CN110078060A - A kind of graphene nano stripping and the preparation method and application thereof - Google Patents
A kind of graphene nano stripping and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110078060A CN110078060A CN201810073684.6A CN201810073684A CN110078060A CN 110078060 A CN110078060 A CN 110078060A CN 201810073684 A CN201810073684 A CN 201810073684A CN 110078060 A CN110078060 A CN 110078060A
- Authority
- CN
- China
- Prior art keywords
- graphene nano
- carbon nanotube
- preparation
- stripping
- stannic oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/06—Graphene nanoribbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of graphene nano strippings and the preparation method and application thereof.The preparation method includes: to carry out longitudinal oxidation removing to carbon nanotube using Hummers method, forms stannic oxide/graphene nano band solution；Freeze-drying process is oriented to stannic oxide/graphene nano band solution, obtains structurally ordered cotton-shaped stannic oxide/graphene nano stripping.Present invention process is simple, obtained graphene nano stripping has three-dimensional porous structure, biggish specific surface area and the oxygen-containing functional group for being largely conducive to store up lithium, thus the negative electrode of lithium ion battery that material is prepared has height ratio capacity (500-650mAh/g), superior chemical property and good high rate performance, is a kind of ideal cell negative electrode material of performance.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material and its preparation process, in particular to a kind of graphene nano item
Carrying material, preparation method and its application in lithium ion battery negative material, lithium ion battery, belong to lithium ion battery
Technical field.
Background technique
Human social development makes rapid progress, and while energy demand increasingly increases, coal, petroleum, natural gas etc. are non-renewable
The storage capacity of the energy is sharply reduced, and finds novel renewable and clean energy resource as the task of top priority, lithium ion battery is superior due to its
Performance show one's talent as specific energy and the highest secondary cell type of efficiency.Nineteen ninety Tazawa et al. starts using carbon materials
Material does cathode, and the compound of lithium and transition metal has prepared lithium ion battery as anode.Carbon material is as lithium ion battery
Negative electrode material has during removal lithium embedded that structure change is smaller, electrode potential is lower, platform stable, electric conductivity are superior, at low cost
Honest and clean, abundance, it is nontoxic the advantages that, therefore up to now, Carbon materials are still most common negative electrode of lithium ion battery material
Material includes mainly graphite-like, amorphous carbons, carbon fibre material etc., however the specific capacity of traditional carbon material is lower, about exists
376mAh/g or so is unable to satisfy requirement in terms of energy density.
2004, British scientist Geim and Novoselov successfully separated two-dimentional carbon material stone from graphite for the first time
Black alkene, different from blocky graphite, it is by sp2Two-dimensional surface unimolecule made of the hexagoinal lattice close-packed arrays of hydridization carbon composition
Layer crystalline material.Graphene has huge specific surface area and excellent electricity, calorifics and power as emerging two-dimentional carbon material
Performance is learned, is expected to obtain important application in terms of lithium ion battery negative material.Boehm etc. selects graphite as lithium-ion electric
Pond cathode measures battery capacity 372mAh/g [Carbon, I975 (13): 337-345], and Zhao etc. prepares graphene nanometer sheet
As negative electrode of lithium ion battery, material capacity reaches 794-1054mA h/g [Chem.Mater.2009,21,3136-3142],
Much higher than traditional carbon material.However, since the diffusion barrier that lithium ion traverses longitudinally through graphene is up to 9eV [ACS
Appl.Mater.Interfaces 2012,4,2432-2438], therefore the huge specific surface area of grapheme material hinders instead
Lithium ion transport in charge and discharge process.
Summary of the invention
The main purpose of the present invention is to provide a kind of graphene nano strippings and the preparation method and application thereof, thus
Overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions:
The embodiment of the invention provides a kind of preparation methods of graphene nano stripping comprising:
Longitudinal oxidation removing is carried out to carbon nanotube using Hummers method, forms stannic oxide/graphene nano band solution；
Freeze-drying process is oriented to the stannic oxide/graphene nano band solution, obtains structurally ordered cotton-shaped oxygen
Graphite alkene nanoribbons material.
In some embodiments, the preparation method include: make comprising carbon nanotube, the concentrated sulfuric acid, phosphoric acid, oxidant it is mixed
Reaction system is closed in 60~80 DEG C of 1~3h of reaction, forms stannic oxide/graphene nano band solution.
