It is ultrasonically formed homogeneous solution in dispersion deionized water, 0.6ml0.01M is added
CTAB and 48 μ l ammonium hydroxide continue ultrasound 0.5h, and 24mg resorcinol and 33.6 μ l formalins are added, obtain mixed solution C, and
Continue to stir 16h.Filtering several times with water and ethanol washing is dried to obtain MWNT@hollow Fe2O3@RF composite material.
8) by MWNT@hollow Fe2O3@RF is placed in tube furnace, and under the atmosphere of argon gas, 550 DEG C of calcining 2h carry out carbon
Change.Cooled to room temperature to get arrive MWNT@hollow Fe3O4@C composite.
9) product of step 8) (80wt%), conductive black (10wt%) and carboxymethyl cellulose (CMC10wt%) is same
When be put into agate mortar and ground, wherein deionized water is as dispersing agent, and nickel foam is as collector.By ground slurry
Material is coated uniformly in the nickel foam of load weighted drying, carries out pressing weighing to electrode slice after dry 12h under 80 DEG C of vacuum,
According to the of poor quality to obtain the stock quality on each electrode slice of collector coating front and back.Continue true by 80 DEG C of the electrode slice
It is put into glove box after the dry 2h of sky, with button cell to be assembled.
10) assembling that button cell is carried out in the glove box full of argon gas, is metal lithium sheet to electrode, and diaphragm is
2300 film of Celgard, made electrode slice are working electrode.Electrolyte is 1M LiPF6At ethylene carbonate (EC): carbonic acid
Methyl ethyl ester (EMC): dimethyl carbonate (DMC) (volume ratio 1:1:1)
11) constant current charge-discharge test mainly examine or check charging and discharging capacity of the lithium ion half-cell under different current densities,
Cycle performance and high rate performance.Lithium ion half-cell first carries out constant-current discharge to 0.05V, is embedded in the lithium ion in metal lithium sheet
Working electrode material；Constant-current charge is to 3V again, with this loop test.
Fig. 2 is MWNT@C (a, b, c) manufactured in the present embodiment, MWNT@C@FeOOH (d, e, f), MWNT@hollow Fe2O3
The representative stereoscan photograph and transmission electron microscope photo of (g, h, i) composite material, in terms of the result of observation, the caliber 5- of MWNT
50nm is mainly distributed on 20-50nm, and MWNT@C carbon-coating is coated in carbon nanotube outer, and the thickness of outer cladding carbon-coating is in 20nm-
200nm has, and is concentrated mainly on 40-80nm, and the carbon layers having thicknesses in MWNT@C can be anti-by the amount and hydro-thermal that control glucose
The condition answered is regulated and controled, and carbon layers having thicknesses can be accomplished 1 micron or more by the dosage of nominal increase glucose and reaction time,
MWNT@C length has between 50nm-10um, is concentrated mainly on 500nm-3um, the carbon nanotube that MWNT@C length is used
Length control, therefore the length of carbon nanotube put into can be selected arbitrarily, therefore the length of MWNT@C can also be controlled arbitrarily
System.MWNT@C@FeOOH is one layer of FeOOH nano particle of cladding on the basis of MWNT@C-structure；MWNT@C@FeOOH caliber exists
60nm-450nm has, and is concentrated mainly on 100-200nm；Have between MWNT@C@FeOOH length 50nm-10um, it is main to concentrate
In 500nm-3um.MWNT@hollow Fe2O3It is that MWNT@C@FeOOH is transformed after high temperature sintering removes C layers,
Fe2O3Form hollow tube, the CNT@hollow Fe2O3Material has tube-in-tube structure, and inner tube is carbon nanotube, and outer tube is
Fe2O3Hollow tube, CNT@hollow Fe2O3Material caliber has in 60nm-450nm, is concentrated mainly on 100-200nm, length
Have between 50nm-10um, is concentrated mainly on 500nm-3um.
Fig. 3 is carbon coating Fe manufactured in the present embodiment3O4The stereoscan photograph (a, b) and transmission electron microscope of composite material shine
Piece (c, d), it can be observed that having layering tubular structure in figure, outermost layer clad is carbon shell, and carbon shell inner wall is Fe3O4Shape
At middle empty nanotube, be carbon nanotube, wherein carbon nanotube and Fe in innermost layer3O4Be reserved between nanotube it is certain between
Gap space forms tube-in-tube structure；Caliber has in 60nm-450nm, is concentrated mainly on 100-200nm, length 50nm-10um
Between have, be concentrated mainly on 500nm-3um, outermost layer carbon layers having thicknesses are concentrated mainly between 3-6nm between 1-15nm.
E, f are respectively carbon coating Fe3O4Composite material high-resolution-ration transmission electric-lens photo and crystal diffraction map, illustrate the composite material
Active material is Fe3O4, Fe3O4In nanometer strip, each strip Fe3O4It is crosslinked together, form porous hollow tube.
Fig. 4 is carbon coating Fe manufactured in the present embodiment3O4The x-ray diffractogram of powder (XRD) of composite material, the composite wood
Active constituent in material is Fe3O4, object phase is consistent with object on JCPDS No.19-0629 standard card.
