CN105152161B - Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof - Google Patents
Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof Download PDFInfo
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- CN105152161B CN105152161B CN201510374574.XA CN201510374574A CN105152161B CN 105152161 B CN105152161 B CN 105152161B CN 201510374574 A CN201510374574 A CN 201510374574A CN 105152161 B CN105152161 B CN 105152161B
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Abstract
Belonging to the field of carbon materials and electrochemistry, the invention discloses a heteroatom doped surface perforated hollow sphere graphene material, a preparation method and application thereof. The method includes: firstly carrying out ultrasonic reaction on concentrated nitric acid and graphene oxide, and performing standing to obtain surface perforated graphene oxide; then adding hexadecyl trimethyl ammonium bromide into a mixed solution of deionized water, ethylene glycol and ammonia water, carrying out dissolving, heating and stirring, then adding tetraethoxysilane and 3-aminopropyltriethoxysilane in order, carrying out stirring reaction, standing and hydrothermal reaction, thus obtaining positively charged silica spheres; carrying out stirring reaction on a surface perforated graphene oxide aqueous dispersion and a pH adjusted silica sphere aqueous dispersion, and performing freeze drying to obtain a composite material; and finally placing the composite material in a plasma high temperature tubular reactor to carry out reaction, thus obtaining the heteroatom doped surface perforated hollow sphere graphene material. The prepared material has a unique hollow structure, and can improve the electrical conductivity and thermal stability of electrode materials.
Description
Technical field
The invention belongs to material with carbon element and electrochemical field, and in particular to a kind of Heteroatom doping surface hollow ball graphite with holes
Alkene material and preparation method thereof and the application in Large Copacity, high multiplying power lithium ion battery.
Background technology
Lithium ion battery, as open-circuit voltage is high, energy density is big, long service life, memory-less effect, it is pollution-free and from
The advantages of discharging little, is the development priority of current secondary cell, and as important power supply source in mobile communication, notebook computer
Deng occupying larger share in electrical equipment market, and it is expected to be applied to the medium-and-large-sized storage device of electric automobile and national grid.
Currently, if by lithium ion battery applications in large-scale energy storage device and powerful device, must be requested that as lithium ion battery
Electrode material keep good capacity characteristic and cyclical stability under the conditions of high rate charge-discharge, therefore develop with Gao Rong
Amount, the electrode material of high power nature are the keys of current research.
The lithium ion battery negative material being currently mainly used is the material with carbon element with graphite as representative, and other negative materials are also
Including：Alloy type material, metal oxide materials, metal nitride materials, sulfide etc..Metal (including silicon), metal oxidation
The materials such as thing, nitride are significantly limit due to the reason such as raw material sources rareness, complicated process of preparation, production cost be higher
Their practical application.Graphite is due to its possess cheap and is close to the removal lithium embedded current potential of lithium metal by as industry
The negative material of change is used.But, due to the closelypacked layer structure of lamella in graphite, make graphite material there are some not
Surmountable shortcoming, such as graphite theoretical capacity are relatively low, the sheet interlayer spacing (d of graphite crystal002=0.34nm) less than lithium/graphite linings
Between compound L ixC6Sheet interlayer spacing (d002=0.37nm), as in graphite, sheet interlayer spacing is less, and in actual production process
The restriction of middle production technology causes the stacked direction of graphite flake layer perpendicular to lithium ion transport direction, so graphite material is used as negative
The high rate performance of the lithium ion battery of pole is often unsatisfactory.These shortcomings cause graphite material need Large Copacity, the long-life,
Application in terms of high-power energy storage device is limited by very large.Therefore, researcher is more suitable in the urgent need to seeking one kind
As the Carbon Materials of ion cathode material lithium.The Graphene of latest find causes the concern of research worker.
Graphene, alternatively referred to as " mono-layer graphite ", due to the flexible and controllability that its lamella has, are to construct all sp2
The elementary cell of hydridization carbonaceous material.As its unique and perfect structure causes Graphene to have excellent electricity, mechanics, heat
The characteristic such as and optics, especially its electronic movement velocity have reached 1000ms-1, considerably beyond fortune of the electronics in other conductors
Dynamic speed, is combined by most stable of benzene hexatomic ring, with bigger theoretical specific surface area (about 2630m2g-1) and more preferably
Electronic conduction ability (about 2 × 105cm2V-1s-1).These characteristics of Graphene are which becomes high power capacity, high power nature
Electrode material is provided may.Compared with other material with carbon elements, Graphene is preferably as high power capacity, high power nature for Graphene
Lithium ion battery electrode material.Such as Wang etc. (Carbon, 47 (2009) 2049-2053) is using hydrazine hydrate reduction graphite oxide
Alkene, obtains the similar petal-shaped grapheme material of microscopic pattern, can stablize through the charge specific capacity of 100 materials of 1C discharge and recharges
In 460mAh g-1。
Under the effort of researcher, preparing now Graphene on a large scale becomes possibility.How graphite material one is being retained
While serial advantage, increase lithium storage content, improve ionic conductivity, improve multiplying power and cycle performance, research worker will be studied
Focus be placed on the doping vario-property of grapheme material.It is to improve Graphene performance that heterogeneous element doping is carried out to grapheme material
A kind of conventional method, by change Graphene microstructure and electronic state improving the embedding lithium behavior of Graphene.Mix
Miscellaneous nonmetalloid typically can be introduced with atomic form and compound form two ways.Can be used for the different of grapheme material doping
Prime element mainly includes boron, nitrogen, sulfur, phosphorus etc..Wu etc. (ACS Nano, 5 (2011) 5463-5471) is using thermal expansion graphite oxide
Synthesizing graphite alkene, subsequently respectively at 600 DEG C and NH3The prepared nitrogen-doped graphene of/Ar reactions, 800 DEG C and BCl3/ Ar reactions are obtained
Boron doped graphene, wherein boron doped graphene is in 50mA g-1There is during discharge and recharge 1549mAh g-1Reversible capacity first simultaneously
And 1227mAh g can be kept through 30 circulations-1。
In sum, Graphene and heterogeneous element doped graphene reversible capacity are high, can be with high current charge-discharge, power
Can be good, but there are numerous defects in which：
(1) due to preparing with during cycle charge-discharge, nano-graphene piece (GNS) is due to piece interlayer Van der Waals force
Exist, can gradually be gathered into Graphene paper-like structure, cause substantial amounts of sheet surfaces to be difficult to be utilized, thus its specific surface is much
Less than theoretical specific surface；
(2) aggregation of lamella causes the active surface of material persistently to reduce, while generating many discontinuous passages, hinders
Ion quick transmission is wherein hindered；
(3) the complete graphene film in surface, it is due to its surface compact, easily interrupted by the ion transmission of graphene film；
Because while ion is very high in the electrical conductivity on parallel to graphenic surface direction, but which is perpendicular to graphene film plane side
Conductance upwards is less efficient.Therefore the migration of ion can be concentrated mainly on the edge of graphene film, greatly hinder its ion
The raising of electrical conductivity.
Answering for Heteroatom doping Graphene is made as Heteroatom doping Graphene prepared by prior art has drawbacks described above
With being limited by very large.
The content of the invention
In order to overcome the shortcoming and defect of prior art, the primary and foremost purpose of the present invention is to provide a kind of Heteroatom doping table
The preparation method of face hollow ball grapheme material with holes.The present invention prepares the negatively charged of different carbon/oxygen ratios using chemical etching method
The surface graphene oxide with holes of lotus, it is with positively charged silica spheres as masterplate, negatively charged by electrostatic interaction
Surface graphene oxide with holes is coated on positively charged silicon dioxide ball surface and forms nucleocapsid structure complex, then by plasma
Body method doping hetero atom has prepared the Heteroatom doping surface hollow ball grapheme material with holes of better performances, structure-controllable.
Another object of the present invention is to provide the Heteroatom doping surface prepared by above-mentioned preparation method it is with holes in
Empty ball grapheme material.