Further, the preparation method specifically includes: carbon nanotube being added in the concentrated sulfuric acid and stirs 1~3h, Zhi Houyi
Secondary addition phosphoric acid, oxidant, form the hybrid reaction system.
Further, the carbon nanotube, the concentrated sulfuric acid, phosphoric acid, oxidant mass volume ratio be 1g:150~500mL:
10~56mL:2~10g.
Further, the preparation method further include: be 0.5 by the hybrid reaction system and concentration after reaction
The hydrogenperoxide steam generator of~1wt% mixes, and carries out eccentric cleaning to precipitating is obtained, and dialyses 8~15 days later, forms uniform oxygen
Graphite alkene nanoribbons solution.
Further, the orientation freeze-drying includes:: by the stannic oxide/graphene nano band solution in vertical direction
On 2h or more in cooling medium immersed with the speed of 1~100mm/min, later in 5 DEG C or less freeze-drying 5~15 days.
Further, the graphene nano stripping is cotton-shaped, the length of the graphene nano stripping
It is 0.5~20 μm, width is 100~500nm, and specific surface area is 200~800m2/g。
The embodiment of the invention provides a kind of graphene nano strippings prepared by preceding method.
The embodiment of the invention also provides foregoing graphites alkene nanoribbons materials in preparing the purposes in lithium ion battery.
The embodiment of the invention also provides a kind of lithium ion battery negative materials, and it includes graphene nano bands above-mentioned
Material.
The embodiment of the invention also provides a kind of negative electrode of lithium ion battery, and it includes negative electrode of lithium ion battery materials above-mentioned
Material.
Compared with the prior art, the beneficial effects of the present invention are:
1) present invention process is simple, wherein removing to form graphene nano item as raw material by using carbon nanotube
Band, the carbon nanotube that part is not completely reduced in stripping process not only play a supportive role, and improve electric conductivity and lithium from
Sub- transfer rate, obtained graphene nano band is since with special two-dimensional structure, edge has accumulated a large amount of active sites, stores up
Lithium performance is higher than most of carbon material.
2) present invention makes hydrone crystallographic orientation in solution, obtains stable structure by using orientation freeze-drying
3-D ordered multiporous stannic oxide/graphene nano strip band network, layer of powder material are spaced about 0.89nm, increase the ratio table of material
Area reduces the reunion and bonding of graphene nano band.
3) graphene nano band itself width that the present invention is obtained is smaller, for graphene nanometer sheet, more has
Conducive to the disengaging of lithium ion, inhibition is reduced, while graphene nano band of the invention does not use any reduction treatment
Deoxidation, most of oxygen-containing functional group is remained by low temperature drying instead, have more active sites, storage lithium performance and
Lithium ion transport rate is significantly improved, and then can greatly improve the battery capacity of lithium ion battery entirety, and leads in battery
Domain obtains and is widely applied.
4) graphene nano stripping specific capacity with higher (the 100mA/g constant current charge-discharge that the present invention is obtained
When specific capacity reach 557.55mAh/g), superior electric conductivity and chemical property, good high rate performance, in all directions
It is a kind of ideal cell negative electrode material of performance with excellent conductive performance and lithium ion transport performance, stable structure.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, but it does not constitute any limitation of the invention.
Fig. 1 is the method flow schematic diagram that a typical method of the invention prepares graphene nano stripping.
Fig. 2 is the atomic force microscopy diagram of the obtained graphene nano stripping of the embodiment of the present invention 1.
Fig. 3 is the XRD curve graph of the obtained graphene nano stripping of the embodiment of the present invention 1.
Fig. 4 is the battery rate charge-discharge curve graph of the obtained graphene nano stripping of the embodiment of the present invention 1.
Fig. 5 is the battery constant current cycle charging and discharging curve figure of the obtained graphene nano stripping of the embodiment of the present invention 1.
Fig. 6 is the electron microscope of the obtained graphene nano stripping of reference examples of the present invention.
Fig. 7 is the XRD curve graph of the obtained graphene nano stripping of reference examples of the present invention.
Fig. 8 is the battery rate charge-discharge curve graph of the obtained graphene nano stripping of reference examples of the present invention.
Specific embodiment
As previously mentioned, inventor is studied for a long period of time and largely practiced in view of deficiency in the prior art, proposed
Technical solution of the present invention.The technical solution, its implementation process and principle etc. will be further explained as follows.
