CN109473649A - A kind of sodium-ion battery composite negative pole material and preparation method thereof - Google Patents
A kind of sodium-ion battery composite negative pole material and preparation method thereof Download PDFInfo
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- CN109473649A CN109473649A CN201811320300.2A CN201811320300A CN109473649A CN 109473649 A CN109473649 A CN 109473649A CN 201811320300 A CN201811320300 A CN 201811320300A CN 109473649 A CN109473649 A CN 109473649A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/64—Carriers or collectors
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- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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Abstract
A kind of sodium-ion battery composite negative pole material and preparation method thereof, it belongs to anode material of lithium-ion battery field.The technical problems to be solved by the invention are the new anode material of lithium-ion battery of exploitation.The present invention prepares grapheme foam material, carbon nanotube is grown on the grapheme foam material of preparation, prepare carbon nanotube-grapheme foam complex material, the carbon nanotube of preparation-grapheme foam complex material is surface-treated, configure vanadium dioxide nano piece reaction solution, the carbon nanotube of preparation-grapheme foam complex material is completely disposed in the vanadium dioxide nano piece reaction solution of configuration, 175~185 DEG C of reaction temperature of control, 3~3.5h of reaction time, product is taken out after reaction, for several times with deionized water and alcohol rinse, it is dry, annealing 2~2.5 hours.The present invention is used for anode material of lithium-ion battery, improves the electric conductivity of active material and the energy density of battery.
Description
Technical field
The invention belongs to anode material of lithium-ion battery fields；More particularly to a kind of sodium-ion battery composite negative pole material and
Preparation method.
Background technique
It is the burning by fossil fuel that the mankind, which obtain the major way of the energy, at present, however a large amount of burnings of fossil fuel
The problems such as not only resulting in resource exhaustion, also bringing serious environmental pollution and climate warming.Therefore, develop it is renewable,
The energy stores and switch technology of environmental protection become the goal in research in global range.Lithium ion battery is long with high reversible specific capacity
Cycle life and the advantages such as environmental-friendly, have attracted the concern of vast researcher, and be widely used in portable electronic
In equipment.But lithium resource is deficient on the earth, it is difficult to maintain the increasingly increased energy demand of the mankind.Therefore, it exploits natural resources rich
The novel energy storage of richness, low cost, green safe alternative lithium ion battery is extremely urgent with converting system.
Sodium element with main group has electrochemical properties similar with lithium, and sodium element is widely distributed in the earth's crust, because
Sodium-ion battery research temperature rises year by year in recent years for this.It is well known that it is similar to lithium ion battery, restrict sodium-ion battery
The principal element of chemical property is electrode material, therefore, explores the most important thing that suitable storage sodium material is research.Sodium ion
With bigger ionic radius, more extensive ion channel is needed in charge and discharge process, cause cannot directly using lithium from
Electrode material of the host material of son as sodium-ion battery.With slow when most of materials are as sodium-ion battery electrode
Electrochemical reaction dynamics, therefore not all lithium ion battery electrode material is suitable for doing sodium ion electrode.
Summary of the invention
It is an object of the present invention to provide a kind of sodium-ion battery composite negative pole materials and preparation method thereof.
The invention is realized by the following technical scheme:
A kind of preparation method of sodium-ion battery composite negative pole material, includes the following steps:
Step a, grapheme foam material is prepared, for use；
Step b, carbon nanotube, preparation carbon nanotube-graphene bubble are grown on the grapheme foam material of step a preparation
Foam complex material, for use；
Step c, carbon nanotube-grapheme foam complex material prepared by step b is surface-treated, after processing to
With；
Step d, vanadium dioxide nano piece reaction solution is configured, for use；
Step e, carbon nanotube-grapheme foam complex material prepared by step c is completely disposed at the two of step d configuration
In vanadium oxide nanometer sheet reaction solution, 175~185 DEG C of reaction temperature are controlled, 3~3.5h of reaction time takes out product after reaction, use
Deionized water and alcohol rinse 3~5 times are placed in 120~130 DEG C of vacuum drying ovens dry 6~7h.Finally, by product 400~
2~2.5 hours are annealed in 420 DEG C of air to get to a kind of sodium-ion battery composite negative pole material.