It is still another object of the present invention to provide the application of above-mentioned Heteroatom doping surface hollow ball grapheme material with holes.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of Heteroatom doping surface hollow ball grapheme material with holes, specifically includes following steps：
(1) synthesis of surface graphene oxide with holes
Add water in graphene oxide, ultrasonic disperse obtains graphene oxide solution；Then under agitation, to
Dense HNO is added in container equipped with graphene oxide solution3, container is sealed, in 4 DEG C～60 DEG C 0.5～10h of ultrasonic reaction, quiet
After putting 1～3h, pour in deionized water, acid is gone in centrifugation, and purification filters, is dried, obtains surface graphene oxide with holes, standby；
(2) preparation of positively charged silicon dioxide ball template
Cetyl trimethylammonium bromide (CTAB) is added to into the reaction vessel equipped with deionized water, ethylene glycol and ammonia
In, stirring and dissolving is warming up to 40～70 DEG C, and then 20～60min of insulated and stirred is added dropwise over tetraethoxysilane (TEOS),
Then 3- aminopropyl triethoxysilanes (APTES) are rapidly joined, in 40-70 DEG C of 2～4h of stirring reaction, insulation stands 12～
24h, carries out hydro-thermal reaction in being subsequently placed at hydrothermal reaction kettle；By the product cleaning of hydro-thermal reaction to filtrate non-foam, it is dried, obtains
To positively charged silica spheres；
(3) preparation of the surface graphene oxide silica spheres complex with holes with nucleocapsid structure
Positively charged silica spheres in step (2) are scattered in deionized water, silica spheres dispersion liquid is obtained；
Then it is 2～2.5 that Deca acid solution adjusts pH, adds surface graphene oxide dispersion with holes, and 24～48h of stirring reaction is cold
Lyophilizing is dry, obtains the surface graphene oxide silica spheres composite with holes with nucleocapsid structure；Wherein described surface band
The graphene oxide dispersion in hole is to be dispersed in water to prepare surface graphene oxide with holes in step (1)；
(4) prepared by the plasma method of Heteroatom doping surface hollow ball Graphene with holes
Graphene oxide silica spheres composite 100mg～1000mg surfaces with holes is placed in into plasma high-temperature
In tubular reactor, evacuation is depressurized to 1～10Pa, is further evacuated to 10-2～10-3Pa, is passed through protective gas and gaseous state
Heteroatom doping source is 0.1～20Pa to pressure, and plasma high-temperature tubular reactor is added with 5～10 DEG C/min heating rates
Then heat open radio-frequency power supply to 300～600 DEG C, under conditions of radio-frequency power is 100～600W, plasma discharge 10
～60min, is then shut off radio frequency and heating power supply, and stopping is passed through Heteroatom doping source, cools down, is cleaned with HF solution, then with third
Ketone-aqueous mixtures washing, is finally washed with deionized to the conductivity of filtrate and is less than 10 μ S, and filtrate solid material is as miscellaneous
Atom doped surface hollow ball grapheme material with holes.
The frequency of ultrasonic disperse described in step (1) is 20～100KHz, and the power of ultrasonic disperse is 40～1000W, is surpassed
The sound scattered time is 30～120min；The frequency of the ultrasonic reaction is 20～100KHz, the power of ultrasonic reaction is 40～
1000W, the time of ultrasonic reaction is 0.5～10h；The mass percent concentration of the graphene oxide solution be 0.1～
1.0%；Centrifugal rotational speed is 8000～13000rpm；The temperature of the drying is 40～60 DEG C, and the dry time is 12～24h.
Described in step (1), graphene oxide is prepared by the following method and forms：Under the conditions of ice-water bath, by quality percentage
Number is added in sodium nitrate and graphite mixture for 95～98% concentrated sulphuric acid, 10～60min of stirring reaction；It is gradually added permanganic acid
Potassium, controlling reaction temperature are less than 20 DEG C, and addition continues 6～24h of reaction after finishing, and add deionized water dilution, stirring reaction
30～60min, is warming up to 20～98 DEG C, reacts 12～48h, is added dropwise over the hydrogen peroxide that mass percent is 30～35%, drips
Continue 30～60min of reaction after adding, filter, be that 5～10%HCl solution and deionized water are washed with mass percent,
Till sulfate radical-free is detected in the filtrate；Filter cake is obtained into graphite oxide in 40～60 DEG C of 12～24h of drying finally
Alkene；It is described be gradually added that potassium permanganate refers to that each addition of potassium permanganate is potassium permanganate gross weight 1/60, per minor tick 1
～2min；The rotating speed of the stirring is 200～1000r/min；The speed of the Deca is 5～10 drops/min；The speed that heats up
Rate is 10～20 DEG C/min；
The graphite powder：Sodium nitrate：Concentrated sulphuric acid：Potassium permanganate：For the deionized water of dilution：The amount ratio of hydrogen peroxide is
(1～5) g：(1～5) g：(90～300) mL：(5～25) g：(50～300) mL：(50～100) mL.
The graphite powder is all kinds of native graphites or expanded graphite.
In the graphene oxide, oxygen atomicity content accounts for the 20～60% of total atom number.
Dense HNO described in step (1)3Volume ratio with graphene oxide solution is (1～20)：1；The matter of the concentrated nitric acid
Amount percent concentration is 60～65%；The deionized water is (100～200) mL with the volume ratio of graphene oxide solution：(50
～500) mL.
The mass percent concentration of ammonia described in step (2) is 25～28%；The rotating speed of the stirring be 200～
1000r/min；The temperature of the hydro-thermal reaction is 80～120 DEG C, and the time of hydro-thermal reaction is 12～48h；The temperature of the drying
Spend for 60～80 DEG C, the dry time is 12～24h；The speed of the Deca is 5～10 drops/min；The cleaning is to adopt successively
Deionized water and ethanol are cleaned to hydro-thermal reaction product.
Cetyl trimethylammonium bromide (CTAB) described in step (2)：Deionized water：Ethylene glycol：Ammonia：Tetraethoxy
Silane (TEOS)：The amount ratio of 3- aminopropyl triethoxysilanes (APTES) is (0.5～2) g：(100～300) g：(10～
100)mL：(5～25) mL：(0.5～3) mL：(100～300) μ L.
The concentration of surface graphene oxide dispersion with holes described in step (3) is (1～10) mg/mL；The positive charge
The mass volume ratio of silica spheres and deionized water be (0.1～2) g：(20～50) mL；The positively charged titanium dioxide
Silicon ball is (0.1～2) g with the mass volume ratio of surface graphene oxide dispersion with holes：15mL；The acid solution is hydrochloric acid,
The concentration of the acid solution is 0.5～2mol/L；The rotating speed of the stirring is 200～1000r/min, and the temperature of the reaction is
Room temperature；The cryodesiccated temperature is -28～48 DEG C, and the cryodesiccated time is 12～48h.
Protective gas described in step (4) is argon, helium or nitrogen；The Heteroatom doping source be diborane, ammonia,
One or more of hydrogen sulfide or Phosphorous chloride.；The protective gas is (0.1～10) with the volume ratio in Heteroatom doping source：1.
The concentration of HF described in step (4) is 5～20wt%；The number of times of the cleaning is 2～3 times；The acetone-water is mixed
In compound, acetone and water volume ratio are (1～3)：1.
In the hollow ball grapheme material with holes of this described Heteroatom doping surface content of heteroatoms account for total atom number 2.5～
40%, oxygen atomicity accounts for the 1-8% of total atom number.
Heteroatom doping surface hollow ball grapheme material with holes is prepared by above-mentioned preparation method.
Heteroatom doping surface hollow ball grapheme material with holes is in Large Copacity, high multiplying power lithium ion battery
Using.
The application is specially to be used to prepare lithium ion battery by hollow ball grapheme material Heteroatom doping surface with holes
Electrode material.
The preparation method of the electrode material is：By hollow ball grapheme material Heteroatom doping surface with holes, conductive carbon
The mixing of black and binding agent, obtains mixture；Solvent is added, is applied after grinding on a current collector, drying, shearing, after tabletting be
Working electrode；Wherein in the mixture, by mass percentage, Heteroatom doping surface hollow ball Graphene content with holes is
50%～98%, the content of conductive carbon black is 25%～1%, and the content of binding agent is 25%～1%；The consumption of solvent is described
50～1000wt% of mixture.