As the one aspect of technical solution of the present invention, involved in be a kind of graphene nano stripping preparation
Method comprising:
Longitudinal oxidation removing is carried out to carbon nanotube using Hummers method, forms stannic oxide/graphene nano band solution；
Freeze-drying process is oriented to the stannic oxide/graphene nano band solution, obtains structurally ordered cotton-shaped oxygen
Graphite alkene nanoribbons material.
In some embodiments, the preparation method include: make comprising carbon nanotube, the concentrated sulfuric acid, phosphoric acid, oxidant it is mixed
Reaction system is closed in 60~80 DEG C of 1~3h of reaction, forms stannic oxide/graphene nano band solution.
Further, the preparation method specifically includes: carbon nanotube being added in the concentrated sulfuric acid and stirs 1~3h, Zhi Houyi
Secondary addition phosphoric acid, oxidant, form the hybrid reaction system.
Further, the carbon nanotube, the concentrated sulfuric acid, phosphoric acid, oxidant mass volume ratio be 1g:150~500mL:
10~56mL:2~10g.
Further, the oxidant is selected from potassium permanganate, but not limited to this.
Further, the preparation method specifically includes: 1g carbon nanotube being added in 150~500mL concentrated sulfuric acid and is stirred
After mixing 1~3h, 10~56mL phosphoric acid is at the uniform velocity instilled in 30min, mixing is added with the speed of 1~2g/h in 2~10g potassium permanganate
In solution；Thereafter make comprising carbon nanotube, the concentrated sulfuric acid, phosphoric acid, potassium permanganate hybrid reaction system in 60~80 DEG C react 1~
3h, mixed system are poured slowly into 0 DEG C or so of deionized water and are stirred continuously after being cooled to room temperature.
Further, the carbon nanotube includes few layer carbon nanotube.
Preferably, the carbon nanotube includes single-walled carbon nanotube or multi-walled carbon nanotube.
Preferably, the length of the carbon nanotube is 0.5~20 μm, and diameter is 2~50nm.
The present invention uses carbon nanotube as raw material, the carbon nanotube that part is not completely reduced in stripping process, no
It only plays a supportive role, and improves electric conductivity and lithium ion transfer rate.
Further, the preparation method further include: be 0.5 by the hybrid reaction system and concentration after reaction
The hydrogenperoxide steam generator of~1wt% mixes, and carries out eccentric cleaning to precipitating is obtained, and dialyses 8~15 days, is added a certain amount of later
Stannic oxide/graphene nano band solution is ultrasonically formed after deionized water.
Preferably, the molecular cut off of bag filter that uses of dialysing is 3500~15000.
Wherein, among one more specifically case study on implementation, the preparation method is specifically included:
Carbon nanotube is added in the concentrated sulfuric acid and phosphoric acid mixed solution, then potassium permanganate oxidant is added portionwise, 60~80
DEG C heated at constant temperature stirs 1~3h, and mixed solution is poured slowly into the peroxidating of a certain concentration (0.5~1wt%) in ice-water bath
Overnight precipitation in hydrogen solution finally uses 5wt% hydrochloric acid eccentric cleaning, dialyses 8~15 days, surpasses after a certain amount of deionized water is added
Sound forms stannic oxide/graphene nano band solution.
Further, the orientation freeze-drying includes liquid nitrogen frozen and vacuum drying.Present invention employs freeze-dryings
Method reduces the reunion and bonding of graphene nano band.
Further, the orientation freeze-drying includes: that stannic oxide/graphene nano band solution is poured into cylindric plastics
It in container, is slowly immersed in the cooling mediums such as liquid nitrogen with the speed of 1~100mm/min, is protected after being completely immersed in vertical direction
2h or more is held, completely rear taking-up to be frozen is put into 5~15 days dry in 5 DEG C or less in freeze drier later.
Wherein, among one more specifically case study on implementation, the preparation method specifically includes the following steps:
(1) few layer carbon nanotube is passed through into the longitudinally oxidation removing of Hummers method, oxygen is obtained by centrifuge washing and dialysis
Graphite alkene nanoribbons solution；
(2) the stannic oxide/graphene nano band solution is oriented freeze-drying, obtains cotton-shaped graphene oxide and receives
Rice stripping.
The other side of the embodiment of the present invention additionally provides a kind of graphene nano piece of tape prepared by preceding method
Material.
Further, the graphene nano stripping is cotton-shaped.