A kind of preparation method of sodium-ion battery composite negative pole material of the present invention, grapheme foam material in step a
The preparation method of material includes the following steps:
Step a1, nickel foam substrate is cleaned up, and impregnates 4~6h with 5% dilute hydrochloric acid, rinse 3 with deionized water
~5 times, 60 DEG C of dryings, for use；
Step a2, by step a1, treated that nickel foam substrate is placed in horizontal quartz tube furnace, to horizontal quartz tube
The mixed gas of argon gas and hydrogen is passed through in furnace, be heated to 1000 DEG C after keep 5min, then with the mixed gas of argon gas, hydrogen
It as carrier gas, is brought into reaction cavity through liquid ethanol, in 1000 DEG C of holding 5min, is then return to be passed through argon gas and hydrogen
Mixed gas is cooled to rapidly room temperature, obtained sample, for use；
Step a3, the obtained sample of step a2 is immersed in the FeCl of 1mol/l3With the mixed solution of the dilute hydrochloric acid of 5wt%
In, it is taken out after 48 hours, obtains grapheme foam material.
A kind of preparation method of sodium-ion battery composite negative pole material of the present invention, the nickel foam substrate in step a1
Having a size of 2cm × 2cm~8cm × 8cm, nickel foam substrate with a thickness of 0.9~1.1mm.
A kind of preparation method of sodium-ion battery composite negative pole material of the present invention, argon gas and hydrogen in step a2
The flow velocity of argon gas is 280sccm in mixed gas, the flow velocity of hydrogen is 20sccm, argon gas, hydrogen carrier gas mixed gas in argon
The flow velocity of gas is 160sccm, the flow velocity of hydrogen is 40sccm.
A kind of preparation method of sodium-ion battery composite negative pole material of the present invention, carbon nanotube-graphite in step b
The preparation method of alkene foam complex material includes the following steps:
Step b1, nickel-cobalt catalyst is configured, by 1mmolNi (NO3)2·6H2O and 2mmol Co (NO3)2·6H2O is first respectively
After be added in 40 ml deionized waters, 12mmol urea, then ultrasound 15 minutes are added in ultrasound after 15 minutes, obtain the nickel
Co catalysts；
Step b2, growth carbon nanotube on grapheme foam material prepared by step a is placed in described in step b1 obtains
Nickel-cobalt catalyst, in 120 DEG C of progress hydro-thermal reaction 2h, cooled to room temperature obtains nickel cobalt composite graphite alkene foamed material；
Step b3, nickel cobalt composite graphite alkene foamed material made from step b2 is placed in horizontal quartz tube furnace, Xiang Shui
Argon gas is passed through in flat quartz tube furnace, be heated to 750 DEG C after be passed through argon gas, hydrogen, ethylene mixed gas keep 10min, so
After revert to and be passed through argon gas and be cooled to room temperature rapidly, obtain carbon nanotube-grapheme foam complex material.
A kind of preparation method of sodium-ion battery composite negative pole material of the present invention, the flow velocity of argon gas is in step b3
100sccm, argon gas, hydrogen, ethylene mixed gas in argon gas flow velocity be 100sccm, the flow velocity of hydrogen is 40sccm, ethylene
Flow velocity be 20sccm.
A kind of preparation method of sodium-ion battery composite negative pole material of the present invention, carbon nanotube-stone in step c
Black alkene foam complex material surface treatment is dense for carbon nanotube made from step b-grapheme foam complex material to be placed in
In sulfuric acid, 120 DEG C are boiled 2h.
A kind of preparation method of sodium-ion battery composite negative pole material of the present invention, the carbon nanometer after surface treatment
Pipe-grapheme foam complex material mass density is 0.65~0.66mg/cm2。
A kind of preparation method of sodium-ion battery composite negative pole material of the present invention, vanadium dioxide nano in step d
The configuration method of piece reaction solution includes the following steps:
Step d1,1.2gV is weighed2O5Powder and 1.8g oxalic acid powder, are dissolved in 40ml deionized water, and 75 DEG C of hot bath, directly
It is all dissolved to powder, obtains mixed solution, for use；
Step d2, the mixed solution that 5ml step 1 obtains is measured, 30ml reaction kettle is transferred to, and is added 1ml's thereto
The hydrogen peroxide and 20ml dehydrated alcohol of 30wt%, persistently stirs 20min, obtains vanadium dioxide nano piece reaction solution.
A kind of a kind of sodium-ion battery of the preparation method preparation of sodium-ion battery composite negative pole material of the present invention
Composite negative pole material, a kind of Rong Liang≤650mAhg of sodium-ion battery composite negative pole material-1。
A kind of sodium-ion battery composite negative pole material of the present invention is usually chased after compared to traditional powdery electrode material
Ask lesser particle size, i.e. nano material.Nano material has bigger active surface area compared to bulk material, more conducively
The insertion and abjection of sodium ion, however, too small nano-scale, is easy to produce particle agglomeration phenomenon in charge and discharge process, it is weak
The advantage of nano material is changed.The present invention by nano material in conjunction with array electrode, successfully utilize a step solvent heat method,
By VO2Nanometer sheet be uniformly embedded in conductive substrates GF (foamy graphite alkene, graphene Foam)/CNTs (carbon nanotube,
Carbon nanotubes, CNTs) surface, the advantage of nano material high activity surface was not only played, but also improve active material
Electric conductivity, while improving the energy density of battery.