Described solvent is one or more of ethanol, acetone or N-Methyl pyrrolidone；The collector is Copper Foil, aluminum
Paper tinsel, titanium sheet, corrosion resistant plate or platinized platinum.
A kind of assembling of lithium ion half-cell, with above-mentioned electrode material as working electrode, using lithium piece as to electrode/reference
Electrode, adds the electrolyte containing lithium salts, button-shaped lithium ion half-cell is assembled in glove box；
Described lithium salts is LiPF6、LiClO4Or LiAsF6, the organic solvent in the electrolyte is Allyl carbonate
(PC), one or more of dimethyl carbonate (DMC) or ethylene carbonate (EC).The molar concentration of the electrolyte be 0.1～
3mol/L。
The test of lithium ion half-cell：Constant current charge-discharge test is carried out under the big current density condition of starting；Described
Constant current charge-discharge test condition is carried out for 50mAg under the big current density condition of starting-1～20A g-1.The present invention is using chemistry
Etching method prepares the negatively charged surface graphene oxide with holes of different carbon/oxygen ratios, with positively charged silica spheres as mould
Version, is coated on positively charged silicon dioxide ball surface shape by the negatively charged surface of electrostatic interaction graphene oxide with holes
Into nucleocapsid structure complex, then under the conditions of protective gas and uniform temperature, heteroatomic compound gas is passed through, is turned on the power sharp
Plasma discharge is sent out, the reduction of graphene oxide is realized by the effect of high energy particle and electronics and Heteroatom doping is existed,
Heteroatom doping surface hollow ball grapheme material with holes is obtained, the material is used for lithium ion battery to be had preferably electrically
Energy.In addition, in plasma method, the present invention can control high energy particle and electronics by the regulation of plasma parameter
Energy, so as to realize the regulation and control of heteroatomic doping content, the state of foreign atom and structure etc..
Described plasma high-temperature tubular reactor includes plasma high-temperature quartz tube furnace, described plasma
High quartz tube furnace one end is provided with protective gas air inlet pipe and Heteroatom doping source reacting gas air inlet pipe, described grade from
The daughter high quartz tube furnace other end is provided with 2 exhaust tubes, exhaust tube connection liquid nitrogen cold trap, another exhaust tube connection point
Sub- pump, the liquid nitrogen cold trap are connected with mechanical pump by pipeline, described plasma high-temperature quartz tube furnace outer surface winding
The two ends for having inductively coupled plasma coil, described inductively coupled plasma coil connect radio frequency power source.Described
Digital display mass flowmenter and control valve are connected with protective gas air inlet pipe, on described Heteroatom doping source gas inlet pipe
Digital display mass flowmenter and control valve are connected with, described being connected on the exhaust tube of liquid nitrogen cold trap is provided with the first control valve,
Described being connected on the exhaust tube of liquid nitrogen cold trap is provided with air intake duct, and the air intake duct is provided with air shut-off valve door；
Be provided with the 3rd control valve on the pipeline of the liquid nitrogen cold trap and mechanical pump, the control valve with connect with liquid nitrogen cold trap
Vacuometer is provided with pipeline, in the vacuometer and the bypass of pipeline communication, the 4th control valve, described connection is provided with
The exhaust tube for having molecular pump is provided with the second control valve.Heteroatom doping source gas inlet pipe is many gas circuit air inlet pipe,
Connect digital display mass flowmenter and control valve in each gas circuit air inlet pipe.
The invention has the advantages that and beneficial effect：
(1) material hollow graphite alkene ball prepared by the present invention has very unified size, by hollow ball and very thin Graphene
Shell is constituted；Exist in a large number perpendicular to the mesoporous of spherome surface in the Graphene shell of outer layer, can be lithium ion in different directions
Diffusion transport provides path；
(2) in material prepared by the present invention, unique hollow-core construction can provide bigger specific surface and shorter diffusion
Distance is so as to promoting transmission of the lithium ion in electrode material；The nano material of hollow-core construction can solve electrode material due to mistake
Big volumetric expansion and the too fast problem of capacity attenuation in the cyclic process that produces, in this case, the nanometer material of hollow-core construction
Material can hinder the reunion of active particle and provide sufficiently large space to alleviate volumetric expansion；
(3) present invention prepare Heteroatom doping surface hollow ball Graphene with holes as lithium ion battery electrode material,
The Large Copacity that can be used under the conditions of fast charging and discharging, high magnification electrode material, the material significantly improve electrode material
Electrical conductance and thermostability, there is provided the reversible active sites of more storage lithiums；
(4) using plasma method of the present invention prepares Heteroatom doping surface hollow ball grapheme material with holes, and general
High-temperature direct thermal decomposition-reduction doping method compare, plasma-assisted process of the present invention has reaction temperature low (≤500 DEG C), anti-
Between seasonable the features such as short, low cost；And Heteroatom doping amount and its uniformity can pass through the tune of plasma discharge parameter
Section is effectively controlled；
(5) present invention process flow process is simple, processing ease, and doping efficiency is fast, storage lithium performance is high, can be expected to a large amount of productions.
In a word, the graphene oxide silica spheres with holes with nucleocapsid structure by being prepared using masterplate method are combined
Material is raw material, and using plasma electric discharge is reduced and doping obtains Heteroatom doping surface hollow ball Graphene with holes, not only
Doping of the hetero atom in hollow ball Graphene lattice is realized, and further removes oxygen-containing functional group, improve the electricity of Graphene
The property led and heat stability, increase the reversible active sites of storage lithium, obtain a kind of Large Copacity, powerful Graphene electrodes material.