Further, the length of the graphene nano stripping is 0.5~20 μm, and width is 100~500nm, than
Surface area is 200~800m2/g。
The stannic oxide/graphene nano band powder that the preparation method of the present embodiment is obtained can be used as negative electrode of lithium ion battery material
Material.
The other side of the embodiment of the present invention additionally provides foregoing graphites alkene nanoribbons material in preparing lithium-ion electric
Purposes in pond.
For example, the other side of the embodiment of the present invention additionally provides a kind of lithium ion battery negative material, it includes preceding
The graphene nano stripping stated.
The other side of the embodiment of the present invention additionally provides a kind of negative electrode of lithium ion battery, and it includes lithium ions above-mentioned
Cell negative electrode material.
The other side of the embodiment of the present invention additionally provides a kind of lithium ion battery comprising anode, cathode and electrolysis
Matter, the cathode include negative electrode of lithium ion battery above-mentioned.
Present invention process is simple, wherein remove to form graphene nano band as raw material by using carbon nanotube,
The carbon nanotube that part is not completely reduced in stripping process not only plays a supportive role, but also improves electric conductivity and lithium ion turn
Rate is moved, obtained graphene nano band is since with special two-dimensional structure, edge has accumulated a large amount of active sites, stores up lithium
Most of carbon material can be higher than, while by using orientation freeze-drying, the 3-D ordered multiporous of stable structure also can be obtained
Graphene oxide network, the reunion and bonding for reducing graphene nano band.The graphene nano band itself that the present invention is obtained
Width is smaller, for graphene nanometer sheet, is more advantageous to the disengaging of lithium ion, reduces inhibition, while this hair
Bright graphene nano band has more active sites, stores up lithium performance and lithium ion transport rate is significantly improved, in turn
The battery capacity of lithium ion battery entirety can be greatly improved, and is widely applied in field of batteries acquirement.
The graphene nano stripping specific capacity with higher that the present invention is obtained is (when 100mA/g constant current charge-discharge
Specific capacity reaches 655.23mAh/g), superior electric conductivity and chemical property, good high rate performance, have in all directions
There are excellent conductive performance and lithium ion transport performance, stable structure, is a kind of ideal cell negative electrode material of performance.
Below with reference to several preferred embodiments and attached drawing, further details of the technical solution of the present invention, it is clear that
Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, those of ordinary skill in the art's every other embodiment obtained without making creative work, all belongs to
In the scope of protection of the invention.
Embodiment 1
The preparation process of graphene nano stripping includes the following steps: in the present embodiment
1) 1g multi-walled carbon nanotube (length is 5-20 μm, average diameter 45nm) is added in 250mL concentrated sulfuric acid solution, room
Temperature stirring 2h；28mL phosphoric acid solution is at the uniform velocity added dropwise in 30min, mixed solution is added with the speed of 2g/h in 6g potassium permanganate
In, 1h is stirred at room temperature；It is heated to cooled to room temperature after 70 DEG C of stirring 2h；Mixed solution is poured slowly under the conditions of ice-water bath
In the hydrogenperoxide steam generator that 400mL concentration is 0.73%, overnight；Centrifuge washing, dialysis 10 are carried out using 5wt% hydrochloric acid solution
It.
2) the stannic oxide/graphene nano band solution ultrasound 1h that will be obtained after dialysis, with the speed of 10mm/min by built-in oxygen
The 50mL needle tubing of graphite alkene nanoribbons solution quickly immerses in liquid nitrogen, and after freezing completely, taking-up is placed in vacuum drier
Interior 10 days removal excessive moistures.
The length for the graphene nano stripping that the present embodiment obtains is 3.2 μm, width 121nm, and specific surface area is
221m2/ g is 557.55mAh/g with 100 average discharge capacities of 100mA/g constant current charge-discharge.
Embodiment 2
The preparation process of graphene nano stripping includes the following steps: in the present embodiment
1) 1g multi-walled carbon nanotube (length is 5-20 μm, average diameter 45nm) is added in 250mL concentrated sulfuric acid solution, room
Temperature stirring 2h；28mL phosphoric acid solution is at the uniform velocity added dropwise in 30min, mixed solution is added with the speed of 2g/h in 6g potassium permanganate
In, 1h is stirred at room temperature；It is heated to cooled to room temperature after 70 DEG C of stirring 2h；Mixed solution is poured slowly under the conditions of ice-water bath
In the hydrogenperoxide steam generator that 400mL concentration is 0.73%, overnight；Centrifuge washing, dialysis 10 are carried out using 5wt% hydrochloric acid solution
It.