A kind of sodium-ion battery composite negative pole material of the present invention has the beneficial effect that:
(1) GF is the fabulous a kind of base material of porous, light weight, electric conductivity, and growing the CNTs on GF is a kind of offer
High porosity, high suppleness, the one-dimensional material of high length-diameter ratio.The GF/CNTs nano compound film of three-dimensional structure has super large
Specific surface area, the conductive capability of superelevation, high porosity and good wellability, therefore be fabulous ion and electron-transport bone
Frame structure；
(2) three-dimensional CNTs/GF film is fabulous as flexible flexible flexible substrates electric conductivity with super strength
Collector, and its ultralight quality, substantially increase the specific capacity of sodium-ion battery；
(3) VO of two-dimensional ultrathin2Nanometer sheet is directly embedded in GF/CNTs film surface, does not need conductive materials and adhesive
The addition of sum further improves the energy density of conventional powder electrode material；
(4) nano material has a bigger active surface area compared to bulk material, more conducively the insertion of sodium ion and de-
Out, however, too small nano-scale, is easy to produce particle phenomenon in charge and discharge process, the advantage of nano material is weakened.This
Invention a kind of sodium-ion battery composite negative pole material, by nano material in conjunction with array electrode, successfully by VO2 nanometer sheet
It uniformly is embedded in the surface conductive substrates GF/CNTs, the reunion of nano material is overcome, has both played the advantage of nano material, together
When, improve the electric conductivity of active material；
(5) VO of layer structure2Be conducive to the insertion and deintercalation of sodium ion, ultra-thin VO2Pattern shortens ion/electronics
Diffusion length, and provide bigger surface for sodium ion storage, enhance the diffusion and electric charge transfer of sodium ion.
(6)VO2The flexibility characteristics of/CNTs/GF composite materials, can effectively alleviate charge and discharge to a certain extent
Volume change in journey, to improve the cyclical stability of battery.
A kind of sodium-ion battery composite negative pole material of the present invention, it is low to overcome traditional anode material of lithium-ion battery
The shortcomings that active surface, increases specific capacity, meanwhile, the addition of conductive materials and binder is eliminated, the energy of battery is improved
Metric density is a kind of promising anode material of lithium-ion battery.
Detailed description of the invention
Fig. 1 is a kind of X-ray diffractogram of sodium-ion battery composite negative pole material of one method of specific embodiment preparation
Spectrum；
Fig. 2 is a kind of sweeping for 150 times of sodium-ion battery composite negative pole material of one method of specific embodiment preparation
Retouch electron microscopic picture；
Fig. 3 is 10,000 times of a kind of sodium-ion battery composite negative pole material of one method of specific embodiment preparation
Scanning electron microscopic picture；
Fig. 4 is a kind of sweeping for 100,000 times of sodium-ion battery composite negative pole material of one method of specific embodiment preparation
Retouch electron microscopic picture；
Fig. 5 is a kind of the saturating of 100,000 times of sodium-ion battery composite negative pole material of one method of specific embodiment preparation
Penetrate electron microscopic picture；
Fig. 6 is a kind of the saturating of 2,000,000 times of sodium-ion battery composite negative pole material of one method of specific embodiment preparation
Penetrate electron microscopic picture；
Fig. 7 is that a kind of high-resolution of sodium-ion battery composite negative pole material of one method of specific embodiment preparation transmits electricity
Mirror picture；
Fig. 8 is a kind of selective electron diffraction of sodium-ion battery composite negative pole material of one method of specific embodiment preparation
Figure；
Fig. 9 is that a kind of cycle performance of sodium-ion battery composite negative pole material of one method of specific embodiment preparation is bent
Line；
Figure 10 is that a kind of high rate performance of sodium-ion battery composite negative pole material of one method of specific embodiment preparation is bent
Line.
Specific embodiment
Specific embodiment 1:
A kind of preparation method of sodium-ion battery composite negative pole material, includes the following steps:
Step a, grapheme foam material is prepared, for use；
Step b, carbon nanotube, preparation carbon nanotube-graphene bubble are grown on the grapheme foam material of step a preparation
Foam complex material, for use；
Step c, carbon nanotube-grapheme foam complex material prepared by step b is surface-treated, after processing to
With；
Step d, vanadium dioxide nano piece reaction solution is configured, for use；
Step e, carbon nanotube-grapheme foam complex material prepared by step c is completely disposed at the two of step d configuration
In vanadium oxide nanometer sheet reaction solution, control 180 DEG C of reaction temperature, reaction time 3h takes out product after reaction, with deionized water and
Alcohol rinse 4 times, dry 6h is placed in 120 DEG C of vacuum drying ovens.Finally, product is annealed 2 hours in 400 DEG C of air, i.e.,
Obtain a kind of sodium-ion battery composite negative pole material.