Description of the drawings
Fig. 1 is the structural representation of the plasma high-temperature tubular reactor of the present invention；Wherein 1- quartz tube furnaces, 2- matter
Amount effusion meter, 3- regulating valves (needle-valve), 4- liquid nitrogen cold traps, 5- mechanical pumps, 6- coils (copper tube coil), 7- radio frequency power sources,
8- molecular pumps, the first control valves of 9- (butterfly valve), the second control valves of 10- (butterfly valve), 11- protective gas air inlet pipe, 12- gaseous states
Heteroatom doping source air inlet pipe, 13- molecular pump exhaust tubes, 14- exhaust tubes, 15- sample mounting tables, 16- vacuometers, 17- the 3rd
Control valve, the 4th control valves of 18-；
Fig. 2 is the structural characterization figure of N doping surface hollow ball grapheme material with holes prepared by embodiment 1；Wherein (a)
For SEM photograph, it is (b) transmission electron microscope photo；
Fig. 3 be embodiment 1 prepare N doping surface hollow ball grapheme material with holes as electrode material in low current
Electric performance test curve under density；Wherein (a) is constant current charge-discharge voltage curve, (b) is respectively cycle performance and storehouse with (c)
Logical sequence efficiency, electric current density are 50mAg-1；
Fig. 4 is the electrical property of the N doping surface hollow ball grapheme material with holes as electrode material of the preparation of embodiment 1
Test curve；The wherein constant current charge-discharge voltage curve of (a) for high current density lower electrode material, in figure, 0.5～20 represents electricity
Current density 0.5Ag-1～20Ag-1；B () is that the high rate performance of different high current density lower electrode materials and cycle performance are bent
Line, electric current density are 0.5Ag-1To 20Ag-1, Ag in figure-1Represent Ag-1。
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
A kind of preparation method of Heteroatom doping surface hollow ball grapheme material with holes, specifically includes following steps：
(1) synthesis of graphene oxide
(1-1) reaction bulb is assembled in ice-water bath, (rotating speed of stirring is 500r/min) is to reaction under agitation
The solid mixture of 1g expanded graphites powder and 2.5g sodium nitrates is added in bottle, add 150mL mass percents be 95% it is dense
Sulphuric acid, reacts 30min in ice-water bath；Subsequently, 60 times (per minor tick 1min) are divided to add 15g potassium permanganate, control reaction temperature
Spend for 0 DEG C, continue reaction 12h；The dilution of 150mL deionized waters is added, (rotating speed of stirring is 500r/ after stirring reaction 30min
Min), 98 DEG C are warming up to the heating rate of 10 DEG C/min, insulation reaction 48h, solution colour are obtained from black transitions into brown color
To the crude product of graphene oxide；
(1-2) to the hydrogen peroxide reduction that Deca in crude product (rate of addition is 5 drops/min) 50mL mass fractions are 35%
The oxidant of residual, continues reaction 30min after dripping off, solution is changed into glassy yellow；Filtered while hot, and with mass fraction be successively
Till the 5%HCl solution and deionized water wash sulfate radical-free in the filtrate is detected, 60 DEG C of vacuum drying is finally placed in
12h is dried in case, graphene oxide is obtained；
(2) synthesis of surface graphene oxide with holes
By the graphene oxide deionized water ultrasonic disperse 60min of above-mentioned preparation, (frequency is 50KHz, power is
150W), obtain the graphene oxide solution that mass percent concentration is 0.5%；(rotating speed of stirring is under agitation
500r/min), to equipped with 50mL graphene oxide solution container in add 250mL mass percent concentrations be 65% it is dense
HNO3, container is put in closed glass container, supersound process 1h (frequency is 100KHz, and power is 500W, and temperature is 25 DEG C),
After standing 1h, pour in the deionized water of 100mL, centrifugation is gone sour (centrifugal rotational speed is 13000rpm), purification, filter, in 60 DEG C
12h is dried, surface graphene oxide with holes is obtained final product；
(3) preparation of positively charged silicon dioxide ball template
0.8624g cetyl trimethylammonium bromide (CTAB) is added to equipped with 149.5g deionized waters, 25mL second two
In the three-neck flask of alcohol and ammonia that 7.2mL mass percent concentrations are 25%, (rotating speed of stirring is 500r/ to stirring and dissolving
Min after), reaction temperature is risen to into 50 DEG C, stirs 30min, 1mL tetraethoxysilanes (TEOS) are added dropwise over into (Deca then
Speed is 5 drops/min), then 140.0 μ L 3- aminopropyl triethoxysilanes (APTES) are once injected with liquid-transfering gun, at 50 DEG C
Under the conditions of, stirring reaction 2h, after insulation stands 20h, is transferred in the hydrothermal reaction kettle that inner bag is politef, in 100 DEG C
Hydro-thermal reaction 24h, by the product deionized water and ethanol purge of hydro-thermal reaction up to filtrate non-foam, then in 60 DEG C of conditions
Under be dried 12h, obtain final product positively charged silica spheres；
(4) preparation of the surface graphene oxide silica spheres complex with holes with nucleocapsid structure
The surface graphene oxide with holes of step (2) is scattered in deionized water, surface graphite oxide with holes is configured to
Alkene solution, its concentration are 2mg/mL；
0.3g positively charged silica spheres are scattered in 30mL deionized waters, then Deca 1.0mol/L hydrochloric acid is (every
The drop hydrochloric acid solution of Deca 1 determines a pH value) pH value is adjusted to 2.5, the surface graphene oxide solution with holes of 15mL is added,
Magnetic agitation reaction 24h (it is 500r/min that the rotating speed of magnetic agitation is the rotating speed of stirring) under room temperature condition, using lyophilization
Instrument obtains the surface graphene oxide silica spheres composite with holes with nucleocapsid structure in -40 DEG C of lyophilization 24h；
(5) prepared by the plasma method of Heteroatom doping surface hollow sphere grapheme material with holes
Graphene oxide silica spheres composite 300mg surface in step (4) with holes is placed in into plasma high-temperature
In tubular reactor, impurity and vapor are removed using mechanical pump evacuation, and is depressurized to 5Pa, then further use molecule
Pump is evacuated to 10-3Pa, is then passed through protective gas N at one end2And gaseous state Heteroatom doping source NH3(N2And gaseous state hetero atom is mixed
Miscellaneous source NH3The flow being passed through be respectively 5sccm and 10sccm) to pressure be 10Pa (N2With NH3Volume ratio be 0.5：1), incite somebody to action etc.
Gas ions high-temperature tubular reactor is heated to 500 DEG C with 5 DEG C/min heating rates, then opens radio-frequency power supply, in radio-frequency power
Under conditions of for 200W, plasma discharge 30min is carried out, be then shut off radio frequency and heating power supply, continue to be passed through protectiveness gas
Body, stopping are passed through NH3, after being cooled to room temperature, products therefrom is cleaned into removing silicon dioxide masterplate twice with the HF of 10wt%, most
With acetone-water mixture, (acetone is 1 with the volume ratio of water afterwards：1) clean, then deionized water is cleaned until filtrate again
Conductivity is less than 10 μ S, and filtrate solid material is the surface hollow sphere grapheme material with holes of N doping.
Can be obtained by elementary analysiss, in N doping hollow ball grapheme material, nitrogen-atoms numbers account for total atom number
14.3%, oxygen atomicity accounts for the 4.4% of total atom number.
The structural representation of plasma high-temperature tubular reactor is as shown in Figure 1.
The N doping hollow ball Graphene that the present embodiment 1 is obtained is scanned Electronic Speculum and transmission electron microscope observing, the nitrogen of gained
The scanning electron microscope and transmission electron microscope photo of atom doped hollow ball Graphene is as shown in Figure 2.Figure it is seen that this enforcement
N doping hollow ball Graphene prepared by example 1, almost all of Graphene ball have hollow structure.
Application performance test in lithium ion battery
By N doping hollow ball grapheme material, conductive carbon black, Kynoar binding agent by certain mass ratio (80:
10: 10) mix, obtain mixture；Addition accounts for the N-Methyl pyrrolidone of the mixture 200wt%, makes through grinding to form
Homogenate pasty state, is then coated in slurry on Cu paper tinsels, and 100 DEG C are dried 5h, after making N-Methyl pyrrolidone volatilize, shearing, tabletting,
20h is dried under 100 DEG C of vacuum, electrode material is obtained；With electrode material as working electrode, using lithium piece as to electrode/reference electricity
Pole, with 1M (mol/L) LiPF6Ethylene carbonate EC/ dimethyl carbonate DMC (volume ratio 1：1) solution is used as electrolyte, in handss
Button-shaped lithium ion half-cell is assembled in casing, constant current charge-discharge test is then carried out under different current density conditions.
Test result is as shown in Figure 3,4.In low current density 50mAg-1Under, reversible specific capacity is 1848.6mAhg first-1；
High current density 20Ag-1Under, reversible specific capacity is 205mAhg-1。
Fig. 3 represents battery of the N doping surface hollow ball grapheme material with holes as electrode material under low current density
From Fig. 3 a constant current charge-discharge voltage curves, performance test curve, can be found that the material first discharge specific capacity reaches
2385.5mAh·g-1, the 2nd specific discharge capacity is 1835.5mAhg-1, the 5th, the 10th time, the 25th specific discharge capacity point
Wei not 1815.7mAhg-1, 1802.6mAhg-1, 1726.0mAhg-1, show that the material starts tool from second discharge and recharge
There is preferable Reversible Cycle.Fig. 3 b cycle performance curves show that the charging capacity conservation rate of the material is 91.9%.Fig. 3 c storehouses
Logical sequence efficiency curve shows that the initial coulomb efficiency of the material is 77.5%, starts coulombic efficiency from second discharge and recharge and is close to
100%.Understand, N doping surface hollow ball grapheme material with holes has excellent chemical property under low current density,
It is 1848.6mAhg which not only has high reversible charge specific capacity-1, and improve the initial coulomb efficiency of electrode material
77.5% and capability retention 91.9%.This is primarily due to the unique hollow-core construction of N doping surface hollow ball Graphene with holes
Bigger specific surface and shorter diffusion length can be provided so as to the transmission for promoting lithium ion in electrode material；Can solve
The too fast problem of capacity attenuation in the cyclic process that certainly electrode material is produced due to excessive volumetric expansion；Can hinder in addition
The reunion of active particle and provide sufficiently large space to alleviate volumetric expansion.