2) the stannic oxide/graphene nano band solution ultrasound 1h that will be obtained after dialysis, will be built-in with the speed of 100mm/min
The 50mL needle tubing of stannic oxide/graphene nano band solution is slowly immersed in liquid nitrogen, and after freezing completely, taking-up is placed in vacuum drying
10 days removal excessive moistures in machine.
3.2 μm, width 121nm, specific surface area 200m of the obtained graphene nano band powder length of the present embodiment2/ g,
Total oxygen is 33.6at%, is 586.37mAh/g with 100 average discharge capacities of 100mA/g constant current charge-discharge.
Embodiment 3
The preparation process of graphene nano stripping includes the following steps: in the present embodiment
1) 1g single-walled carbon nanotube (length is 2-5 μm, average diameter 2nm) is added in 500mL concentrated sulfuric acid solution, room temperature
Stir 3h；56mL phosphoric acid solution is at the uniform velocity added dropwise in 30min, 10g potassium permanganate is added in mixed solution with the speed of 2g/h,
1h is stirred at room temperature；It is heated to cooled to room temperature after 80 DEG C of stirring 3h；Mixed solution is poured slowly under the conditions of ice-water bath
In the hydrogenperoxide steam generator that 400mL concentration is 0.73%, overnight；Centrifuge washing, dialysis 15 are carried out using 5wt% hydrochloric acid solution
It.
2) the stannic oxide/graphene nano band solution ultrasound 6h that will be obtained after dialysis, with the speed of 1mm/min by built-in oxygen
The 50mL needle tubing of graphite alkene nanoribbons solution is slowly immersed in liquid nitrogen, and after freezing completely, taking-up is placed in vacuum drier
Interior 15 days removal excessive moistures.
The length of the obtained graphene nano band of the present embodiment is 0.5 μm, width 100nm, specific surface area 335m2/
G is 655.23mAh/g with 100 average discharge capacities of 100mA/g constant current charge-discharge.
Embodiment 4
The preparation process of graphene nano stripping includes the following steps: in the present embodiment
1) 1g few-wall carbon nanotube (length is 2-5 μm, average diameter 7nm) is added in 250mL concentrated sulfuric acid solution, room temperature
Stir 1h；28mL phosphoric acid solution is at the uniform velocity added dropwise in 30min, 6g potassium permanganate is added in mixed solution with the speed of 2g/h,
1h is stirred at room temperature；It is heated to cooled to room temperature after 70 DEG C of stirring 1h；Mixed solution is poured slowly under the conditions of ice-water bath
In the hydrogenperoxide steam generator that 400mL concentration is 0.73%, overnight；Centrifuge washing is carried out using 5wt% hydrochloric acid solution, is dialysed 8 days.
2) the stannic oxide/graphene nano band solution ultrasound 0.5h that will be obtained after dialysis, will be built-in with the speed of 10mm/min
The 50mL needle tubing of stannic oxide/graphene nano band solution quickly immerses in liquid nitrogen, and after freezing completely, taking-up is placed in vacuum drying
8 days removal excessive moistures in machine.
The length of the obtained graphene nano band of the present embodiment is 0.7 μm, width 500nm, specific surface area 265m2/
G is 616.74mAh/g with 100 average discharge capacities of 100mA/g constant current charge-discharge.
Embodiment 5
The preparation process of graphene nano stripping includes the following steps: in the present embodiment
1) 1g multi-walled carbon nanotube (length is 5-20 μm, average diameter 50nm) is added in 150mL concentrated sulfuric acid solution, room
Temperature stirring 2h；10mL phosphoric acid solution is at the uniform velocity added dropwise in 30min, mixed solution is added with the speed of 1g/h in 2g potassium permanganate
In, 1h is stirred at room temperature；It is heated to cooled to room temperature after 60 DEG C of stirring 1h；Mixed solution is poured slowly under the conditions of ice-water bath
In the hydrogenperoxide steam generator that 400mL concentration is 0.73%, overnight；Centrifuge washing, dialysis 10 are carried out using 5wt% hydrochloric acid solution
It.
2) the stannic oxide/graphene nano band solution ultrasound 1h that will be obtained after dialysis, with the speed of 10mm/min by built-in oxygen
The 50mL needle tubing of graphite alkene nanoribbons solution quickly immerses in liquid nitrogen, and after freezing completely, taking-up is placed in vacuum drier
Interior 5 days removal excessive moistures.