A kind of preparation method of sodium-ion battery composite negative pole material described in present embodiment, graphene bubble in step a
The preparation method of foam material includes the following steps:
Step a1, nickel foam substrate is cleaned up, and impregnates 5h with 5% dilute hydrochloric acid, rinsed 4 times with deionized water,
60 DEG C of dryings, for use；
Step a2, by step a1, treated that nickel foam substrate is placed in horizontal quartz tube furnace, to horizontal quartz tube
The mixed gas of argon gas and hydrogen is passed through in furnace, be heated to 1000 DEG C after keep 5min, then with the mixed gas of argon gas, hydrogen
It as carrier gas, is brought into reaction cavity through liquid ethanol, in 1000 DEG C of holding 5min, is then return to be passed through argon gas and hydrogen
Mixed gas is cooled to rapidly room temperature, obtained sample, for use；
Step a3, the obtained sample of step a2 is immersed in the FeCl of 1mol/l3With the mixed solution of the dilute hydrochloric acid of 5wt%
In, it is taken out after 48 hours, obtains grapheme foam material.
A kind of preparation method of sodium-ion battery composite negative pole material described in present embodiment, the nickel foam in step a1
Size of foundation base be 8cm × 8cm, nickel foam substrate with a thickness of 1mm.
A kind of preparation method of sodium-ion battery composite negative pole material described in present embodiment, argon gas and hydrogen in step a2
The flow velocity of argon gas is 280sccm in the mixed gas of gas, the flow velocity of hydrogen is 20sccm, then with argon gas, the gaseous mixture of hydrogen
Body is brought into reaction cavity as carrier gas through liquid ethanol, argon gas, hydrogen carrier gas mixed gas in the flow velocity of argon gas be
160sccm, hydrogen flow velocity be 40sccm be then return to be passed through the gaseous mixture of argon gas and hydrogen in 1000 DEG C of holding 5min
Body is cooled to rapidly room temperature, obtained sample.
A kind of preparation method of sodium-ion battery composite negative pole material described in present embodiment, carbon nanotube-in step b
The preparation method of grapheme foam complex material includes the following steps:
Step b1, nickel-cobalt catalyst is configured, by 1mmolNi (NO3)2·6H2O and 2mmol Co (NO3)2·6H2O is first respectively
After be added in 40 ml deionized waters, 12mmol urea, then ultrasound 15 minutes are added in ultrasound after 15 minutes, obtain the nickel
Co catalysts；
Step b2, growth carbon nanotube on grapheme foam material prepared by step a is placed in described in step b1 obtains
Nickel-cobalt catalyst, in 120 DEG C of progress hydro-thermal reaction 2h, cooled to room temperature obtains nickel cobalt composite graphite alkene foamed material；
Step b3, nickel cobalt composite graphite alkene foamed material made from step b2 is placed in horizontal quartz tube furnace, Xiang Shui
Argon gas is passed through in flat quartz tube furnace, be heated to 750 DEG C after be passed through argon gas, hydrogen, ethylene mixed gas keep 10min, so
After revert to and be passed through argon gas and be cooled to room temperature rapidly, obtain carbon nanotube-grapheme foam complex material.
A kind of preparation method of sodium-ion battery composite negative pole material described in present embodiment, the stream of argon gas in step b3
Speed be 100sccm, argon gas, hydrogen, ethylene mixed gas in argon gas flow velocity be 100sccm, the flow velocity of hydrogen is 40sccm,
The flow velocity of ethylene is 20sccm.
A kind of preparation method of sodium-ion battery composite negative pole material described in present embodiment, the carbon nanometer in step c
Pipe-grapheme foam complex material surface treatment is to set carbon nanotube made from step b-grapheme foam complex material
In the concentrated sulfuric acid, 120 DEG C are boiled 2h.
A kind of preparation method of sodium-ion battery composite negative pole material, the carbon after surface treatment described in present embodiment are received
Mitron-grapheme foam complex material mass density is 0.65mg/cm2。
A kind of preparation method of sodium-ion battery composite negative pole material described in present embodiment, vanadium dioxide in step d
The configuration method of nanometer sheet reaction solution includes the following steps:
Step d1,1.2gV is weighed2O5Powder and 1.8g oxalic acid powder, are dissolved in 40ml deionized water, and 75 DEG C of hot bath, directly
It is all dissolved to powder, obtains mixed solution, for use；
Step d2, the mixed solution that 5ml step 1 obtains is measured, 30ml reaction kettle is transferred to, and is added 1ml's thereto
The hydrogen peroxide and 20ml dehydrated alcohol of 30wt%, persistently stirs 20min, obtains vanadium dioxide nano piece reaction solution.
