CN105870419B - A kind of preparation method and applications of graphene/fullerene composite nano materials - Google Patents
A kind of preparation method and applications of graphene/fullerene composite nano materials Download PDFInfo
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- H01M4/00—Electrodes
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- 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
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- H—ELECTRICITY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
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Abstract
The invention discloses a kind of preparation method of graphene/fullerene composite nano materials; it is that solid-phase carbon source and sulphur source are used as using thioretinite; catalyst precursor is used as using transition metal acetate; air inlet end of the thioretinite close to heating furnace; transition metal acetate is close to the outlet side of heating furnace; it is heat-treated under inert gas shielding, collects heat-treated products, through acid treatment, washing, is filtered, is drying to obtain graphene/fullerene composite nano materials；The temperature of the heat treatment is 600~900 DEG C, and heating time is 10 min~60min, and programming rate is 5~20 DEG C/min；This method is based on the class chemical vapour deposition technique that " thioretinite " is solid-phase carbon source/sulphur source, " transient metal sulfide " is catalyst, an extensive step prepares " graphene/fullerene " composite nano materials, solve the problems such as the step of current its faces is complicated, equipment is expensive, cumbersome, and hardly possible is produced in batches.
Description
Technical field
The present invention relates to graphene-based technical field of composite preparation, more particularly, to a kind of graphene/fullerene
The preparation method and applications of composite nano materials.
Background technology
Fullerene and graphene have attracted numerous researchers' note that people by each excellent physicochemical characteristics
Wish the special construction of fullerene and graphene and excellent properties can be brought to electrochemical energy source material and micro-nano electronic device it is prominent
The progress of broken property.Currently, the research and development in relation to fullerene and graphene has become an international hot spot.Fullerene and
Graphene is all the carbon material of nano-scale, has great specific surface area, good electric conductivity and excellent chemical characteristic.
But the dissolubility of fullerene and dispersiveness are poor, it is difficult to device is made, thus its practical application is limited significantly.Selection is suitable
Method prepare " graphene/fullerene " composite nano materials, a kind of cooperative effect can be produced between them, make its various
Physical and chemical performance is strengthened, thus this composite material has great application prospect in many fields.
First, by the supporting role of two-dimensional graphene can effectively solve the problems, such as fullerene dispersiveness it is poor this；Together
When, the particular interface effects of composite nano materials, small-size effect, quantum size effect etc., make it have the light of uniqueness, electricity,
The physicochemical properties such as magnetic, heat.Thus, " graphene/fullerene " composite nano materials are passed in electrochemical catalysis and energy storage, biology
The fields such as sense, electronic device will obtain extremely wide application.
In view of the excellent performance of " graphene/fullerene " composite nano materials and wide application prospect, explore synthesis " stone
The high efficiency preparation method of black alkene/fullerene " composite nano materials, control fullerene is in the growth and distribution of graphene surface, tool
There are important scientific meaning and practical value.Currently, the preparation process of " graphene/fullerene " composite nano materials generally includes
Three steps：（1）Graphene nanometer sheet is first prepared in the method for chemical oxidation or metal catalytic；（2）Pass through arc discharge method, laser
The technologies such as evaporation, flame combustion process prepare fullerene nano particle；（3）Disperseed by solution with chemical Coupling method in stone
Fullerene is loaded in black alkene nanometer sheet and forms composite construction.Obviously, above-mentioned multistep preparation process is cumbersome and energy consumption is higher, very
Hardly possible realizes the mass production of " graphene/fullerene " composite nano materials.Particularly, fullerene traditional preparation methods（Electric arc
Electric discharge, laser evaporization method, flame combustion process etc.）Device therefor is complicated and expensive, and follow-up composite material is opened
Hair brings great problem.In consideration of it, a kind of cheap, simple preparation method of exploitation is multiple to promoting " graphene/fullerene "
The industrialization of conjunction nano material will be played the role of vital.
The content of the invention
The technical problems to be solved by the invention are to overcome graphene existing in the prior art/fullerene composite nano materials
Cumbersome, of high cost, energy consumption the is big technical problem of preparation process, there is provided a kind of new graphene/fullerene composite nano materials
Preparation method.
Second object of the present invention is to provide graphene/fullerene composite nano materials that the above method obtains.
Third object of the present invention is to provide the application of above-mentioned graphene/fullerene composite nano materials.