The length of the obtained graphene nano band of the present embodiment is 4.1 μm, width 186nm, specific surface area 207m2/
G is 531.27mAh/g with 100 average discharge capacities of 100mA/g constant current charge-discharge.
Reference examples
The preparation process of graphene nano stripping includes the following steps: in the present embodiment
1) 1g multi-walled carbon nanotube (average diameter 45nm) is added in 250mL concentrated sulfuric acid solution, and 2h is stirred at room temperature；?
28mL phosphoric acid solution is at the uniform velocity added dropwise in 30min, 6g potassium permanganate is added in mixed solution with the speed of 2g/h, is stirred at room temperature
1h；It is heated to cooled to room temperature after 70 DEG C of stirring 2h；Mixed solution, which is poured slowly into 400mL concentration, under the conditions of ice-water bath is
In 0.73% hydrogenperoxide steam generator, overnight；Centrifuge washing is carried out using 5wt% hydrochloric acid solution, is dialysed 10 days.
2) the stannic oxide/graphene nano band solution ultrasound 1h that will be obtained after dialysis, with the speed of 10mm/min by built-in oxygen
The 50mL needle tubing of graphite alkene nanoribbons solution quickly immerses in liquid nitrogen, and it is more that taking-up is placed on removal in 10 days in vacuum drier
Remaining moisture.
3) the cotton-shaped stannic oxide/graphene nano band obtained after freeze-drying is put into tube furnace, the stream of argon gas and hydrogen
Speed is respectively 150sccm, 10sccm, is warming up to 800 DEG C with the speed of 5 DEG C/h, is slowly cooled to room temperature after keeping 30min, most
Grinding obtains redox graphene nanoribbons material powder afterwards.
The obtained graphene nano band powder oxygen content of this reference examples is 8.83at%, with 100mA/g constant current charge-discharge
100 average discharge capacities are 231.74mAh/g.
Present invention process is simple, as shown in Fig. 2, 1 gained stannic oxide/graphene nano stripping width of embodiment is in 120nm
Left and right, height 0.88nm, Fig. 3 show that the carbon nanotube overwhelming majority has been oxidized in 10 ° of typical graphene oxidation peaks of display
It splits.Powder sample is prepared into after half-cell with 100mAg-1The obtained result of electric current type cyclic charging and discharging test such as
Shown in Fig. 4, the stannic oxide/graphene nano stripping of embodiment 1 is due to without reduction, containing a large amount of oxygen-containing functional group, significantly
Battery capacity is improved, 100 times circulation average size has reached 557.55mAhg-1.As shown in figure 5, the oxidation stone of embodiment 1
The high rate performance of black alkene nanoribbons material is good, most starts with 100mAg-1Current cycle charge and discharge when averaged discharge hold
Measure 588.36mAhg-1, after respectively recycling 20 times with different multiplying, again with 100mAg-1Current cycle charge and discharge when it is average
Discharge capacity is down to 557.29mAhg-1, high rate performance is relatively stable.
The pattern of the obtained graphene nano band active material of reference examples is as shown in fig. 6, material produces after thermal reduction
Curling stacks to a certain degree.As shown in fig. 7, the XRD spectra of the obtained graphene nano stripping of reference examples compare embodiment 1 and
Speech, oxidation peak weaken, and graphite peaks occur, and illustrate that material part restores.Although the coulombic efficiency for the first time of material after thermal reduction processing
And cyclical stability is risen, however since the oxygen-containing functional group with electro-chemical activity is greatly decreased, nanoribbons are also
Interlamellar spacing reduction, material stacking agglomeration are obvious during original, and average size sharply drops to 231.74mAhg-1, such as Fig. 8
It is shown.
In conclusion simple process, graphene nano band is due to special by the technical solution of embodiment 1-5
Two-dimensional structure, the oxygenated functional group at edge, defect and abundance provides a large amount of active sites, and storage lithium performance is higher than most of carbon
Material；The reunion and bonding of graphene nano band are reduced using freeze-drying；It is improved using carbon nanotube as raw material
Electric conductivity and lithium ion transfer rate；Meanwhile it is graphene nano stripping specific capacity with higher of the invention, superior
Electric conductivity and chemical property, good high rate performance, be a kind of ideal cell negative electrode material of performance.