Specific embodiment 2:
The one of the preparation method preparation of a kind of sodium-ion battery composite negative pole material according to specific embodiment one
Kind sodium-ion battery composite negative pole material, a kind of Rong Liang≤650mAhg of sodium-ion battery composite negative pole material-1。
A kind of a kind of sodium ion of the preparation method preparation of sodium-ion battery composite negative pole material described in present embodiment
Battery composite cathode material carries out X-ray diffraction test as shown in Figure 1, can be seen that from X-ray diffraction spectra at 26 ° or so
There is a strong diffraction maximum, be the diffraction maximum of graphene (JCPDS-NO.75-1621), (002) for corresponding to 2H phase graphene is brilliant
Face, remaining all diffraction maximum can match with the monocline crystal phase VO2 (B) (JCPDS-NO.31-1438) in PDF card,
Without other miscellaneous peaks, the results showed that be successfully prepared out the VO2 nanometer sheet of pure phase.
A kind of a kind of sodium ion of the preparation method preparation of sodium-ion battery composite negative pole material described in present embodiment
Battery composite cathode material is scanned Electronic Speculum test, and the scanning electron microscopic picture of different amplification is as shown in Figure 2,3, 4, from
As can be seen that carbon nanotube is evenly distributed on foamy graphite alkene in figure, and VO2Nanometer sheet it is vertical be embedded in carbon nanotube table
Face forms a kind of high porosity, the structure of bigger serface.This structure is conducive to contact of the active material with electrolyte, and
And Particle diffusion distance is shortened, a kind of unique structure design of sodium-ion battery composite negative pole material may be implemented big
The storage of multiplying power sodium ion can obtain good chemical property.
A kind of a kind of sodium ion of the preparation method preparation of sodium-ion battery composite negative pole material described in present embodiment
Battery composite cathode material, carry out transmissioning electric mirror test, the transmission electron microscope picture of different amplification as viewed in figures 5-8, into one
Step demonstrates the structure of VO2/CNTs/GF composite Nano chip arrays, Fig. 5 VO2Scheme with the TEM of CNTs composite nano plate, from figure
In can clearly find out, VO2 nanometer sheet is uniformly wrapped in carbon nano tube surface.Fig. 6 is red dotted box portion in Fig. 5
Enlarged drawing, as can be seen from Figure 6 the diameter of carbon nanotube is about 20nm, and VO2 nanometer sheet and CNTs are closely coupled.Fig. 7 is height
Times transmission electron microscope photo, can be clearly seen that interplanar distance is about from photoWith (200) crystal face of VO2
It is consistent.The VO2 nanometer sheet of mono-crystalline structures can pass through Fig. 8 secondary evidence.
A kind of a kind of sodium ion of the preparation method preparation of sodium-ion battery composite negative pole material described in present embodiment
Battery composite cathode material carries out electrochemical property test, as shown in Figure 9, Figure 10.Fig. 9 is cyclical stability test, from Fig. 9
In, it can be seen that in 0.2Ag-1250 circle of circulation under current density, for capacity almost without decaying, coulombic efficiency is about 100%, exhibition
Good cyclical stability is revealed, a kind of sodium-ion battery composite negative pole material improves VO with CNTs/GF substrate2
The electric conductivity of nanometer sheet increases VO2The specific capacity of nanometer sheet, and be conducive to a kind of following for sodium-ion battery composite negative pole material
The raising of ring stability.Figure 10 is in different current density lower electrode material stability curves, and electrode material is respectively in 0.1Ag-1,
0.2Ag-1, 0.5Ag-1, 1Ag-1, 2Ag-1, 3Ag-1, 5Ag-1, 10Ag-1Current density under recycle, capacity can be stablized
650mAhg-1, 600mAhg-1, 560mAhg-1, 490mAhg-1, 440mAhg-1, 375mAhg-1, 300mAhg-1, 200mAhg-1It is left
The right side, also, when circulation is restored to low current density 2Ag-1When lower test, capacity is similarly increased to 410mAhg-1.Illustrate,
No matter under high current density or under low current density, the electrode material of the composite construction of this unique texture all has good
Good high rate performance, a kind of unique structure design of sodium-ion battery composite negative pole material realize big multiplying power sodium ion
Storage.