As shown in figure 4, from N doping surface hollow ball Graphene with holes (0.5Ag under high current density-1To 20A
g-1) high rate performance (Fig. 4 a) and stable circulation linearity curve (Fig. 4 b) understand, in 0.5Ag-1, 1Ag-1, 2.5Ag-1,
5A·g-1, 10Ag-1, 15Ag-1Charge specific capacity reversible first under electric current density is respectively 1148.8mAhg-1,
985.8mAh·g-1, 746.4mAhg-1, 531.5mAhg-1, 345.6mAhg-1, or even in 20Ag-1High current it is close
Under degree, reversible charge specific capacity still reaches 244.7mAh g first-1.Through 0.5Ag-1To 20Ag-1Different electric currents it is close
After degree discharge and recharge is each 10 times, charging and discharging currents density is down to 0.5Ag-1When, its charge specific capacity goes back up to 995.7mAh again
g-1.Prove that N doping surface hollow ball Graphene with holes has excellent fast charging and discharging under high current density from these data
Performance, high specific capacity, excellent high rate performance and cyclical stability.
Embodiment 2
A kind of preparation method of Heteroatom doping surface hollow ball grapheme material with holes, specifically includes following steps：
(1) synthesis of graphene oxide：It is identical with step (1) in embodiment 1；
(2) synthesis of surface graphene oxide with holes：It is identical with step (2) in embodiment 1；
(3) preparation of positively charged silicon dioxide ball template：It is identical with step (3) in embodiment 1；
(4) the graphene oxide@silica spheres complex with holes with nucleocapsid structure：With step (4) phase in embodiment 1
Together；
(5) graphene oxide silica spheres complex 300mg surface with holes is placed in into plasma high-temperature pipe reaction
Device center, removes impurity and vapor using mechanical pump evacuation, and is depressurized to 5Pa, then further uses molecular pump
It is evacuated to 1 × 10-3Pa, is then passed through protective gas N at one end2And gaseous state Heteroatom doping source diborane to pressure is 10Pa
(N2Volume ratio with diborane is 0.5：1)(N2And the flow that is passed through of gaseous state Heteroatom doping source diborane be respectively 5sccm and
10sccm), plasma high-temperature tubular reactor is heated to into 500 DEG C with 5 DEG C/min heating rates, then opens radio frequency electrical
Source, under conditions of radio-frequency power is 200W, carries out plasma discharge 30min, is then shut off radio frequency and heating power supply, stop
Diborane is passed through, after being cooled to room temperature, products therefrom is cleaned into removing silicon dioxide masterplate twice with the HF of 10wt%, is finally used
(acetone is 1 with the volume ratio of water to acetone-water mixture：1) clean, then deionized water is cleaned until the conduction of filtrate again
Rate is less than 10 μ S, and filtrate solid material is boron doped surface hollow ball grapheme material with holes.Can by elementary analysiss
With, the boron doping amount of the boron doped surface for preparing hollow sphere Graphene with holes is 6.3%, and oxygen content is 3.2%.
Resulting boron doped surface hollow sphere grapheme material with holes is characterized using SEM and TEM, as a result
It is similar to Example 1, and be applied to, during the electrode material of lithium ion battery (test condition is same as Example 1), show good
Good performance.In low current density 50mAg-1Under, reversible specific capacity is 1907mAhg first-1；In high current density
20A·g-1Under, reversible specific capacity is 225mAhg-1。
Embodiment 3
A kind of preparation method of Heteroatom doping surface hollow ball grapheme material with holes, specifically includes following steps：
(1) synthesis of graphene oxide：It is identical with step (1) in embodiment 1；
(2) synthesis of surface graphene oxide with holes：It is identical with step (2) in embodiment 1；
(3) preparation of positively charged silicon dioxide ball template：It is identical with step (3) in embodiment 1；
(4) the surface graphene oxide silica spheres complex with holes with nucleocapsid structure：With step in embodiment 1
(4) it is identical；
(5) the graphene oxide silica spheres complex 300mg surface of above-mentioned preparation with holes is placed in into plasma high
Warm tubular reactor center, removes impurity and vapor using mechanical pump evacuation, and is depressurized to 5Pa, then further
1 × 10 is evacuated to using molecular pump-3Pa, is then passed through protective gas N at one end2And gaseous state Heteroatom doping source Phosphorous chloride.
It is 10Pa (N to pressure2Volume ratio with Phosphorous chloride. is 0.5：1)(N2And the stream that gaseous state Heteroatom doping source Phosphorous chloride. is passed through
Amount is respectively 5sccm and 10sccm), plasma high-temperature tubular reactor is heated to into 500 DEG C with 5 DEG C/min heating rates,
Then radio-frequency power supply is opened, under conditions of radio-frequency power is 200W, plasma discharge 30min is carried out, is then shut off radio frequency
And heating power supply, stop being passed through Phosphorous chloride., after being cooled to room temperature, products therefrom is cleaned with the HF of 10wt% and remove twice two
Silicon oxide masterplate, cleans with acetone-water mixture that (volume ratio of acetone and water is 1：1), then deionized water cleaning is straight again
Conductivity to filtrate is less than 10 μ S, and filtrate solid material is the surface hollow sphere Graphene material with holes of phosphorus doping
Material.Can be obtained by elementary analysiss, the phosphorus doping amount of the surface hollow sphere Graphene with holes of the phosphorus doping for preparing is
5.1%, oxygen content is 4.2%.
The surface hollow sphere grapheme material with holes of resulting phosphorus doping is characterized using SEM and TEM, as a result
It is similar to Example 1, and be applied to, during the electrode material of lithium ion battery (test condition is same as Example 1), show good
Good performance.In low current density 50mAg-1Under, reversible specific capacity is 1705mAhg first-1；In high current density
20A·g-1Under, reversible specific capacity is 196mAhg-1。
Embodiment 4
A kind of preparation method of Heteroatom doping surface hollow ball grapheme material with holes, specifically includes following steps：
(1) synthesis of graphene oxide：It is identical with step (1) in embodiment 1；
(2) synthesis of surface graphene oxide with holes：It is identical with step (2) in embodiment 1；
(3) preparation of positively charged silicon dioxide ball template：It is identical with step (3) in embodiment 1；
(4) the graphene oxide@silica spheres complex with holes with nucleocapsid structure：With step (4) phase in embodiment 1
Together；
(5) the graphene oxide silica spheres complex 300mg surface of above-mentioned preparation with holes is placed in into plasma high
Warm tubular reactor center, removes impurity and vapor using mechanical pump evacuation, and is depressurized to 5Pa, then further
1 × 10 is evacuated to using molecular pump-3Pa, is then passed through protective gas N at one end2And gaseous state Heteroatom doping source ammonia and three
Phosphorus chloride to pressure is that (nitrogen is 0.5 with the volume ratio of Phosphorous chloride. and ammonia to 10Pa：1：1)(N2And gaseous state Heteroatom doping
The flow that source Phosphorous chloride. and ammonia are passed through is respectively 5sccm, 10sccm and 10sccm), by plasma high-temperature pipe reaction
Device is heated to 500 DEG C with 5 DEG C/min heating rates, then opens radio-frequency power supply, under conditions of radio-frequency power is 200W, carries out
Plasma discharge 30min, is then shut off radio frequency and heating power supply, and stopping is passed through ammonia and Phosphorous chloride., after being cooled to room temperature,
Products therefrom is cleaned into removing silicon dioxide masterplate twice with the HF of 10wt%, with the acetone-water mixture (volume of acetone and water
Than for 1：1) clean, then deionized water cleaning until filtrate conductivity be less than 10 μ S, filtrate solid material be phosphorus,
Nitrogen co-doped surface hollow ball grapheme material with holes.Can be obtained by elementary analysiss, it is the phosphorus for preparing, nitrogen co-doped
The phosphorus doping amount of surface hollow sphere Graphene with holes is 3.1%, and N doping amount is 8.3%, and oxygen content is 4.9%.
Table is carried out using SEM and TEM to resulting phosphorus, nitrogen co-doped surface hollow sphere grapheme material with holes
Levy, it is as a result similar to Example 1, and be applied to during the electrode material of lithium ion battery (test condition is same as Example 1), table
Reveal good performance.In low current density 50mAg-1Under, reversible specific capacity is 1987mAhg first-1；It is close in high current
Degree 20Ag-1Under, reversible specific capacity is 229mAhg-1。
Embodiment 5
A kind of preparation method of Heteroatom doping surface hollow ball grapheme material with holes, specifically includes following steps：
(1) synthesis of graphene oxide
Graphene oxide is prepared using improved Hummers methods, its technological process is as follows：Assemble in ice-water bath anti-
Bottle is answered, the solid mixing of 5g expanded graphites powder and 5g sodium nitrates under conditions of stirring (rotating speed is 1000r/min), is sequentially added
Thing, adds the concentrated sulphuric acid that 300mL mass fractions are 95%, 60min is reacted in ice-water bath；Subsequently, 60 times are divided (per minor tick
2min) add 25g potassium permanganate, controlling reaction temperature to be less than 10 DEG C, continue reaction 24h, be subsequently adding 300mL deionized waters
Dilution, after stirring reaction 60min, is warming up to 98 DEG C with 20 DEG C/min heating rates, insulation reaction 48h, and solution colour is from black
It is transformed into brown color；It is added dropwise over the oxidant (Deca per minute 10 of the hydrogen peroxide reduction residual that 100mL mass fractions are 35%
Drop), continue reaction 60min after dripping off, solution is changed into glassy yellow；Filtered while hot, and be 10%HCl molten with mass percent successively
Till the liquid and deionized water wash sulfate radical-free in the filtrate is detected；Filter cake is finally placed in 60 DEG C of vacuum drying oven
In be fully dried 12h, obtain graphene oxide；
(2) synthesis of surface graphene oxide with holes
By the graphene oxide deionized water ultrasonic disperse 120min of above-mentioned preparation, (frequency is 100KHz, power is
1000W), obtain the graphene oxide solution that mass percent concentration is 1.0%；(rotating speed of stirring is under agitation
1000r/min), to equipped with 50mL graphene oxide solution container in add 1000mL mass percent concentrations be 65% it is dense
HNO3, container finish is sealed, supersound process 10h (frequency is 100KHz, and power is 1000W, and bath temperature is 60 DEG C) stands
After 3h, pour in the deionized water of 200mL, be centrifuged under high speed of the rotating speed for 13000rpm and go acid, purification, after filtering, will
Gained solid is placed in 60 DEG C of vacuum drying oven and is fully dried 12h, obtains surface graphene oxide with holes；
(3) preparation of positively charged silicon dioxide ball template
By cetyl trimethylammonium bromide (CTAB) 2g be added to equipped with 300g deionized waters, 100mL ethylene glycol and
During 25mL mass percent concentrations are the there-necked flask of 25% ammonia, after stirring and dissolving (rotating speed of stirring is 1000r/min),
Reaction temperature is risen to into 70 DEG C, 60min is stirred, 3mL tetraethoxysilanes (TEOS) is then added dropwise over (rate of addition is 10
Drop/min), the 3- aminopropyl triethoxysilanes (APTES) of 300.0 μ L are then once injected with liquid-transfering gun, then in 70 DEG C of bars
Stirring reaction 4h under part, insulation are transferred in hydrothermal reaction kettle after standing 24h, and hydro-thermal reaction 48h under the conditions of 120 DEG C；Will
The product deionized water of acquisition and ethanol are cleaned multiple times until filtrate non-foam, then under the conditions of 80 DEG C is dried 12h, obtains
Positively charged silica spheres；
(4) the surface graphene oxide silica spheres complex with holes with nucleocapsid structure
Graphene oxide surface with holes is scattered in deionized water, the surface oxygen with holes that concentration is 10mg/mL is configured to
Graphite alkene solution；
2g positively charged silica spheres are scattered in 50mL deionized waters, then Deca 2.0mol/L salt acid for adjusting pH
It is worth to 2.5, is subsequently adding 15mL surfaces graphene oxide solution with holes, (magnetic force is stirred magnetic agitation reaction 24h at ambient temperature
It is 1000r/min that the rotating speed mixed is the rotating speed of stirring), using freeze drier in -48 DEG C of lyophilization 12h, obtain with core
The surface graphene oxide silica spheres composite with holes of shell structure；
(5) prepared by the plasma method of Heteroatom doping surface hollow ball Graphene with holes
Graphene oxide silica spheres composite 1000mg surface in step (4) with holes is placed in into plasma high
In warm tubular reactor, impurity and vapor are removed using mechanical pump evacuation, and is depressurized to 10Pa, then further used and divide
Sub- pump is evacuated to 1.0 × 10-2Pa, is then passed through protective gas N at one end2And gaseous state Heteroatom doping source NH3(N2And gaseous state
Heteroatom doping source NH3The flow being passed through is respectively 50sccm and 5sccm), it is 20Pa (N to pressure2With NH3Volume ratio be
10：1) plasma high-temperature tubular reactor is heated to into 600 DEG C with 10 DEG C/min heating rates, radio-frequency power supply is then opened,
Under conditions of radio-frequency power is 600W, plasma discharge 60min is carried out, be then shut off radio frequency and heating power supply, continue logical
Enter N2, stop being passed through NH3, after being cooled to room temperature, products therefrom is cleaned into removing silicon dioxide masterplate twice with the HF of 20wt%,
With acetone-water mixture, (acetone is 3 with water volume ratio：1) clean, then deionized water is cleaned until the conduction of filtrate again
Rate is less than 10 μ S, and filtrate solid material is N doping surface hollow ball grapheme material with holes.
Can be obtained by elementary analysiss, in the hollow ball grapheme material with holes of N doping surface, nitrogen-atoms numbers account for total atom
Several 13.7%, oxygen atomicity account for the 2.4% of total atom number.
Resulting N doping surface hollow ball grapheme material with holes is characterized using SEM and TEM, as a result with reality
Apply that example 1 is similar, and be applied to, during the electrode material of lithium ion battery (test condition is same as Example 1), show good
Performance.In low current density 50mAg-1Under, reversible specific capacity is 1927mAhg first-1；In high current density 20Ag-1
Under, reversible specific capacity is 255mAhg-1。
Embodiment 6
A kind of preparation method of Heteroatom doping surface hollow ball grapheme material with holes, specifically includes following steps：
(1) synthesis of graphene oxide
Graphene oxide is prepared using improved Hummers methods, its technological process is as follows：Assemble in ice-water bath anti-
Bottle is answered, (rotating speed of stirring is 200r/min) adds 1g expanded graphites powder and 1g sodium nitrates in reaction bulb under agitation
Mixture, adds the concentrated sulphuric acid that 90mL mass fractions are 95%, 10min is reacted in ice-water bath；Subsequently, 60 times are divided (every time
Interval 1min) add 5g potassium permanganate, controlling reaction temperature to be less than 5 DEG C, continue reaction 6h, be subsequently adding 50mL deionized waters
Reaction temperature, after stirring reaction 30min, is risen rapidly to 98 DEG C with 10 DEG C/min heating rates by dilution, insulation reaction 12h,
Solution colour is from black transitions into brown color；Then, it is added dropwise over the hydrogen peroxide reduction residual that 50mL mass fractions are 35%
Oxidant (Deca per minute 5 is dripped), continues reaction 30min after dripping off, solution is changed into glassy yellow；Filtered while hot, and matter is used successively
Till amount percent is 5%HCl solution and deionized water wash sulfate radical-free is detected in the filtrate；Finally filter cake is put
24h is fully dried in 40 DEG C of vacuum drying oven, graphene oxide is obtained；
(2) synthesis of surface graphene oxide with holes
By the graphene oxide deionized water ultrasonic disperse 30min (frequency is 20KHz, power is 40W) of above-mentioned preparation,
Obtain the graphene oxide solution that mass percent concentration is 0.1%；Under agitation (rotating speed of stirring is 200r/min),
The dense HNO that 500mL mass percent concentrations are 65% is added in the graphene oxide solution container equipped with 500mL3, by container
Bottle sealing, supersound process 0.5h (frequency is 20KHz, and power is 40W, and temperature is 4 DEG C), after standing 1h, pours going for 100mL into
In ionized water, acid is gone in the centrifugation under high speed of the rotating speed for 8000rpm, purification, after filtering, gained solid is placed in 40 DEG C true
24h is fully dried in empty drying baker, surface graphene oxide with holes is obtained；
(3) preparation of positively charged silicon dioxide ball template
By cetyl trimethylammonium bromide (CTAB) 0.5g be added to equipped with 100g deionized waters, 10mL ethylene glycol and
During 5mL mass percent concentrations are the three-neck flask of 25% ammonia, after stirring and dissolving (rotating speed of stirring is 200r/min), will
Reaction temperature rises to 40 DEG C, stirs 20min, 0.5mL tetraethoxysilanes (TEOS) are then added dropwise over (rate of addition is 5
Drop/min), the 3- aminopropyl triethoxysilanes (APTES) of 100.0 μ L are then once injected with liquid-transfering gun, then in 40 DEG C of bars
Stirring reaction 2h under part, insulation are transferred in hydrothermal reaction kettle after standing 12h, and hydro-thermal reaction 12h under the conditions of 80 DEG C；To obtain
Product deionized water and the ethanol purge for obtaining is until filtrate non-foam, then under the conditions of 60 DEG C is dried 24h, obtains positively charged
The silica spheres of lotus；
(4) the surface graphene oxide silica spheres complex with holes with nucleocapsid structure
Graphene oxide surface with holes is scattered in deionized water, the surface oxidation with holes that concentration is 1mg/mL is configured to
Graphene solution；
0.1g positively charged silica spheres are scattered in 20mL deionized waters, then Deca 0.5mol/L hydrochloric acid is adjusted
PH value adds 15mL surfaces graphene oxide solution with holes to 2.5, at ambient temperature magnetic agitation reaction 48h (magnetic agitation
Rotating speed be stirring rotating speed be 200r/min), using freeze drier in -28 DEG C of lyophilization 48h, obtain with nucleocapsid tie
The surface graphene oxide silica spheres composite with holes of structure；
(5) prepared by the plasma method of Heteroatom doping surface hollow ball Graphene with holes
Graphene oxide silica spheres composite 100mg surface in step (4) with holes is placed in into plasma high-temperature
In tubular reactor, impurity and vapor are removed using mechanical pump evacuation, and is depressurized to 1Pa, then further use molecule
Pump is evacuated to 1.0 × 10-3Pa, is then passed through protective gas N at one end2And gaseous state Heteroatom doping source NH3(N2And gaseous state is miscellaneous
Atom doped source NH3The flow being passed through is respectively 5sccm and 50sccm), it is 20Pa (N to pressure2With NH3Volume ratio be 0.1：
1) plasma high-temperature tubular reactor is heated to into 300 DEG C with 5 DEG C/min heating rates, radio-frequency power supply is then opened, is being penetrated
Under conditions of frequency power is 100W, plasma discharge 10min is then shut off radio frequency and heating power supply, continues to be passed through N2, stop
It is passed through NH3, after being cooled to room temperature, products therefrom is cleaned into removing silicon dioxide masterplate twice with the HF of 5wt%, acetone-water is used
(acetone is 3 with water volume ratio to mixture：1) clean, then deionized water is cleaned and is less than 10 μ until the conductivity of filtrate again
S, filtrate solid material are N doping surface hollow ball grapheme material with holes.
Can be obtained by elementary analysiss, in the hollow ball grapheme material with holes of N doping surface, nitrogen-atoms numbers account for total atom
Several 3.7%, oxygen atomicity account for the 7.9% of total atom number.
Resulting N doping surface hollow ball grapheme material with holes is characterized using SEM and TEM, as a result with reality
Apply that example 1 is similar, and be applied to, during the electrode material of lithium ion battery (test condition is same as Example 1), show good
Performance.In low current density 50mAg-1Under, reversible specific capacity is 1427mAhg first-1；In high current density 20Ag-1
Under, reversible specific capacity is 155mAhg-1。
Embodiment result shows, the present invention is by the graphite oxide with holes of the surface with nucleocapsid structure for preparing to template
Alkene@silica composites carry out doping and the reduction reaction of heteroatom, are reduced by plasma method and are adulterated and are improved
The electric conductivity and heat stability of Graphene, there is provided the reversible active sites of more storage lithiums, significantly improves the electrochemistry of Graphene
Storage lithium performance, obtains Large Copacity, powerful Heteroatom doping surface hollow ball Graphene electrodes material with holes.Heteroatom doping
The sharpest edges of surface hollow ball Graphene with holes are the electrode stability that improve material under the conditions of high current density, real
Heteroatom doping surface hollow ball Graphene with holes is showed and there is very high specific capacity within a short period of time, and there is excellent cycling
Performance.Its chemical property is substantially better than graphene film and other Carbon Materials, discloses Heteroatom doping surface hollow ball stone with holes
Black alkene is a kind of very promising electrode material.
Finally also should be noted that：Various embodiments above only to illustrate technical scheme, rather than a limitation；
Although being described in detail to the present invention with reference to foregoing embodiments, it will be understood by those within the art that：Its
Still the technical scheme described in foregoing embodiments can be modified, or to which part or all technical characteristic
Carry out equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention skill
The scope of art scheme.
Claims (10)
1. the preparation method of a kind of Heteroatom doping surface hollow ball grapheme material with holes, it is characterised in that：Specifically include with
Lower step：
(1) synthesis of surface graphene oxide with holes
Add water in graphene oxide, ultrasonic disperse obtains graphene oxide solution；Then under agitation, to being equipped with
Dense HNO is added in the container of graphene oxide solution3, container sealing, in 4 DEG C～60 DEG C 0.5～10h of ultrasonic reaction, stand 1～
After 3h, pour in deionized water, acid is gone in centrifugation, and purification filters, is dried, obtains surface graphene oxide with holes, standby；
(2) preparation of positively charged silicon dioxide ball template
Cetyl trimethylammonium bromide is added in the reaction vessel equipped with deionized water, ethylene glycol and ammonia, is stirred molten
Solution, is warming up to 40～70 DEG C, and then 20～60min of insulated and stirred is added dropwise over tetraethoxysilane, then rapidly joins 3- ammonia
Propyl-triethoxysilicane, in 40～70 DEG C of 2～4h of stirring reaction, insulation stands 12～24h, is subsequently placed in hydrothermal reaction kettle
Carry out hydro-thermal reaction；By the product cleaning of hydro-thermal reaction to filtrate non-foam, it is dried, obtains positively charged silica spheres；
(3) preparation of the surface graphene oxide silica spheres complex with holes with nucleocapsid structure
Positively charged silica spheres in step (2) are scattered in deionized water, silica spheres dispersion liquid is obtained；Then
It is 2～2.5 that Deca acid solution adjusts pH, adds surface graphene oxide dispersion with holes, and 24～48h of stirring reaction, freezing are dry
It is dry, obtain the surface graphene oxide silica spheres composite with holes with nucleocapsid structure；Wherein described surface band hole
Graphene oxide dispersion is to be dispersed in water to prepare surface graphene oxide with holes in step (1)；
(4) prepared by the plasma method of Heteroatom doping surface hollow ball Graphene with holes
Graphene oxide silica spheres composite 100mg～1000mg surfaces with holes is placed in into plasma high-temperature tubular type
In reactor, evacuation is depressurized to 1～10Pa, is further evacuated to 10-2～10-3Pa, is passed through protective gas and the miscellaneous original of gaseous state
Sub- doped source is 0.1～20Pa to pressure, and plasma high-temperature tubular reactor is warming up to 300～600 DEG C, then opens and penetrates
Frequency power, under conditions of radio-frequency power is 100～600W, 10～60min of plasma discharge is then shut off radio frequency and heating
Power supply, stopping be passed through Heteroatom doping source, cool down, cleaned with HF solution, then washed with acetone-water mixture, finally spend from
The conductivity of sub- water washing to filtrate is less than 10 μ S, and filtrate solid material is Heteroatom doping surface hollow ball graphite with holes
Alkene material；The Heteroatom doping source be gaseous state heteroatomic compound, the hetero atom be boron, nitrogen, sulfur or phosphorus in one kind with
On.
2. the preparation method of Heteroatom doping surface hollow ball grapheme material with holes according to claim 1, its feature exist
In：Dense HNO described in step (1)3Volume ratio with graphene oxide solution is (1～20)：1；The deionized water and oxidation
The volume ratio of graphene solution is (100～200) mL：(50～500) mL；
The mass percent concentration of concentrated nitric acid described in step (1) is 60～65%；The quality hundred of the graphene oxide solution
Specific concentration is divided to be 0.1～1.0%；
Cetyl trimethylammonium bromide described in step (2)：Deionized water：Ethylene glycol：Ammonia：Tetraethoxysilane：3- ammonia
The amount ratio of propyl-triethoxysilicane is (0.5～2) g：(100～300) g：(10～100) mL：(5～25) mL：(0.5～
3)mL：(100～300) μ L；
The concentration of surface graphene oxide dispersion with holes described in step (3) is (1～10) mg/mL；It is described positively charged
Silica spheres are (0.1～2) g with the mass volume ratio of deionized water：(20～50) mL；The positively charged silicon dioxide
Ball is (0.1～2) g with the mass volume ratio of surface graphene oxide dispersion with holes：15mL.
3. the preparation method of Heteroatom doping surface hollow ball grapheme material with holes according to claim 1, its feature exist
In：Protective gas described in step (4) is argon, helium or nitrogen；The protective gas and the volume ratio in Heteroatom doping source
For (0.1～10)：1；
The mass percent concentration of ammonia described in step (2) is 25～28%；Described in step (2), the temperature of hydro-thermal reaction is
80～120 DEG C, the time of hydro-thermal reaction is 12～48h.
4. the preparation method of Heteroatom doping surface hollow ball grapheme material with holes according to claim 3, its feature exist
In：Heteroatom doping source described in step (4) is one or more of diborane, ammonia, hydrogen sulfide or Phosphorous chloride..
5. the preparation method of Heteroatom doping surface hollow ball grapheme material with holes according to claim 1, its feature exist
In：Described in step (1), graphene oxide is prepared by the following method and forms：Under the conditions of ice-water bath, by mass percent it is
During 95～98% concentrated sulphuric acid adds sodium nitrate and graphite mixture, 10～60min of stirring reaction；It is gradually added potassium permanganate,
Controlling reaction temperature is less than 20 DEG C, and addition continues 6～24h of reaction after finishing, and adds deionized water dilution, and stirring reaction 30～
60min, is warming up to 20～98 DEG C, reacts 12-48h, is added dropwise over the hydrogen peroxide that mass percent is 30～35%, after dripping
Continue 30～60min of reaction, filter, washed with HCl solution and deionized water that mass percent is 5～10%, until
Till in filtrate, sulfate radical-free is detected；Filter cake is obtained into graphene oxide in 40～60 DEG C of 12～24h of drying finally.
6. the preparation method of Heteroatom doping surface hollow ball grapheme material with holes according to claim 5, its feature exist
In：It is described be gradually added that potassium permanganate refers to that each addition of potassium permanganate is potassium permanganate gross weight 1/60, per minor tick 1
～2min；The rotating speed of the stirring is 200～1000r/min；The speed of the Deca is 5～10 drops/min；The speed that heats up
Rate is 10～20 DEG C/min；
The graphite：Sodium nitrate：Concentrated sulphuric acid：Potassium permanganate：For the deionized water of dilution：The amount ratio of hydrogen peroxide is (1～5)
g：(1～5) g：(90～300) mL：(5～25) g：(50～300) mL：(50～100) mL.
7. the preparation method of Heteroatom doping surface hollow ball grapheme material with holes according to claim 1, its feature exist
In：
The frequency of ultrasonic disperse described in step (1) is 20～100KHz, and the power of ultrasonic disperse is 40～1000W, ultrasonic point
The scattered time is 30～120min；The frequency of the ultrasonic reaction is 20～100KHz, the power of ultrasonic reaction is 40～
1000W, the time of ultrasonic reaction is 0.5～10h；Centrifugal rotational speed is 8000～13000rpm；The temperature of the drying be 40～
60 DEG C, the dry time is 12～24h；
The rotating speed stirred described in step (2) is 200～1000r/min；The temperature being dried described in step (2) is 60～80
DEG C, the dry time is 12～24h；The speed of Deca described in step (2) is 5～10 drops/min；Clean described in step (2)
It is hydro-thermal reaction product to be cleaned using deionized water and ethanol successively；
Acid solution described in step (3) is hydrochloric acid, and the concentration of the acid solution is 0.5～2mol/L；The rotating speed of the stirring is
200～1000r/min, the temperature of the reaction is room temperature；The cryodesiccated temperature is -28～-48 DEG C, cryodesiccated
Time is 12～48h；
The concentration of HF described in step (4) is 5～20wt%；The number of times of the cleaning is 2～3 times；The acetone-water mixture
Middle acetone is (1～3) with water volume ratio：1；The heating rate is 5～10 DEG C/min.
8. the preparation method of Heteroatom doping surface hollow ball grapheme material with holes according to claim 1, its feature exist
In：Described plasma high-temperature tubular reactor includes plasma high-temperature quartz tube furnace, described plasma high-temperature
Quartz tube furnace one end is provided with protective gas air inlet pipe and Heteroatom doping source reacting gas air inlet pipe, described plasma
The high quartz tube furnace other end is provided with 2 exhaust tubes, exhaust tube connection liquid nitrogen cold trap, another exhaust tube connection molecule
Pump, the liquid nitrogen cold trap are connected with mechanical pump by pipeline, and described plasma high-temperature quartz tube furnace outer surface is wound with
Inductively coupled plasma coil, the two ends of described inductively coupled plasma coil connect radio frequency power source, described guarantor
Digital display mass flowmenter and control valve are connected with shield gas inlet pipe, are connected on described Heteroatom doping source gas inlet pipe
Digital display mass flowmenter and control valve are connected to, described being connected on the exhaust tube of liquid nitrogen cold trap is provided with the first control valve, institute
Be provided with the 3rd control valve on the pipeline for stating liquid nitrogen cold trap and mechanical pump, the 3rd control valve with connect with liquid nitrogen cold trap
Pipeline on be provided with vacuometer, be provided with the 4th control valve, described company in the vacuometer and the bypass of pipeline communication
The exhaust tube for being connected to molecular pump is provided with the second control valve, and described being connected on the exhaust tube of liquid nitrogen cold trap is provided with air inlet
Pipe, the air intake duct are provided with air shut-off valve door.
9. the Heteroatom doping surface hollow ball with holes that a kind of preparation method by described in any one of claim 1～8 is prepared
Grapheme material.
10. according to claim 9 Heteroatom doping surface hollow ball grapheme material with holes in lithium ion battery should
With.
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| CN111554869A (en) * | 2020-04-09 | 2020-08-18 | 上海应用技术大学 | Efficient heteroatom doping method |
| CN111668449A (en) * | 2020-07-15 | 2020-09-15 | 广州市豪越新能源设备有限公司 | Silicon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN114773642B (en) * | 2022-06-17 | 2022-09-20 | 中北大学 | Preparation of graphene/natural rubber with simultaneously improved mechanics, heat conductivity and wear resistance |
| US11732112B1 (en) | 2022-12-07 | 2023-08-22 | North University Of China | Method of preparing graphene/natural rubber composite with enhanced mechanical properties, thermal conductivity, and wear resistance |
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