In addition, inventor also refers to the mode of embodiment 1- embodiment 5, with the other raw materials listed in this specification
Tested with condition etc., and be equally successfully made specific capacity, superior electric conductivity and chemical property with higher,
The graphene nano stripping of good high rate performance.
It should be noted that, in this document, under normal circumstances, the element limited by sentence " including ... " is not arranged
Except there is also other identical elements in including the steps that the element, process, method or experimental facilities.
It should be appreciated that the above preferred embodiment is merely to illustrate the contents of the present invention, in addition to this, there are also other by the present invention
Embodiment, as long as those skilled in the art because of technical inspiration involved in the present invention, and use equivalent replacement or equivalent deformation
The technical solution that mode is formed is fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of graphene nano stripping, characterized by comprising:
Longitudinal oxidation removing is carried out to carbon nanotube using Hummers method, forms stannic oxide/graphene nano band solution；
Freeze-drying process is oriented to the stannic oxide/graphene nano band solution, obtains cotton-shaped stannic oxide/graphene nano item
Carrying material.
2. preparation method according to claim 1, characterized by comprising: make comprising carbon nanotube, the concentrated sulfuric acid, phosphoric acid,
The hybrid reaction system of oxidant forms stannic oxide/graphene nano band solution in 60~80 DEG C of 1~3h of reaction；Preferably, institute
It states preparation method to specifically include: carbon nanotube being added in the concentrated sulfuric acid and stirs 1~3h, sequentially adds phosphoric acid, oxidant, shape later
At the hybrid reaction system；Preferably, the carbon nanotube, the concentrated sulfuric acid, phosphoric acid, oxidant mass volume ratio be 1g:150
~500mL:10~56mL:2~10g；Preferably, the oxidant includes potassium permanganate.
3. preparation method according to claim 1 or 2, it is characterised in that: the carbon nanotube includes few layer carbon nanotube；
Preferably, the carbon nanotube includes single-walled carbon nanotube or multi-walled carbon nanotube；Preferably, the length of the carbon nanotube is
0.5~20 μm, diameter is 2~50nm.
4. preparation method according to claim 2, it is characterised in that further include: after reaction, by the hybrid reaction
System mixes with the hydrogenperoxide steam generator that concentration is 0.5~1wt%, and carries out eccentric cleaning to precipitating is obtained, and dialysis 8 later~
15 days, form stannic oxide/graphene nano band solution；Preferably, the molecular cut off of bag filter that uses of dialysing is 3500
~15000.
5. preparation method according to claim 1, it is characterised in that specifically include: by the stannic oxide/graphene nano band
Solution immerses 2h or more in cooling medium in vertical direction with the speed of 1~100mm/min, dry in 5 DEG C or less freezings later
Dry 5~15 days.
6. preparation method according to any one of claims 1-5, it is characterised in that: the graphene nano stripping
To be cotton-shaped, the length of the graphene nano stripping is 0.5~20 μm, and width is 100~500nm, and specific surface area is
200~800m2/g。
7. the graphene nano stripping prepared by any one of claim 1-6 the method.
8. graphene nano stripping as claimed in claim 7 is in preparing the purposes in lithium ion battery.
9. a kind of lithium ion battery negative material, it is characterised in that include graphene nano stripping according to any one of claims 8.