Specific embodiment 3:
A kind of preparation method of sodium-ion battery composite negative pole material, includes the following steps:
Step a, grapheme foam material is prepared, for use；
Step b, carbon nanotube, preparation carbon nanotube-graphene bubble are grown on the grapheme foam material of step a preparation
Foam complex material, for use；
Step c, carbon nanotube-grapheme foam complex material prepared by step b is surface-treated, after processing to
With；
Step d, vanadium dioxide nano piece reaction solution is configured, for use；
Step e, carbon nanotube-grapheme foam complex material prepared by step c is completely disposed at the two of step d configuration
In vanadium oxide nanometer sheet reaction solution, 175~185 DEG C of reaction temperature are controlled, 3~3.5h of reaction time takes out product after reaction, use
Deionized water and alcohol rinse 3~5 times are placed in 120~130 DEG C of vacuum drying ovens dry 6~7h.Finally, by product 400~
2~2.5 hours are annealed in 420 DEG C of air to get to a kind of sodium-ion battery composite negative pole material.
Described in present embodiment the advantages of a kind of sodium-ion battery composite negative pole material are as follows: GF be it is porous, light weight, lead
A kind of electrically fabulous base material, growing the CNTs on GF is a kind of offer high porosity, high suppleness, the one of high length-diameter ratio
Tie up material.The GF/CNTs nano compound film of three-dimensional structure has the specific surface area of super large, the conductive capability of superelevation, high hole
Rate and good wellability, therefore be fabulous ion and electron-transport skeleton structure.
Described in present embodiment the advantages of a kind of sodium-ion battery composite negative pole material are as follows: three-dimensional CNTs/GF film
It is fabulous collector, and its ultralight quality, significantly as flexible flexible flexible substrates electric conductivity with super strength
Improve the specific capacity of sodium-ion battery.
Described in present embodiment the advantages of a kind of sodium-ion battery composite negative pole material are as follows: the VO of two-dimensional ultrathin2Nanometer
Piece is directly embedded in GF/CNTs film surface, does not need the addition of conductive materials and adhesive sum, further improves conventional powder
The energy density of electrode material.
Described in present embodiment the advantages of a kind of sodium-ion battery composite negative pole material are as follows: nano material is compared to bulk
Material has bigger active surface area, the more conducively insertion and abjection of sodium ion, however, too small nano-scale, in charge and discharge
It is easy to produce particle phenomenon in electric process, weakens the advantage of nano material.A kind of sodium-ion battery of the present invention is compound
VO2 nanometer sheet is successfully uniformly embedded in conductive substrates GF/CNTs table by nano material in conjunction with array electrode by negative electrode material
Face, overcomes the reunion of nano material, has both played the advantage of nano material, meanwhile, improve the electric conductivity of active material.
Described in present embodiment the advantages of a kind of sodium-ion battery composite negative pole material are as follows: the VO of layer structure2Favorably
In the insertion and deintercalation of sodium ion, ultra-thin VO2Pattern shortens ion/electronics diffusion length, and stores for sodium ion
Bigger surface is provided, the diffusion and electric charge transfer of sodium ion are enhanced.
Described in present embodiment the advantages of a kind of sodium-ion battery composite negative pole material are as follows: VO2/ CNTs/GF compound
The flexibility characteristics of material can effectively alleviate the volume change in charge and discharge process, to improve battery to a certain extent
Cyclical stability.
Specific embodiment 4:
A kind of preparation method of sodium-ion battery composite negative pole material according to specific embodiment three, in step a
The preparation method of grapheme foam material includes the following steps:
Step a1, nickel foam substrate is cleaned up, and impregnates 4~6h with 5% dilute hydrochloric acid, rinse 3 with deionized water
~5 times, 60 DEG C of dryings, for use；
Step a2, by step a1, treated that nickel foam substrate is placed in horizontal quartz tube furnace, to horizontal quartz tube
The mixed gas of argon gas and hydrogen is passed through in furnace, be heated to 1000 DEG C after keep 5min, then with the mixed gas of argon gas, hydrogen
It as carrier gas, is brought into reaction cavity through liquid ethanol, in 1000 DEG C of holding 5min, is then return to be passed through argon gas and hydrogen
Mixed gas is cooled to rapidly room temperature, obtained sample, for use；
Step a3, the obtained sample of step a2 is immersed in the FeCl of 1mol/l3With the mixed solution of the dilute hydrochloric acid of 5wt%
In, it is taken out after 48 hours, obtains grapheme foam material.
Specific embodiment 5:
A kind of preparation method of sodium-ion battery composite negative pole material according to specific embodiment three, in step a1
Nickel foam size of foundation base be 2cm × 2cm~8cm × 8cm, nickel foam substrate with a thickness of 0.9~1.1mm.
Specific embodiment 6:
A kind of preparation method of sodium-ion battery composite negative pole material according to specific embodiment three, in step a2
The flow velocity of argon gas is 280sccm in the mixed gas of argon gas and hydrogen, the flow velocity of hydrogen is 20sccm, then with argon gas, hydrogen
Mixed gas as carrier gas, brought into reaction cavity through liquid ethanol, argon gas, hydrogen carrier gas mixed gas in argon gas stream
Speed is 160sccm, the flow velocity of hydrogen is 40sccm, in 1000 DEG C of holding 5min, is then return to be passed through the mixed of argon gas and hydrogen
It closes gas and is cooled to room temperature rapidly, obtained sample.