Fig. 5 is MWNT@hollow Fe manufactured in the present embodiment2O3Composite material and MWNT@hollow Fe3O4The heat of@C
Multigraph calculates it is found that Fe in figure2O3Content 82wt%, MWNT@hollow Fe3O4In@C, the content 68.6wt% of Fe3O4,
Multi-walled carbon nanotube content 15.6wt%, carbon-coating content 15.8wt%.
Fig. 6 is the thermal multigraph of MWNT@C composite manufactured in the present embodiment, and the temperature of removal carbon-coating can be determined in figure
Between 230-550nm DEG C, 400 DEG C of optimal selection.
Fig. 7 is the XRD spectrum of MWNT@C@FeOOH composite material manufactured in the present embodiment, can determine FeOOH's in figure
Object is consistent in object phase and JCPDS No.34-1266 standard card.
Fig. 8 is MWNT@hollow Fe manufactured in the present embodiment2O3The XRD spectrum of composite material can determine in figure
Object is consistent in the object phase and JCPDS No.33-0664 standard card of Fe2O3.
Fig. 9 is MWNT@hollow Fe manufactured in the present embodiment3O4The isothermal nitrogen adsorption desorption curve of@C composite, warp
Analytical calculation MWNT@hollow Fe3O4The pore volume of@C composite is 0.27cm3/g。
Figure 10,11 are MWNT@hollow Fe manufactured in the present embodiment3O4When being used as ion battery cathode of@C composite
Charge-discharge performance figure, in 0.2 and 4A g-1Current density under show 859 and 428mA h g respectively-1Fabrication of High Specific Capacitance
Amount.In 0.2A g-1758mA h g is still kept after lower 500 circulations-1Specific capacity.In addition, in 1.5Ag-1High-speed under
After 1000 circulations, there is 409mA h g-1Specific capacity, with the long-life cycle performance；As a comparison case, outermost layer does not have
There is the MWNT@hollow Fe of C layers of cladding2O3Charge-discharge performance is significantly worse than MWNT@when as ion battery cathode
hollow Fe3O4@C, MWNT@hollow Fe2O3In 0.2A g-1Only residue 450mA h g after lower circulation 130 times-1Specific volume
Amount.
Figure 12 is the lithium ion battery that comparative example is used and 1 same method of embodiment assembles and the test of identical test method
Business preparation Fe3O4And Fe2O3Charge-discharge performance figure, they are respectively in 0.15A g-1Current density under recycle 150 times
Specific capacity is significantly lower than MWNT@hollow Fe afterwards2O3With MWNT@hollow Fe3O4@C。
Embodiment 2
The present embodiment difference from example 1 is that: in step 3) hydrothermal reaction condition be respectively 200 DEG C holding
3h, 160 DEG C of holdings 48h, 180 DEG C of holding 12h；Step 8) high temperature cabonization temperature is selected from 450-600 DEG C, and the time is selected from 1-5h, gas
Atmosphere is selected from nitrogen.
Embodiment 3
The present embodiment difference from example 1 is that: step 6) in air calcination temperature be 230-550 DEG C,
The retention time is 0.5-12h at such a temperature.
Claims (20)
1. a kind of carbon coating Fe3O4Composite material, which is characterized in that the composite material has the following structure general formula: CNT@
hollow Fe3O4@C, wherein CNT is carbon nanotube, hollow Fe3O4It is Fe3O4Hollow tube, be in hollow tubular structure, C
It is to be coated on hollow Fe3O4Outermost layer carbon shell, the material have layering tubular structure, outermost layer clad be carbon shell
Layer, carbon shell inner wall are Fe3O4The hollow tube of composition is carbon nanotube in innermost layer, wherein carbon nanotube and Fe3O4Between pipe
It is reserved with certain clearance space, forms tube-in-tube structure.
2. composite material according to claim 1, which is characterized in that the carbon nanotube is multi-walled carbon nanotube, list
One of wall carbon nano tube or single-walled carbon nanotube tube bank.
3. composite material according to claim 2, which is characterized in that the single-walled carbon nanotube tube bank and multi wall carbon are received
The caliber of mitron is 5-50nm, preferably 20-50nm.
4. composite material according to claim 1, which is characterized in that the Fe3O4In nanometer strip, each strip Fe3O4
It is crosslinked together, form porous Fe3O4Hollow tube.
5. composite material according to claim 1, which is characterized in that the carbon nanotube and Fe3O4It is reserved between pipe
The volume of certain clearance space is greater than or equal to Fe3O4Fe in hollow pipe3O4The 74% of mass volume.
6. composite material according to claim 1, which is characterized in that described is coated on hollow Fe3O4Outermost layer
Carbon shell with a thickness of 1-15nm, preferably 3-6nm.
7. composite material according to claim 1, which is characterized in that the caliber of the composite material is 60nm-
450nm, length 50nm-10um；It is preferred that caliber is 100-200nm, length 500nm-3um.
8. a kind of such as the described in any item carbon coating Fe of claim 1-73O4The preparation method of composite material, comprising the following steps:
By CNT@hollow Fe2O3Material is distributed in deionized water into homogeneous solution, and cetyl trimethylammonium bromide is added
(CTAB) and ammonium hydroxide redisperse is uniform, adds resorcinol and formalin, obtains mixed solution and continues to stir 16h or more,
Filtering, after washing, is dried to obtain CNT@hollow Fe2O3@RF composite material；By CNT@hollow Fe2O3@RF inert atmosphere
Lower 450-600 DEG C of carbonization 1-5h finally obtains CNT@hollow Fe3O4@C composite is the carbon coating Fe3O4It is multiple
Condensation material；
The CNT@hollow Fe2O3Material has tube-in-tube structure, and inner tube is carbon nanotube, outer tube Fe2O3Hollow tube；
The carbon nanotube is one of multi-walled carbon nanotube or single-walled carbon nanotube；
The RF is phenolic resin, the CNT@hollow Fe2O3@RF composite material is CNT@hollow Fe2O3Outer layer
Coat one layer of novolac resin layer；
The inert atmosphere refers to one of high pure nitrogen, high-purity argon gas, high-purity helium, high-purity neon, high-purity Krypton or several
Kind.
9. according to the method described in claim 8, it is characterized in that, the CNT@hollow Fe2O3The preparation method of material,
The following steps are included:
CNT@C@FeOOH is placed in calcination in air, the middle carbon in whole CNT@C@FeOOH is fallen in calcination to selective removal
Layer, finally obtains CNT@hollow Fe2O3Composite material；
The CNT@C@FeOOH has multilayer coating structure, and most kernel axle center is carbon nanotube, carbon nano tube surface cladding one
Layer carbon-coating, carbon-coating coat one layer of FeOOH again outside.
10. according to the method described in claim 9, it is characterized in that, the FeOOH is nanoparticle, nano-particles size
For 3-10nm.
11. according to the method described in claim 9, it is characterized in that, calcination in the air, is 230- selected from calcination temperature
550 DEG C, the time keeps 0.5-12h.
12. according to the method described in claim 9, it is characterized in that, calcination in the air, is selected from 1-20 DEG C/min's
Rate is warming up to 400 DEG C, and the time keeps 2h.
13. according to the described in any item methods of claim 9-12, which is characterized in that the preparation side of the CNT@C@FeOOH
Method, comprising the following steps:
1) carboxylic carbon nano-tube is prepared；
2) CNT@C composite nano materials are prepared；
3) it prepares CNT@C@FeOOH composite material: CNT@C composite nano materials is dissolved in the mixed solution of ethyl alcohol and deionized water
In, after ultrasonic disperse is uniform, ferric salt and urea is added, continues ultrasonic disperse, obtains mixed solution B；Mixed solution B is existed
At 60-80 DEG C heating stirring for 24 hours more than；CNT@C@FeOOH composite material is obtained after filtration, washing and drying；
The structure of the CNT@C composite nano materials is one layer of carbon-coating of carbon nanotube outer cladding；
The carboxylic carbon nano-tube is the carbon nanotube that carboxylic group is contained on surface.
14. according to the method for claim 13, which is characterized in that the volume ratio of the ethyl alcohol and deionized water is selected from
32:5.3。
15. according to the method for claim 13, which is characterized in that the preparation method of the carboxylic carbon nano-tube, packet
Include following steps: after carbon nanotube is placed in concentrated nitric acid the 1-6h that flows back, cold filtration is simultaneously washed with deionized to neutrality, is done
It is dry spare.
16. according to the method for claim 13, which is characterized in that the preparation method of the CNT@C composite nano materials,
Include the following steps: drying for standby carboxylic carbon nano-tube, lauryl sodium sulfate and glucose are dispersed in deionized water
In, mixture solution A is obtained after being uniformly dispersed；Mixture solution A is transferred in reactor and carries out hydro-thermal reaction, 160~
3h~48h is kept at 200 DEG C, after completion of the reaction, is filtered, and washing obtains CNT@C composite nano materials after dry；
The mass ratio of the carboxylic carbon nano-tube, lauryl sodium sulfate and glucose is 20:2:(400~800).
17. according to the method for claim 16, which is characterized in that the temperature of the hydro-thermal reaction is selected from 180-190 DEG C,
Retention time is selected from 12~15h.
18. according to the method for claim 13, which is characterized in that the thickness of carbon-coating in the CNT@C composite nano materials
Degree is greater than 1nm, preferably 20-40nm.
19. a kind of carbon coating Fe according to any one of claims 1 to 73O4Composite material is in the power generation of primary or secondary electrochemical
Device, high-energy power generation device and the application in electrochemical luminescence modulating system, which is characterized in that as negative electrode material be applied to lithium from
Sub- battery, sodium-ion battery or kalium ion battery.
20. one kind includes carbon coating Fe of any of claims 1-73O4The secondary cell of composite material, it is described
Secondary cell includes lithium ion battery, sodium-ion battery or kalium ion battery, the lithium ion battery, sodium-ion battery or potassium
Ion battery includes anode, cathode and electrolyte；The cathode includes: collector and the cathode material that is supported on the collector
Material；Wherein, the negative electrode material contains the composite material.
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