The purpose of the present invention is what is be achieved by the following technical programs：
A kind of preparation method of graphene/fullerene composite nano materials, is to be used as solid-phase carbon source and sulphur using thioretinite
Source, using transition metal acetate as catalyst precursor, the thioretinite is close to the air inlet end of heating furnace, transition metal vinegar
Hydrochlorate is heat-treated under inert gas shielding close to the outlet side of heating furnace, collects heat-treated products, through acid treatment, wash
Wash, filter, being drying to obtain graphene/fullerene composite nano materials；The temperature of the heat treatment is 600~900 DEG C, during heating
Between be 10 min~60min, programming rate is 5~20 DEG C/min.
The present invention is used as solid-phase carbon source and sulphur source using multi-functional " thioretinite ", and what is discharged in heat treatment process contains
Carbon and sulfur-bearing atmosphere can be as the carbon sources and sulphur source of vapour deposition.The process belongs to the class chemical vapor deposition for automatically supplying atmosphere
Technology, fundamentally reduces the manufacturing cost of material.In addition, air inlet end of the thioretinite close to heating furnace, thioretinite gas
Become carbon containing and sulfur-bearing atmosphere, using transition metal acetate as catalyst precursor, the acetic acid in heat treatment process after change
Salt is reduced to nano metal nickel first and then catalysis carbon-containing atmosphere obtains fullerene；Metallic nickel is further reacted with sulfur-bearing atmosphere gives birth to
Continue catalysis carbon-containing atmosphere into metal sulfide and obtain graphene.
Preferably, the mass ratio of thioretinite and the transition metal acetate is 1：0.1~0.5.
Preferably, the acid treatment refers to 1~3h of salt acid soak of 1~5mol/L of heat-treated products.
Preferably, before being heat-treated, the thioretinite drying pulverization process, after crushing particle diameter for 50 μm~
100μm。
Preferably, before being heat-treated, the transition metal acetate salt is through ball-milling treatment, and particle diameter is 1 μ after ball milling
M~5 μm.
Preferably, the transition metal acetate is selected from more than one or both of nickel acetate, cobalt acetate, manganese acetate.
Preferably, the thioretinite be selected from thiourea resin, thiol resin, one or both of sulfonic group resin with
On.
As a kind of specific embodiment, the above-mentioned preparation method of the present invention comprises the following steps：
（1）The selection and pre-treatment of solid-phase carbon source/sulphur source：Selection thioretinite is solid-phase carbon source and sulphur source, dries pulverizing
Processing, particle diameter is 50 μm~100 μm after crushing；
（2）The selection and pre-treatment of catalyst precursor：Cheap transition metal acetate is selected as complex catalyst precursor
Body, and place and ball-milling treatment is carried out in ball mill, particle diameter is 1 μm~5 μm after ball milling；
（3）By step（1）Solid-phase carbon source/sulphur source of gained is positioned over the heating region of tube furnace（Air inlet end direction）, will walk
Suddenly（2）The catalyst precursor of gained is positioned over the heating region of tube furnace（Outlet extreme direction）, and under the protection of inert gas
Carry out a step heat treatment, the temperature of the heat treatment is 600~900 DEG C, and heating time is 10 min~60min, programming rate
For 5~20 DEG C/min.
（4）Product post-processes：By step（3）The catalysate of gained is collected, cleans, washing, filtering, dry i.e. system
Obtain " graphene/fullerene " composite nano materials.
Step（4）Dedoping step be acid treatment, that is, refer to 1~3h of salt acid soak of 1~5mol/L of heat-treated products.
The present invention also provides graphene/fullerene composite nano materials that above-mentioned preparation method obtains.
The present invention also provides the application of above-mentioned graphene/fullerene composite nano materials；Specifically, the application is utilization
Graphene/fullerene composite nano materials prepare negative electrode of lithium ion battery.
Compared with prior art, the invention has the advantages that：
The present invention provides a kind of preparation method of graphene/fullerene composite nano materials, be using thioretinite as
Solid-phase carbon source and sulphur source, using transition metal acetate as catalyst precursor, the thioretinite enters gas close to heating furnace
End, transition metal acetate are heat-treated under inert gas shielding close to the outlet side of heating furnace, collect heat treatment production
Thing, through acid treatment, washing, filters, is drying to obtain graphene/fullerene composite nano materials；The temperature of the heat treatment is 600
~900 DEG C, heating time is 10 min~60min, and programming rate is 5~20 DEG C/min；This method is to be based on " thioretinite "
For solid-phase carbon source/sulphur source, the class chemical vapour deposition technique that " transient metal sulfide " is catalyst, prepared by an extensive step
The step of " graphene/fullerene " composite nano materials, current its of solution faces, is complicated, equipment is expensive, cumbersome, hardly possible batch
The problems such as amount production.
Brief description of the drawings
Fig. 1 is the schematic diagram that the present invention prepares " graphene/fullerene " composite nano materials device therefor device：1 is to urge
Agent presoma, 2 be solid-phase carbon source/sulphur source, 3 be heating region, 4 be tube furnace, 5 be air inlet end, 6 be outlet side.
Fig. 2 is the X-ray diffraction of " graphene/fullerene " composite nano materials prepared by embodiment 1（XRD）Figure
Spectrum.
Fig. 3 is the scanning electron microscope of " graphene/fullerene " composite nano materials prepared by embodiment 1（SEM）
Image, Fig. 3 A are that scale is schemed for 1 μm, and Fig. 3 B are that scale is schemed for 100nm.
Fig. 4 is the transmission electron microscope of " graphene/fullerene " composite nano materials prepared by embodiment 1（TEM）
Image, wherein, Fig. 4 A are that scale is schemed for 200nm, and Fig. 4 B are that scale is schemed for 2nm.
Fig. 5 is the constant current charge-discharge of " graphene/fullerene " composite cathode material for lithium ion cell prepared by embodiment 1
Curve, current density 1000mA/g.
Embodiment
Present disclosure is further illustrated with reference to Figure of description and specific embodiment, but should not be construed as to this
The limitation of invention.Without departing from the spirit and substance of the case in the present invention, the method for the present invention, step or condition are made simple
Modifications or substitutions, belong to the scope of the present invention；Unless otherwise specified, technological means used in embodiment is art technology
Conventional means known to personnel.
Embodiment 1
Solid-phase carbon source/sulphur source " thiourea resin " is placed into 80 DEG C of dry 12h in an oven, then broken place is carried out with pulverizer
Reason, average grain diameter is 100 μm after crushing；Catalyst precursor " nickel acetate " is placed in ball mill and carries out ball-milling treatment, ball milling
Average grain diameter is 5 μm afterwards；" nickel acetate " particle obtained by " thiourea resin " particle obtained by 20g and 7g is taken to be positioned in tube furnace, and
It is heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 700 DEG C, heating time 30min,
Programming rate is 5 DEG C/min；Finally gained catalysate is collected, and is 2h with 2mol/L hydrochloric acid soaking times, then is used
Distill water washing, filtering, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " nanocomposite prepared by the above method, wherein graphene size is about 150nm,
Fullerene size is about 20nm, and composite material specific surface area is 425 m2 g-1；Applied to lithium ion battery negative material its can
Inverse put capacitance is 568 mAh g-1.Fig. 2 is the X-ray diffracting spectrum of the composite nano materials prepared by embodiment 1.Fig. 3 is
The scanning electron microscope image of composite nano materials prepared by embodiment 1.Fig. 4 is the composite Nano prepared by embodiment 1
The transmission electron microscope image of material.Fig. 5 is the constant current charge-discharge curve of the combination electrode material prepared by embodiment 1（Electricity
Current density 1000mA/g）.
Embodiment 2
Solid-phase carbon source/sulphur source " thiourea resin " is placed into 80 DEG C of dry 12h in an oven, then broken place is carried out with pulverizer
Reason, average grain diameter is 100 μm after crushing；Catalyst precursor " nickel acetate " is placed in ball mill and carries out ball-milling treatment, ball milling
Average grain diameter is 5 μm afterwards；" nickel acetate " particle obtained by " thiourea resin " particle obtained by 20g and 7g is taken to be positioned in tube furnace, and
It is heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 700 DEG C, heating time 30min,
Programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with 2mol/L hydrochloric acid soaking times, then is used
Distill water washing, filtering, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " composite nano materials prepared by the above method, wherein graphene size is about 300nm,
Fullerene size is about 15nm, and composite material specific surface area is 448 m2 g-1, applied to lithium ion battery negative material its can
Inverse put capacitance is 595 mAh g-1。
Embodiment 3
Solid-phase carbon source/sulphur source " thiourea resin " is placed into 80 DEG C of dry 12h in an oven, then broken place is carried out with pulverizer
Reason, average grain diameter is 100 μm after crushing；Catalyst precursor " nickel acetate " is placed in ball mill and carries out ball-milling treatment, ball milling
Average grain diameter is 5 μm afterwards；" nickel acetate " particle obtained by " thiourea resin " particle obtained by 20g and 7g is taken to be positioned in tube furnace, and
It is heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 700 DEG C, heating time 30min,
Programming rate is 20 DEG C/min；Finally gained catalysate is collected, and is 2h with 2mol/L hydrochloric acid soaking times, then is used
Distill water washing, filtering, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " composite nano materials prepared by the above method, wherein graphene size is about 250nm,
Fullerene size is about 12nm, and composite material specific surface area is 430 m2 g-1, applied to lithium ion battery negative material its can
Inverse put capacitance is 568 mAh g-1。
Embodiment 4
Solid-phase carbon source/sulphur source " thiourea resin " is placed into 80 DEG C of dry 12h in an oven, then broken place is carried out with pulverizer
Reason, average grain diameter is 100 μm after crushing；Catalyst precursor " nickel acetate " is placed in ball mill and carries out ball-milling treatment, ball milling
Average grain diameter is 5 μm afterwards；" nickel acetate " particle obtained by " thiourea resin " particle obtained by 20g and 7g is taken to be positioned in tube furnace, and
It is heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 600 DEG C, heating time 30min,
Programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with 2mol/L hydrochloric acid soaking times, then is used
Distill water washing, filtering, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " composite nano materials prepared by the above method, wherein graphene size is about 200nm,
Fullerene size is about 18nm, and composite material specific surface area is 441 m2 g-1, applied to lithium ion battery negative material its can
Inverse put capacitance is 581 mAh g-1。
Embodiment 5
Solid-phase carbon source/sulphur source " thiourea resin " is placed into 80 DEG C of dry 12h in an oven, then broken place is carried out with pulverizer
Reason, average grain diameter is 100 μm after crushing；Catalyst precursor " nickel acetate " is placed in ball mill and carries out ball-milling treatment, ball milling
Average grain diameter is 5 μm afterwards；" nickel acetate " particle obtained by " thiourea resin " particle obtained by 20g and 7g is taken to be positioned in tube furnace, and
It is heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 900 DEG C, heating time 30min,
Programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with 2mol/L hydrochloric acid soaking times, then is used
Distill water washing, filtering, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " composite nano materials prepared by the above method, wherein graphene size is about 400nm,
Fullerene size is about 30nm, and composite material specific surface area is 395 m2 g-1, applied to lithium ion battery negative material its can
Inverse put capacitance is 548 mAh g-1。
Embodiment 6
Solid-phase carbon source/sulphur source " thiol resin " is placed into 80 DEG C of dry 12h in an oven, then broken place is carried out with pulverizer
Reason, average grain diameter is 100 μm after crushing；Catalyst precursor " nickel acetate " is placed in ball mill and carries out ball-milling treatment, ball milling
Average grain diameter is 5 μm afterwards；" nickel acetate " particle obtained by " thiol resin " particle obtained by 20g and 7g is taken to be positioned in tube furnace, and
It is heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 700 DEG C, heating time 30min,
Programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with 2mol/L hydrochloric acid soaking times, then is used
Distill water washing, filtering, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " composite nano materials prepared by the above method, wherein graphene size is about 500nm,
Fullerene size is about 25nm, and composite material specific surface area is 434 m2 g-1, applied to lithium ion battery negative material its can
Inverse put capacitance is 587 mAh g-1。
Embodiment 7
Solid-phase carbon source/sulphur source " sulfonic group resin " is placed into 80 DEG C of dry 12h in an oven, then is crushed with pulverizer
Processing, average grain diameter is 100 μm after crushing；Catalyst precursor " nickel acetate " is placed in ball mill and carries out ball-milling treatment, ball
Average grain diameter is 5 μm after mill；" nickel acetate " particle obtained by " sulfonic group resin " particle obtained by 20g and 7g is taken to be positioned over tube furnace
In, and be heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 700 DEG C, and heating time is
30min, programming rate are 10 DEG C/min；Finally gained catalysate is collected, and is with 2mol/L hydrochloric acid soaking times
2h, then be washed with distilled water, filter, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " composite nano materials prepared by the above method, wherein graphene size is about 450nm,
Fullerene size is about 20nm, and composite material specific surface area is 445 m2 g-1, applied to lithium ion battery negative material its can
Inverse put capacitance is 591 mAh g-1。
Embodiment 8
Solid-phase carbon source/sulphur source " thiourea resin " is placed into 80 DEG C of dry 12h in an oven, then broken place is carried out with pulverizer
Reason, average grain diameter is 100 μm after crushing；Catalyst precursor " cobalt acetate " is placed in ball mill and carries out ball-milling treatment, ball milling
Average grain diameter is 5 μm afterwards；" cobalt acetate " particle obtained by " thiourea resin " particle obtained by 20g and 7g is taken to be positioned in tube furnace, and
It is heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 700 DEG C, heating time 30min,
Programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with 2mol/L hydrochloric acid soaking times, then is used
Distill water washing, filtering, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " composite nano materials prepared by the above method, wherein graphene size is about 600nm,
Fullerene size is about 35nm, and composite material specific surface area is 423 m2 g-1, applied to lithium ion battery negative material its can
Inverse put capacitance is 576 mAh g-1。
Embodiment 9
Solid-phase carbon source/sulphur source " thiourea resin " is placed into 80 DEG C of dry 12h in an oven, then broken place is carried out with pulverizer
Reason, average grain diameter is 100 μm after crushing；Catalyst precursor " manganese acetate " is placed in ball mill and carries out ball-milling treatment, ball milling
Average grain diameter is 5 μm afterwards；" manganese acetate " particle obtained by " thiourea resin " particle obtained by 20g and 7g is taken to be positioned in tube furnace, and
It is heat-treated under the protection of inert gas（As shown in Figure 1）, the temperature of heat treatment is 700 DEG C, heating time 30min,
Programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with 2mol/L hydrochloric acid soaking times, then is used
Distill water washing, filtering, dry i.e. obtained " graphene/fullerene " composite nano materials.
" graphene/fullerene " composite nano materials prepared by the above method, wherein graphene size is about 700nm,
Fullerene size is about 40nm, and composite material specific surface area is 407 m2 g-1, applied to lithium ion battery negative material its can
Inverse put capacitance is 552 mAh g-1。
Comparative example 1
Experimental method is with embodiment 1, and uniquely the difference is that, the mass ratio of thiourea resin and nickel acetate is 1：1；The method
" graphene/fullerene " composite nano materials prepared, wherein graphene size is about 100m, multiple almost without fullerene structure
Condensation material specific surface area is 325 m2 g-1；Applied to the negative material of lithium ion battery, its reversible discharge capacity is 436 mAh g-1。
Comparative example 2
Experimental method is with embodiment 1, and uniquely the difference is that, the average grain diameter of thioretinite is 20 μm, prepared by the method
" graphene/fullerene " composite nano materials, wherein graphene size is about 200m, almost without fullerene structure, composite wood
Material specific surface area is 307 m2 g-1；Applied to the negative material of lithium ion battery, its reversible discharge capacity is 412 mAh g-1。
Comparative example 3
Experimental method is with embodiment 1, and uniquely the difference is that, the average grain diameter of nickel acetate is 10 μm, prepared by the method
" graphene // fullerene " composite nano materials, wherein graphene size is about 500m, almost without fullerene structure, composite material
Specific surface area is 286 m2 g-1；Applied to the negative material of lithium ion battery, its reversible discharge capacity is 395 mAh g-1。
Claims (7)
1. the preparation method of a kind of graphene/fullerene composite nano materials, it is characterised in that solid carbon is used as using thioretinite
Source and sulphur source, using transition metal acetate as catalyst precursor, the thioretinite is close to the air inlet end of heating furnace, transition
Metal acetate salt is heat-treated under inert gas shielding close to the outlet side of heating furnace, collects heat-treated products, at acid
Manage, wash, filtering, being drying to obtain graphene/fullerene composite nano materials；The temperature of the heat treatment is 600~900 DEG C,
Heating time is 10 min~60min, and programming rate is 5~20 DEG C/min；Thioretinite and the transition metal acetate
Mass ratio is 1：0.1~0.5；Before being heat-treated, the thioretinite drying pulverization process, particle diameter is 50 after crushing
μm~100 μm；Before being heat-treated, the transition metal acetate is through ball-milling treatment, and particle diameter is 1 μm~5 μm after ball milling.
2. the preparation method of graphene/fullerene composite nano materials according to claim 1, it is characterised in that the acid
Processing refers to 1~3h of salt acid soak of 1~5mol/L of heat-treated products.
3. the preparation method of graphene/fullerene composite nano materials according to claim 1, it is characterised in that the mistake
Metal acetate salt is crossed to be selected from more than one or both of nickel acetate, cobalt acetate, manganese acetate.
4. the preparation method of graphene/fullerene composite nano materials according to claim 1, it is characterised in that described to contain
Sulphur resin is selected from more than one or both of thiourea resin, thiol resin, sulfonic group resin.
5. graphene/fullerene composite nano materials that any one of Claims 1-4 preparation method obtains.
6. the application in battery electrode is prepared of graphene described in claim 5/fullerene composite nano materials.
7. application according to claim 6, it is characterised in that the application is to utilize graphene/fullerene composite Nano
Material prepares negative electrode of lithium ion battery.
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| CN106006617B (en) * | 2016-05-25 | 2018-04-13 | 广东石油化工学院 | A kind of preparation method and applications of graphene hollow nano cages |
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