Specific embodiment 7:
A kind of preparation method of sodium-ion battery composite negative pole material according to specific embodiment three, in step b
Carbon nanotube-grapheme foam complex material preparation method includes the following steps:
Step b1, nickel-cobalt catalyst is configured, by 1mmolNi (NO3)2·6H2O and 2mmol Co (NO3)2·6H2O is first respectively
After be added in 40 ml deionized waters, 12mmol urea, then ultrasound 15 minutes are added in ultrasound after 15 minutes, obtain the nickel
Co catalysts；
Step b2, growth carbon nanotube on grapheme foam material prepared by step a is placed in described in step b1 obtains
Nickel-cobalt catalyst, in 120 DEG C of progress hydro-thermal reaction 2h, cooled to room temperature obtains nickel cobalt composite graphite alkene foamed material；
Step b3, nickel cobalt composite graphite alkene foamed material made from step b2 is placed in horizontal quartz tube furnace, Xiang Shui
Argon gas is passed through in flat quartz tube furnace, be heated to 750 DEG C after be passed through argon gas, hydrogen, ethylene mixed gas keep 10min, so
After revert to and be passed through argon gas and be cooled to room temperature rapidly, obtain carbon nanotube-grapheme foam complex material.
Specific embodiment 8:
A kind of preparation method of sodium-ion battery composite negative pole material according to specific embodiment three, in step b3
The flow velocity of argon gas be 100sccm, argon gas, hydrogen, ethylene mixed gas in argon gas flow velocity be 100sccm, hydrogen flow velocity
For 40sccm, the flow velocity of ethylene is 20sccm.
Specific embodiment 9:
A kind of preparation method of sodium-ion battery composite negative pole material according to specific embodiment three, in step c
Carbon nanotube-grapheme foam complex material surface treatment for by carbon nanotube-grapheme foam made from step b it is compound
Body material is placed in the concentrated sulfuric acid, and 120 DEG C are boiled 2h.
Specific embodiment 10:
A kind of preparation method of sodium-ion battery composite negative pole material according to specific embodiment three, surface treatment
Carbon nanotube afterwards-grapheme foam complex material mass density is 0.65~0.66mg/cm2。
Specific embodiment 11:
A kind of preparation method of sodium-ion battery composite negative pole material according to specific embodiment three, in step d
The configuration method of vanadium dioxide nano piece reaction solution includes the following steps:
Step d1,1.2gV is weighed2O5Powder and 1.8g oxalic acid powder, are dissolved in 40ml deionized water, and 75 DEG C of hot bath, directly
It is all dissolved to powder, obtains mixed solution, for use；
Step d2, the mixed solution that 5ml step 1 obtains is measured, 30ml reaction kettle is transferred to, and is added 1ml's thereto
The hydrogen peroxide and 20ml dehydrated alcohol of 30wt%, persistently stirs 20min, obtains vanadium dioxide nano piece reaction solution.
Specific embodiment 12:
A kind of preparation method system of sodium-ion battery composite negative pole material according to specific embodiment three to 11
A kind of standby sodium-ion battery composite negative pole material, the Rong Liang of sodium-ion battery composite negative pole material a kind of≤
650mAhg-1。
Claims (10)
1. a kind of preparation method of sodium-ion battery composite negative pole material, characterized by the following steps:
Step a, grapheme foam material is prepared, for use；
Step b, carbon nanotube is grown on the grapheme foam material of step a preparation, preparation carbon nanotube-grapheme foam is multiple
Polymer material, for use；
Step c, carbon nanotube-grapheme foam complex material prepared by step b is surface-treated, it is stand-by after processing；
Step d, vanadium dioxide nano piece reaction solution is configured, for use；
Step e, carbon nanotube-grapheme foam complex material prepared by step c is completely disposed to the titanium dioxide of step d configuration
In vanadium nanometer sheet reaction solution, control 175~185 DEG C of reaction temperature, 3~3.5h of reaction time takes out product after reaction, spend from
Sub- water and alcohol rinse 3~5 times are placed in 120~130 DEG C of vacuum drying ovens dry 6~7h.Finally, by product 400~420
DEG C air in anneal 2~2.5 hours to get to a kind of sodium-ion battery composite negative pole material.
2. a kind of preparation method of sodium-ion battery composite negative pole material according to claim 1, it is characterised in that: step
The preparation method of grapheme foam material includes the following steps: in a
Step a1, nickel foam substrate is cleaned up, and impregnates 4~6h with 5% dilute hydrochloric acid, rinse 3~5 with deionized water
It is secondary, 60 DEG C of dryings, for use；
Step a2, by step a1, treated that nickel foam substrate is placed in horizontal quartz tube furnace, into horizontal quartz tube furnace
Be passed through the mixed gas of argon gas and hydrogen, be heated to 1000 DEG C after keep 5min, then using argon gas, hydrogen mixed gas as
Carrier gas is brought into reaction cavity through liquid ethanol, in 1000 DEG C of holding 5min, is then return to be passed through the mixing of argon gas and hydrogen
Gas is cooled to rapidly room temperature, obtained sample, for use；
Step a3, the obtained sample of step a2 is immersed in the FeCl of 1mol/l3In the mixed solution of the dilute hydrochloric acid of 5wt%, 48
It is taken out after hour, obtains grapheme foam material.
3. according to a kind of preparation method of sodium-ion battery composite negative pole material according to claim 2, it is characterised in that:
Nickel foam size of foundation base in step a1 is 2cm × 2cm~8cm × 8cm, nickel foam substrate with a thickness of 0.9~1.1mm.
4. a kind of preparation method of sodium-ion battery composite negative pole material according to claim 2, it is characterised in that: step
The flow velocity of argon gas is 280sccm in the mixed gas of argon gas and hydrogen in a2, the flow velocity of hydrogen is 20sccm, and argon gas, hydrogen carry
The flow velocity of argon gas is 160sccm in the mixed gas of gas, the flow velocity of hydrogen is 40sccm.
5. a kind of preparation method of sodium-ion battery composite negative pole material according to claim 1, it is characterised in that: step
Carbon nanotube-grapheme foam complex material preparation method includes the following steps: in b
Step b1, nickel-cobalt catalyst is configured, by 1mmolNi (NO3)2·6H2O and 2mmol Co (NO3)2·6H2O, which is taken up in order of priority, to be added
Enter into 40 ml deionized waters, 12mmol urea, then ultrasound 15 minutes are added in ultrasound after 15 minutes, obtain the nickel cobalt and urge
Agent；
Step b2, growth carbon nanotube on grapheme foam material prepared by step a is placed in the nickel that step b1 is obtained
Co catalysts, in 120 DEG C of progress hydro-thermal reaction 2h, cooled to room temperature obtains nickel cobalt composite graphite alkene foamed material；
Step b3, nickel cobalt composite graphite alkene foamed material made from step b2 is placed in horizontal quartz tube furnace, Xiang Shuiping stone
Argon gas is passed through in English tube furnace, be heated to 750 DEG C after be passed through argon gas, hydrogen, ethylene mixed gas keep 10min, it is then extensive
It is multiple to be cooled to room temperature rapidly to be passed through argon gas, obtain carbon nanotube-grapheme foam complex material.
6. a kind of preparation method of sodium-ion battery composite negative pole material according to claim 5, it is characterised in that: step
The flow velocity of argon gas is 100sccm in b3, argon gas, hydrogen, ethylene mixed gas in the flow velocity of argon gas be 100sccm, hydrogen
Flow velocity is 40sccm, and the flow velocity of ethylene is 20sccm.
7. a kind of preparation method of sodium-ion battery composite negative pole material according to claim 1, it is characterised in that: step
Carbon nanotube-grapheme foam complex material surface treatment in c is by carbon nanotube-grapheme foam made from step b
Complex material is placed in the concentrated sulfuric acid, and 120 DEG C are boiled 2h.
8. a kind of preparation method of sodium-ion battery composite negative pole material according to claim 7, it is characterised in that: surface
Carbon nanotube that treated-grapheme foam complex material mass density is 0.65~0.66mg/cm2。
9. a kind of preparation method of sodium-ion battery composite negative pole material according to claim 1, it is characterised in that: step
The configuration method of vanadium dioxide nano piece reaction solution includes the following steps: in d
Step d1,1.2gV is weighed2O5Powder and 1.8g oxalic acid powder, are dissolved in 40ml deionized water, and 75 DEG C of hot bath, until powder
Last all dissolutions, obtain mixed solution, for use；
Step d2, the mixed solution that 5ml step 1 obtains is measured, 30ml reaction kettle is transferred to, and is added 1ml's thereto
The hydrogen peroxide and 20ml dehydrated alcohol of 30wt%, persistently stirs 20min, obtains vanadium dioxide nano piece reaction solution.
10. the one of a kind of preparation method preparation of sodium-ion battery composite negative pole material described in a kind of one of claim 1-9
Kind sodium-ion battery composite negative pole material, it is characterised in that: a kind of Rong Liang of sodium-ion battery composite negative pole material≤
650mAhg-1。
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