10. a kind of negative electrode of lithium ion battery, it is characterised in that include lithium ion battery negative material as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810073684.6A CN110078060B (en) | 2018-01-25 | 2018-01-25 | Graphene nano strip material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810073684.6A CN110078060B (en) | 2018-01-25 | 2018-01-25 | Graphene nano strip material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110078060A true CN110078060A (en) | 2019-08-02 |
| CN110078060B CN110078060B (en) | 2021-04-30 |
Family
ID=67412171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810073684.6A Active CN110078060B (en) | 2018-01-25 | 2018-01-25 | Graphene nano strip material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078060B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114261960A (en) * | 2021-12-28 | 2022-04-01 | 南京林业大学 | Pyridine N-B configuration doped graphene nanoribbon/amorphous carbon material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634106A (en) * | 2012-04-12 | 2012-08-15 | 上海交通大学 | Preparation method of graphene oxide nanobelt/polar rubber composite material |
| CN104212053A (en) * | 2014-09-18 | 2014-12-17 | 福州大学 | Waterproof and oxygen-insulating sealing film as well as preparation method and application thereof |
| CN104448824A (en) * | 2015-01-05 | 2015-03-25 | 福州大学 | Polyimide-based composite film with optical limiting performance |
| CN106587014A (en) * | 2016-06-06 | 2017-04-26 | 重庆大学 | Preparation method of graphene nanoribbon |
-
2018
- 2018-01-25 CN CN201810073684.6A patent/CN110078060B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634106A (en) * | 2012-04-12 | 2012-08-15 | 上海交通大学 | Preparation method of graphene oxide nanobelt/polar rubber composite material |
| CN104212053A (en) * | 2014-09-18 | 2014-12-17 | 福州大学 | Waterproof and oxygen-insulating sealing film as well as preparation method and application thereof |
| CN104448824A (en) * | 2015-01-05 | 2015-03-25 | 福州大学 | Polyimide-based composite film with optical limiting performance |
| CN106587014A (en) * | 2016-06-06 | 2017-04-26 | 重庆大学 | Preparation method of graphene nanoribbon |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114261960A (en) * | 2021-12-28 | 2022-04-01 | 南京林业大学 | Pyridine N-B configuration doped graphene nanoribbon/amorphous carbon material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110078060B (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Folded-hand silicon/carbon three-dimensional networks as a binder-free advanced anode for high-performance lithium-ion batteries | |
| Chang et al. | Single-layer MoS 2/graphene dispersed in amorphous carbon: towards high electrochemical performances in rechargeable lithium ion batteries | |
| Gao et al. | Electrochemical property studies of carbon nanotube films fabricated by CVD method as anode materials for lithium-ion battery applications | |
| CN106571244A (en) | Two-dimensional transition group metal carbon (nitrogen) compound and two-dimensional transition group metal sulfide nano composite powder, preparation and application | |
| Guo et al. | Vertically aligned ultrathin MoS2 nanosheets grown on graphene-wrapped hollow carbon microtubes derived from loofah sponge as advanced anodes for highly reversible lithium storage | |
| Xia et al. | Supercritical fluid assisted biotemplating synthesis of Si–O–C microspheres from microalgae for advanced Li-ion batteries | |
| CN107959006A (en) | A kind of lignin-base hard carbon/carbon nano tube compound material and preparation method thereof and the application in lithium ion battery negative material | |
| Huang et al. | Carbon-coated silicon/crumpled graphene composite as anode material for lithium-ion batteries | |
| Liu et al. | Hollow-structure engineering of a silicon–carbon anode for ultra-stable lithium-ion batteries | |
| Liu et al. | Self-supported hierarchical porous Li4Ti5O12/carbon arrays for boosted lithium ion storage | |
| CN109904415A (en) | A kind of nano-silicon-graphene aerogel is composite porous and preparation method thereof | |
| An et al. | Surface functionalization of nitrogen-doped carbon derived from protein as anode material for lithium storage | |
| Yin et al. | Synthesis of SiO2@ carbon-graphene hybrids as anode materials of lithium-ion batteries | |
| Li et al. | Cycle and rate performance of chemically modified super-aligned carbon nanotube electrodes for lithium ion batteries | |
| Wang et al. | Controllable synthesis of CNT@ ZnO composites with enhanced electrochemical properties for lithium-ion battery | |
| Aziz et al. | Hierarchical oxygen rich-carbon nanorods: Efficient and durable electrode for all-vanadium redox flow batteries | |
| Oh et al. | Highly integrated and interconnected CNT hybrid nanofibers decorated with α-iron oxide as freestanding anodes for flexible lithium polymer batteries | |
| CN103545521A (en) | Graphite-based carbon negative composite material in special shell structure and preparation method thereof | |
| Jin et al. | Multiwalled carbon nanotubes@ C@ SnO2 quantum dots and SnO2 quantum dots@ C as high rate anode materials for lithium-ion batteries | |
| CN105789628B (en) | A kind of azepine graphene and manganese dioxide hybrid aerogel and its preparation method and application | |
| Qin et al. | Hydrothermal synthesis and electrochemical performance of CuS@ Sisal fiber carbon composite Lithium-ion battery anodes | |
| CN104577126A (en) | Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode | |
| Kim et al. | Vanadium nitride and carbon nanofiber composite membrane as an interlayer for extended life cycle lithium-sulphur batteries | |
| Xu et al. | Electrophoretic Deposition of Binder‐Free MnO2/Graphene Films for Lithium‐Ion Batteries | |
| Liu et al. | 3D hierarchical porous N-doped carbon nanosheets/MgFe2O4 composite as anode material with excellent cycling stability and rate performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |