CN105152161A - 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 PDF

Info

Publication number
CN105152161A
CN105152161A CN201510374574.XA CN201510374574A CN105152161A CN 105152161 A CN105152161 A CN 105152161A CN 201510374574 A CN201510374574 A CN 201510374574A CN 105152161 A CN105152161 A CN 105152161A
Authority
CN
China
Prior art keywords
holes
graphene oxide
reaction
heteroatom doping
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510374574.XA
Other languages
Chinese (zh)
Other versions
CN105152161B (en
Inventor
蒋仲杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201510374574.XA priority Critical patent/CN105152161B/en
Publication of CN105152161A publication Critical patent/CN105152161A/en
Application granted granted Critical
Publication of CN105152161B publication Critical patent/CN105152161B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

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

Heteroatom doping surface hollow ball grapheme material with holes and method for making and application
Technical field
The invention belongs to carbon material and electrochemical field, be specifically related to a kind of Heteroatom doping surface hollow ball grapheme material with holes and preparation method thereof and the application in Large Copacity, high multiplying power lithium ion battery.
Background technology
Lithium ion battery, because open circuit voltage is high, the advantage such as energy density large, long service life, memory-less effect, pollution-free and self-discharge be little, it is the development priority of current secondary cell, and in the electrical equipment such as mobile communication, notebook computer market, occupy larger share as important power supply source, and be expected to be applied to electromobile and the medium-and-large-sized storing device of national grid.Current, if will by lithium ion battery applications in large-scale energy storage device and powerful device, the electrode materials as lithium ion battery is necessarily required to keep good capacity characteristic and cyclical stability under high rate charge-discharge condition, the key that therefore exploitation has heavy body, the electrode materials of high power nature is research at present.
At present the main lithium ion battery negative material used take graphite as the carbon material of representative, and other negative materials also comprise: alloy type material, metal oxide materials, metal nitride materials, sulfide etc.The materials such as metal (comprising silicon), metal oxide, nitride, due to raw material sources rareness, complicated process of preparation, the more high reason of production cost, significantly limit their practical application.Cheap and close to metallic lithium the removal lithium embedded current potential that graphite possesses due to it is used by the negative material as industrialization.But, due to the closelypacked laminate structure of lamella in graphite, make graphite material there are some unsurmountable shortcomings, as lower in graphite theoretical capacity, the sheet interlayer spacing (d of graphite crystal 002=0.34nm) be less than lithium/compound between graphite layers Li xc 6sheet interlayer spacing (d 002=0.37nm), because in graphite, sheet interlayer spacing is less, and the restriction of production technique makes the stacked direction of graphite flake layer perpendicular to lithium ion transport direction in actual production process, so graphite material is often unsatisfactory as the high rate performance of the lithium ion battery of negative pole.These shortcomings make graphite material be limited by very large needing the application in Large Copacity, long lifetime, high-power energy storage device.Therefore, investigator is in the urgent need to seeking a kind of Carbon Materials be more suitable for as ion cathode material lithium.The Graphene of latest find causes the concern of researchist.
Graphene, also can be described as " mono-layer graphite ", the flexibility had due to its lamella and controllability, is the elementary cell of constructing all sp2 hydridization carbonaceous materials.Because it is unique, perfect structure makes Graphene have the characteristics such as excellent electricity, mechanics, calorifics and optics, and its electronic movement velocity reaches 1000ms especially -1, considerably beyond the movement velocity of electronics in other conductors, combined by the most stable benzene six-ring, there is larger theoretical specific surface area and (be about 2630m 2g -1) and better electronic conduction ability (be about 2 × 10 5cm 2v -1s -1).These characteristics of Graphene are that it becomes heavy body, the electrode materials of high power nature provides possibility.Graphene compared with other carbon material, the Graphene lithium ion battery electrode material as heavy body, high power nature preferably.As (Carbon such as Wang, 47 (2009) 2049-2053) adopt hydrazine hydrate reduction graphene oxide, obtain the similar petal-shaped grapheme material of microscopic pattern, the charge specific capacity through 1C discharge and recharge 100 materials can be stabilized in 460mAhg -1.
Under the effort of investigator, preparing now Graphene on a large scale becomes possibility.How while a series of advantage of reservation graphite material, increase lithium storage content, improve ionic conductivity, improve multiplying power and cycle performance, the focus of research has been placed on the doping vario-property of grapheme material by researchist.Carrying out heterogeneous element doping to grapheme material is a kind of conventional method improving Graphene performance, is improved the embedding lithium behavior of Graphene by the microtexture and electronic state changing Graphene.Doped with non-metals element generally can atomic form and compound form two kinds of modes be introduced.The heterogeneous element that can be used for grapheme material doping mainly comprises boron, nitrogen, sulphur, phosphorus etc.Wu etc. (ACSNano, 5 (2011) 5463-5471) adopt thermal expansion graphite oxide synthesizing graphite alkene, subsequently respectively at 600 DEG C and NH 3the obtained nitrogen-doped graphene of/Ar reaction, 800 DEG C and BCl 3the obtained boron doped graphene of/Ar reaction, wherein boron doped graphene is at 50mAg -1during discharge and recharge, there is 1549mAhg -1reversible capacity first and can 1227mAhg be kept through 30 circulations -1.
In sum, Graphene and heterogeneous element doped graphene reversible capacity high, can high current charge-discharge, power-performance is good, but it exists numerous defect:
(1) due in preparation and cycle charge discharge electric process, nano-graphene sheet (GNS) is due to the existence of sheet interlayer Van der Waals force, can be gathered into Graphene paper-like structure gradually, cause a large amount of sheet surfaces to be difficult to be utilized, thus its specific surface is well below theoretical specific surface;
(2) gathering of lamella causes the active surface of material to continue to reduce, and creates many discontinuous passages simultaneously, hinders ion quick transmission wherein;
(3) graphene film that surface is complete, due to its surface compact, easily interrupted by the ion transport of graphene film; Although because ion is to be parallel to the specific conductivity on graphenic surface direction very high, it is lower perpendicular to the conductance efficiency on graphene film in-plane.Therefore the migration of ion mainly can concentrate on the edge of graphene film, greatly hinders the raising of its ionic conductivity.
The Heteroatom doping Graphene prepared due to prior art exists above-mentioned defect makes the application of Heteroatom doping Graphene be limited by very large.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of Heteroatom doping surface hollow ball grapheme material with holes.The present invention adopts chemical etching method to prepare the electronegative surface graphene oxide with holes of different carbon/oxygen ratio, with positively charged silica spheres for masterplate, be coated on positively charged silica spheres surface by the surface graphene oxide with holes that electrostatic interaction is electronegative and form nucleocapsid structure mixture, then prepare the Heteroatom doping surface hollow ball grapheme material with holes of better performances, structure-controllable by plasma method doping heteroatoms.
Another object of the present invention is to provide the Heteroatom doping surface prepared by above-mentioned preparation method hollow ball grapheme material with holes.
Another object of the present invention is the application providing above-mentioned Heteroatom doping surface hollow ball grapheme material with holes.
Object of the present invention is achieved through the following technical solutions:
A preparation method for Heteroatom doping surface hollow ball grapheme material with holes, specifically comprises the following steps:
(1) synthesis of surperficial graphene oxide with holes
Water is added in graphene oxide, ultrasonic disperse, obtain graphene oxide solution; Then under agitation, in the container that graphene oxide solution is housed, dense HNO is added 3, container sealing, in 4 DEG C ~ 60 DEG C ultrasonic reaction 0.5 ~ 10h, after leaving standstill 1 ~ 3h, pours in deionized water, centrifugal disacidify, purifying, filters, dry, obtains surperficial graphene oxide with holes, for subsequent use;
(2) preparation of positively charged silicon-dioxide ball template
Cetyl trimethylammonium bromide (CTAB) is joined in the reaction vessel that deionized water, ethylene glycol and ammoniacal liquor are housed, stirring and dissolving, be warming up to 40 ~ 70 DEG C, insulated and stirred 20 ~ 60min, then dropwise add tetraethoxysilane (TEOS), then add 3-aminopropyl triethoxysilane (APTES) fast, in 40-70 DEG C of stirring reaction 2 ~ 4h, insulation leaves standstill 12 ~ 24h, carries out hydro-thermal reaction with being placed in hydrothermal reaction kettle; By the product cleaning of hydro-thermal reaction to filtrate non-foam, dry, obtain positively charged silica spheres;
(3) there is the preparation of the surface graphene oxide silica spheres with holes mixture of nucleocapsid structure
Positively charged silica spheres in step (2) is scattered in deionized water, obtains silica spheres dispersion liquid; Then dripping acid solution regulates pH to be 2 ~ 2.5, adds surperficial graphene oxide dispersion with holes, stirring reaction 24 ~ 48h, lyophilize, obtains having the surface graphene oxide silica spheres with holes matrix material of nucleocapsid structure; Wherein said surface graphene oxide dispersion with holes is scattered in water by surface graphene oxide with holes in step (1) to prepare;
(4) the plasma method preparation of Heteroatom doping surface hollow ball Graphene with holes
100mg ~ 1000mg surface graphene oxide silica spheres matrix material with holes is placed in plasma high-temperature tubular reactor, vacuumizes and be depressurized to 1 ~ 10Pa, be evacuated to 10 further -2~ 10 -3pa, pass into shielding gas and gaseous state Heteroatom doping source to pressure is 0.1 ~ 20Pa, plasma high-temperature tubular reactor is heated to 300 ~ 600 DEG C with 5 ~ 10 DEG C/min temperature rise rate, then radio-frequency power supply is opened, be under the condition of 100 ~ 600W at radio frequency power, plasma discharge 10 ~ 60min, then radio frequency and heating power supply is closed, stop passing into Heteroatom doping source, cooling, clean with HF solution, wash with acetone-water mixture again, finally with deionized water wash to the electric conductivity of filtrate lower than 10 μ S, filtrate solid material is Heteroatom doping surface hollow ball grapheme material with holes.
Described in step (1), the frequency of ultrasonic disperse is 20 ~ 100KHz, and the power of ultrasonic disperse is 40 ~ 1000W, and the time of ultrasonic disperse is 30 ~ 120min; The frequency of described ultrasonic reaction is 20 ~ 100KHz, and the power of ultrasonic reaction is 40 ~ 1000W, and the time of ultrasonic reaction is 0.5 ~ 10h; The mass percent concentration of described graphene oxide solution is 0.1 ~ 1.0%; Centrifugal rotational speed is 8000 ~ 13000rpm; The temperature of described drying is 40 ~ 60 DEG C, and the dry time is 12 ~ 24h.
Described in step (1), graphene oxide is prepared from by the following method: under ice-water bath condition, is that the vitriol oil of 95 ~ 98% adds in SODIUMNITRATE and graphite mixture by mass percent, stirring reaction 10 ~ 60min; Progressively add potassium permanganate, control temperature of reaction and be no more than 20 DEG C, after adding, continue reaction 6 ~ 24h, add deionized water dilution, stirring reaction 30 ~ 60min, be warming up to 20 ~ 98 DEG C, reaction 12 ~ 48h, dropwise adds the hydrogen peroxide that mass percent is 30 ~ 35%, drip rear continuation reaction 30 ~ 60min, filtering, is that 5 ~ 10%HCl solution and deionized water wash, until sulfate radical-free is detected in filtrate with mass percent; Finally by filter cake in 40 ~ 60 DEG C of drying 12 ~ 24h, obtain graphene oxide; The described potassium permanganate that progressively adds refers to that each add-on of potassium permanganate is 1/60 of potassium permanganate gross weight, every minor tick 1 ~ 2min; The rotating speed of described stirring is 200 ~ 1000r/min; The speed of described dropping is 5 ~ 10/min; Described temperature rise rate is 10 ~ 20 DEG C/min;
Described Graphite Powder 99: SODIUMNITRATE: the vitriol oil: potassium permanganate: the deionized water for diluting: 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.
Described Graphite Powder 99 is all kinds of natural graphite or expanded graphite.
In described graphene oxide, oxygen atomicity content accounts for 20 ~ 60% of total atom number.
Dense HNO described in step (1) 3be (1 ~ 20) with the volume ratio of graphene oxide solution: 1; The mass percent concentration of described concentrated nitric acid is 60 ~ 65%; The volume ratio of described deionized water and graphene oxide solution is (100 ~ 200) mL:(50 ~ 500) mL.
Described in step (2), the mass percent concentration of ammoniacal liquor is 25 ~ 28%; The rotating speed of described stirring is 200 ~ 1000r/min; The temperature of described hydro-thermal reaction is 80 ~ 120 DEG C, and the time of hydro-thermal reaction is 12 ~ 48h; The temperature of described drying is 60 ~ 80 DEG C, and the dry time is 12 ~ 24h; The speed of described dropping is 5 ~ 10/min; Described cleaning adopts deionized water and ethanol to clean hydro-thermal reaction product successively.
Cetyl trimethylammonium bromide (CTAB) described in step (2): deionized water: ethylene glycol: ammoniacal liquor: tetraethoxysilane (TEOS): the amount ratio of 3-aminopropyl triethoxysilane (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 surperficial graphene oxide dispersion with holes described in step (3) is (1 ~ 10) mg/mL; The silica spheres of described positive charge and the mass volume ratio of deionized water are (0.1 ~ 2) g:(20 ~ 50) mL; The mass volume ratio of described positively charged silica spheres and surface graphene oxide dispersion with holes is (0.1 ~ 2) g:15mL; Described acid solution is hydrochloric acid, and the concentration of described acid solution is 0.5 ~ 2mol/L; The rotating speed of described stirring is 200 ~ 1000r/min, and the temperature of described reaction is room temperature; Described cryodesiccated temperature is-28 ~ 48 DEG C, and the cryodesiccated time is 12 ~ 48h.
Described in step (4), shielding gas is argon gas, helium or nitrogen; Described Heteroatom doping source is more than one in diborane, ammonia, hydrogen sulfide or phosphorus trichloride; The volume ratio in described shielding gas and Heteroatom doping source is (0.1 ~ 10): 1.
Described in step (4), the concentration of HF is 5 ~ 20wt%; The number of times of described cleaning is 2 ~ 3 times; In described acetone-water mixture, acetone and water volume ratio are (1 ~ 3): 1.
In this described Heteroatom doping surface hollow ball grapheme material with holes, content of heteroatoms accounts for 2.5 ~ 40% of total atom number, and oxygen atomicity accounts for the 1-8% of total atom number.
Described Heteroatom doping surface hollow ball grapheme material with holes is prepared by above-mentioned preparation method.
Described Heteroatom doping surface hollow ball grapheme material with holes is in the application in Large Copacity, high multiplying power lithium ion battery.
Described application is specially the electrode materials of Heteroatom doping surface hollow ball grapheme material with holes for the preparation of lithium ion battery.
The preparation method of described electrode materials is: by hollow ball grapheme material with holes, conductive carbon black and the binding agent mixing of Heteroatom doping surface, obtain mixture; Add solvent, being coated with on a current collector after grinding, is working electrode after drying, shearing, compressing tablet; Wherein in the mixture, by mass percentage, Heteroatom doping surface hollow ball Graphene content with holes is 50% ~ 98%, and the content of conductive carbon black is 25% ~ 1%, and the content of binding agent is 25% ~ 1%; The consumption of solvent is 50 ~ 1000wt% of described mixture.
Described solvent is more than one in ethanol, acetone or N-Methyl pyrrolidone; Described collector is Copper Foil, aluminium foil, titanium sheet, stainless steel plate or platinized platinum.
An assembling for lithium ion half-cell, with above-mentioned electrode materials for working electrode, using lithium sheet as to electrode/reference electrode, adds the electrolytic solution containing lithium salts, is assembled into button-shaped lithium ion half-cell in glove box;
Described lithium salts is LiPF 6, LiClO 4or LiAsF 6, the organic solvent in described electrolytic solution is more than one in propylene carbonate (PC), methylcarbonate (DMC) or NSC 11801 (EC).The volumetric molar concentration of described electrolytic solution is 0.1 ~ 3mol/L.
The test of lithium ion half-cell: carry out constant current charge-discharge test under initial large current density condition; Carrying out constant current charge-discharge test condition under described initial large current density condition is 50mAg -1~ 20Ag -1.The present invention adopts chemical etching method to prepare the electronegative surface graphene oxide with holes of different carbon/oxygen ratio, with positively charged silica spheres for masterplate, be coated on positively charged silica spheres surface by the surface graphene oxide with holes that electrostatic interaction is electronegative and form nucleocapsid structure mixture, again under shielding gas and certain temperature condition, pass into heteroatomic compound gas, opening power activated plasma discharges, the reduction of graphene oxide is achieved and Heteroatom doping exists by the effect of high energy particle and electronics, obtain Heteroatom doping surface hollow ball grapheme material with holes, this material is used for lithium ion battery and has good electrical property.In addition, in plasma method, the present invention can control the energy of high energy particle and electronics by the adjustment of plasma parameter, thus realizes the regulation and control of state and structure etc. of heteroatomic doping content, foreign atom.
Described plasma high-temperature tubular reactor comprises plasma high-temperature quartz tube furnace, described plasma high-temperature quartz tube furnace one end is provided with shielding gas inlet pipe and Heteroatom doping source reactant gases inlet pipe, the described plasma high-temperature quartz tube furnace the other end is provided with 2 extraction pipes, one extraction pipe connects liquid nitrogen cold trap, another extraction pipe connects molecular pump, described liquid nitrogen cold trap is connected with mechanical pump by pipeline, described plasma high-temperature quartz tube furnace outside surface is wound with inductively coupled plasma coil, the two ends of described inductively coupled plasma coil connect radio frequency power source.Described shielding gas inlet pipe is connected with digital display mass flowmeter and regulated valve, described Heteroatom doping source gas inlet pipe is connected with digital display mass flowmeter and regulated valve, the described extraction pipe being connected to liquid nitrogen cold trap is provided with the first by-pass valve control, the described extraction pipe being connected to liquid nitrogen cold trap is provided with air intake duct, and described air intake duct is provided with air control valve door; The pipeline of described liquid nitrogen cold trap and mechanical pump is provided with the 3rd by-pass valve control, the pipeline that described by-pass valve control is communicated with liquid nitrogen cold trap is provided with vacuumometer, the bypass of described vacuumometer and pipeline communication is provided with the 4th by-pass valve control, the described extraction pipe being connected with molecular pump is provided with the second by-pass valve control.Described Heteroatom doping source gas inlet pipe is many gas circuits inlet pipe, and each gas circuit inlet pipe connects digital display mass flowmeter and regulated valve.
Tool of the present invention has the following advantages and beneficial effect:
(1) the material hollow graphite alkene ball that prepared by the present invention has very unified size, is made up of hollow ball and very thin Graphene shell; A large amount of mesoporous perpendicular to spherome surface is there is in outer field Graphene shell, can in different directions for lithium ion diffusion transport provides path;
(2) in the material prepared of the present invention, unique hollow structure can provide larger specific surface and shorter diffusion length thus promote the transmission of lithium ion in electrode materials; The nano material of hollow structure can solve the problem that in the working cycle that electrode materials produces due to excessive volumetric expansion, capacity attenuation is too fast, in this case, the nano material of hollow structure can hinder the reunion of active particle and provide enough large space to alleviate volumetric expansion;
(3) the present invention prepare Heteroatom doping surface hollow ball Graphene with holes as lithium ion battery electrode material, the Large Copacity, the high magnification electrode materials that use can be carried out under fast charging and discharging condition, this material significantly improves electric conductivity and the thermostability of electrode materials, provides the reversible active sites of more storage lithiums;
(4) using plasma legal system of the present invention is for Heteroatom doping surface hollow ball grapheme material with holes, compared with general high-temperature direct thermal decomposition-reduction doping method, the features such as plasma-assisted process of the present invention has temperature of reaction low (≤500 DEG C), the reaction times is short, cost is low; And Heteroatom doping amount and homogeneity thereof can be effectively controlled by the adjustment of plasma discharge parameter;
(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 production.
In a word, the with holes graphene oxide silica spheres matrix material with nucleocapsid structure standby by employing masterplate legal system is raw material, using plasma electric discharge reduction and doping obtain Heteroatom doping surface hollow ball Graphene with holes, not only achieve the doping of heteroatoms at hollow ball Graphene lattice, and remove oxygen-containing functional group further, improve electric conductivity and the thermostability of Graphene, increase the reversible active sites of storage lithium, obtain a kind of Large Copacity, powerful Graphene electrodes material.
Accompanying drawing explanation
Fig. 1 is the structural representation of plasma high-temperature tubular reactor of the present invention; Wherein 1-quartz tube furnace, 2-mass flowmeter, 3-variable valve (needle-valve), 4-liquid nitrogen cold trap, 5-mechanical pump, 6-coil (copper tube coil), 7-radio frequency power source, 8-molecular pump, 9-first by-pass valve control (butterfly valve), 10-second by-pass valve control (butterfly valve), 11-shielding gas inlet pipe, 12-gaseous state Heteroatom doping source inlet pipe, 13-molecular pump extraction pipe, 14-extraction pipe, 15-sample mounting table, 16-vacuumometer, 17-the 3rd by-pass valve control, 18-the 4th by-pass valve control;
Fig. 2 is the structural characterization figure of N doping surface hollow ball grapheme material with holes prepared by embodiment 1; Wherein (a) is SEM photo, and (b) is transmission electron microscope photo;
Fig. 3 is that the N doping surface hollow ball grapheme material with holes of embodiment 1 preparation is as the electric performance test curve of electrode materials under low current density; Wherein (a) is constant current charge-discharge voltage curve, and (b) and (c) is respectively cycle performance and coulombic efficiency, and current density is 50mAg -1;
Fig. 4 is the electric performance test curve of N doping surface hollow ball grapheme material with holes as electrode materials of embodiment 1 preparation; Wherein (a) constant current charge-discharge voltage curve that is high current density lower electrode material, in figure, 0.5 ~ 20 represents current density 0.5Ag -1~ 20Ag -1; B high rate performance that () is different high current density lower electrode material and cycle performance curve, current density is 0.5Ag -1to 20Ag -1, Ag in figure -1represent Ag -1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A preparation method for Heteroatom doping surface hollow ball grapheme material with holes, specifically comprises the following steps:
(1) synthesis of graphene oxide
(1-1) in ice-water bath, reaction flask is assembled, (rotating speed of stirring is 500r/min) adds the solid mixture of 1g expanded graphite powder and 2.5g SODIUMNITRATE in reaction flask under agitation, add the vitriol oil that 150mL mass percent is 95% again, in ice-water bath, react 30min; Subsequently, point 60 times (every minor tick 1min) add 15g potassium permanganate, and controlling temperature of reaction is 0 DEG C, continue reaction 12h; Add the dilution of 150mL deionized water again, after stirring reaction 30min (rotating speed of stirring is 500r/min), be warming up to 98 DEG C with the temperature rise rate of 10 DEG C/min, insulation reaction 48h, solution colour becomes brown color from black transitions, obtains the crude product of graphene oxide;
(1-2) in crude product, drip the residual oxygenant of hydrogen peroxide reduction that (rate of addition is 5/min) 50mL massfraction is 35%, drip off rear continuations and react 30min, solution becomes glassy yellow; Filtered while hot, and be 5%HCl solution and deionized water wash until sulfate radical-free is detected in filtrate with massfraction successively, be finally placed in the dry 12h of vacuum drying oven of 60 DEG C, obtain graphene oxide;
(2) synthesis of surperficial graphene oxide with holes
By the graphene oxide deionized water ultrasonic disperse 60min of above-mentioned preparation (frequency be 50KHz, power be 150W), obtain the graphene oxide solution that mass percent concentration is 0.5%; Under agitation (rotating speed of stirring is 500r/min), in the graphene oxide solution container that 50mL is housed, the dense HNO that 250mL mass percent concentration is 65% is added 3container is put into closed glass container, (frequency is 100KHz to supersound process 1h, and power is 500W, temperature is 25 DEG C), after leaving standstill 1h, pour in the deionized water of 100mL, centrifugal disacidify (centrifugal rotational speed is 13000rpm), purifying, filter, in 60 DEG C of dry 12h, obtain surperficial graphene oxide with holes;
(3) preparation of positively charged silicon-dioxide ball template
0.8624g cetyl trimethylammonium bromide (CTAB) is joined 149.5g deionized water is housed, 25mL ethylene glycol and 7.2mL mass percent concentration are in the three-necked flask of the ammoniacal liquor of 25%, after stirring and dissolving (rotating speed of stirring is 500r/min), temperature of reaction is risen to 50 DEG C, stir 30min, then 1mL tetraethoxysilane (TEOS) is dropwise added (rate of addition is 5/min), then 140.0 μ L3-aminopropyl triethoxysilanes (APTES) are once injected with liquid-transfering gun, under 50 DEG C of conditions, stirring reaction 2h, after insulation leaves standstill 20h, being transferred to inner bag is in the hydrothermal reaction kettle of tetrafluoroethylene, in 100 DEG C of hydro-thermal reaction 24h, by the product deionized water of hydro-thermal reaction and ethanol purge until filtrate non-foam, then dry 12h under 60 DEG C of conditions, obtain positively charged silica spheres,
(4) there is the preparation of the surface graphene oxide silica spheres with holes mixture of nucleocapsid structure
Be scattered in deionized water by the surface graphene oxide with holes of step (2), be mixed with surperficial graphene oxide solution with holes, its concentration is 2mg/mL;
Positively charged for 0.3g silica spheres is scattered in 30mL deionized water, then 1.0mol/L hydrochloric acid (often drip 1 hydrochloric acid soln and measure a pH value) adjust ph to 2.5 is dripped, add the surface graphene oxide solution with holes of 15mL, magnetic agitation reaction 24h (rotating speed of magnetic agitation is the rotating speed stirred is 500r/min) at ambient temperature, adopt freeze drier in-40 DEG C of lyophilize 24h, obtain having the surface graphene oxide silica spheres with holes matrix material of nucleocapsid structure;
(5) the plasma method preparation of Heteroatom doping surface hollow sphere grapheme material with holes
Graphene oxide silica spheres matrix material 300mg with holes surperficial in step (4) is placed in plasma high-temperature tubular reactor, mechanical pump is adopted to vacuumize removing impurity and water vapour, and be depressurized to 5Pa, then use molecular pump to be evacuated to 10 further -3pa, then at one end passes into shielding gas N 2and gaseous state Heteroatom doping source NH 3(N 2and gaseous state Heteroatom doping source NH 3the flow passed into is respectively 5sccm and 10sccm) to pressure be 10Pa (N 2with NH 3volume ratio be 0.5:1); plasma high-temperature tubular reactor is heated to 500 DEG C with 5 DEG C/min temperature rise rate; then radio-frequency power supply is opened; be under the condition of 200W at radio frequency power; carry out plasma discharge 30min; then close radio frequency and heating power supply, continue to pass into protective gas, stop passing into NH 3after being cooled to room temperature, the HF of products therefrom 10wt% is cleaned twice removing silicon-dioxide masterplate, acetone-water mixture (volume ratio of acetone and water is 1:1) is finally used to clean, then use washed with de-ionized water again until the electric conductivity of filtered liquid is lower than 10 μ S, filtrate solid material is the surface hollow sphere grapheme material with holes of N doping.
Can be obtained by ultimate analysis, in N doping hollow ball grapheme material, nitrogen-atoms number accounts for 14.3% of total atom number, and oxygen atomicity accounts for 4.4% of total atom number.
The structural representation of plasma high-temperature tubular reactor as shown in Figure 1.
The N doping hollow ball Graphene that the present embodiment 1 obtains carries out scanning electron microscope and transmission electron microscope observing, and the scanning electron microscope of the hollow ball Graphene of the nitrogen atom doping of gained and transmission electron microscope photo are as shown in Figure 2.As can be seen from Figure 2, N doping hollow ball Graphene prepared by the present embodiment 1, nearly all Graphene ball has hollow structure.
Application performance test in lithium ion battery
By N doping hollow ball grapheme material, conductive carbon black, polyvinylidene difluoride (PVDF) binding agent by the mixing of certain mass ratio (80: 10: 10), obtain mixture; Adding the N-Methyl pyrrolidone accounting for described mixture 200wt%, making through grinding to form even starchiness, then slurry is coated on Cu paper tinsel, 100 DEG C of dry 5h, after N-Methyl pyrrolidone is volatilized, shearing, compressing tablet, dry 20h under 100 DEG C of vacuum, obtains electrode materials; Take electrode materials as working electrode, using lithium sheet as to electrode/reference electrode, with 1M (mol/L) LiPF 6nSC 11801 EC/ methylcarbonate DMC (volume ratio 1:1) solution as electrolytic solution, in glove box, be assembled into button-shaped lithium ion half-cell, then under different current density condition, carry out constant current charge-discharge test.Test result as shown in Figure 3,4.At low current density 50mAg -1under, reversible specific capacity is 1848.6mAhg first -1; At high current density 20Ag -1under, reversible specific capacity is 205mAhg -1.
Fig. 3 represents from Fig. 3 a constant current charge-discharge voltage curve, N doping surface hollow ball grapheme material with holes is as the battery performance test curve of electrode materials under low current density, can find that this material first discharge specific capacity reaches 2385.5mAhg -1, the 2nd time specific discharge capacity is 1835.5mAhg -1, the 5th, the 10th time, the 25th time specific discharge capacity is respectively 1815.7mAhg -1, 1802.6mAhg -1, 1726.0mAhg -1, show that this material has good reversible cycle from second time discharge and recharge.Fig. 3 b cycle performance curve shows that the charging capacity conservation rate of this material is 91.9%.Fig. 3 c coulombic efficiency curve shows that the initial coulomb efficiency of this material is 77.5%, and from second time discharge and recharge, coulombic efficiency is close to 100%.Known, N doping surface hollow ball grapheme material with holes has excellent chemical property under low current density, and it not only has high reversible charge specific capacity is 1848.6mAhg -1, and improve initial coulomb efficiency 77.5% and the capability retention 91.9% of electrode materials.This is mainly because the hollow structure of N doping surface hollow ball Graphene uniqueness with holes can provide larger specific surface and shorter diffusion length thus promote the transmission of lithium ion in electrode materials; The problem that in the working cycle that electrode materials produces due to excessive volumetric expansion, capacity attenuation is too fast can be solved; The reunion of active particle can be hindered in addition and provide enough 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 20Ag -1) high rate performance (Fig. 4 a) and stable circulation linearity curve (Fig. 4 b) known, at 0.5Ag -1, 1Ag -1, 2.5Ag -1, 5Ag -1, 10Ag -1, 15Ag -1reversible first charge specific capacity under current density is respectively 1148.8mAhg -1, 985.8mAhg -1, 746.4mAhg -1, 531.5mAhg -1, 345.6mAhg -1, even at 20Ag -1high current density under, reversible charge specific capacity still reaches 244.7mAhg first -1.Through 0.5Ag -1to 20Ag -1each 10 times of different current density discharge and recharges after, charging and discharging currents density is down to 0.5Ag -1time, its charge specific capacity goes back up to 995.7mAhg again -1.From these digital proof N doping surface hollow ball Graphenes with holes, there is under high current density excellent fast charging and discharging performance, high specific storage, excellent high rate performance and cyclical stability.
Embodiment 2
A preparation method for Heteroatom doping surface hollow ball grapheme material with holes, specifically comprises the following steps:
(1) synthesis of graphene oxide: identical with step (1) in embodiment 1;
(2) synthesis of surperficial graphene oxide with holes: identical with step (2) in embodiment 1;
(3) preparation of positively charged silicon-dioxide ball template: identical with step (3) in embodiment 1;
(4) there is the graphene oxide silica spheres mixture with holes of nucleocapsid structure: identical with step (4) in embodiment 1;
(5) graphene oxide silica spheres mixture 300mg with holes for surface is placed in plasma high-temperature tubular reactor central position, mechanical pump is adopted to vacuumize removing impurity and water vapour, and be depressurized to 5Pa, then use molecular pump to be evacuated to 1 × 10 further -3pa, then at one end passes into shielding gas N 2and gaseous state Heteroatom doping source diborane is 10Pa (N to pressure 2be 0.5:1 with the volume ratio of diborane) (N 2and the flow that gaseous state Heteroatom doping source diborane passes into is respectively 5sccm and 10sccm), plasma high-temperature tubular reactor is heated to 500 DEG C with 5 DEG C/min temperature rise rate, then radio-frequency power supply is opened, be under the condition of 200W at radio frequency power, carry out plasma discharge 30min, then radio frequency and heating power supply is closed, stop passing into diborane, after being cooled to room temperature, the HF of products therefrom 10wt% is cleaned twice removing silicon-dioxide masterplate, acetone-water mixture (volume ratio of acetone and water is 1:1) is finally used to clean, then washed with de-ionized water is used again until the electric conductivity of filtered liquid is lower than 10 μ S, filtrate solid material is boron doped surface hollow ball grapheme material with holes.Can be obtained by ultimate analysis, the boron doping amount of the boron doped surface prepared hollow sphere Graphene with holes is 6.3%, and oxygen level is 3.2%.
SEM and TEM is utilized to characterize to obtained boron doped surface hollow sphere grapheme material with holes, result is similar to embodiment 1, and when being applied to the electrode materials of lithium ion battery (test condition is identical with embodiment 1), show good performance.At low current density 50mAg -1under, reversible specific capacity is 1907mAhg first -1; At high current density 20Ag -1under, reversible specific capacity is 225mAhg -1.
Embodiment 3
A preparation method for Heteroatom doping surface hollow ball grapheme material with holes, specifically comprises the following steps:
(1) synthesis of graphene oxide: identical with step (1) in embodiment 1;
(2) synthesis of surperficial graphene oxide with holes: identical with step (2) in embodiment 1;
(3) preparation of positively charged silicon-dioxide ball template: identical with step (3) in embodiment 1;
(4) there is the surface graphene oxide with holes silica spheres mixture of nucleocapsid structure: identical with step (4) in embodiment 1;
(5) graphene oxide silica spheres mixture 300mg with holes for the surface of above-mentioned preparation is placed in plasma high-temperature tubular reactor central position, mechanical pump is adopted to vacuumize removing impurity and water vapour, and be depressurized to 5Pa, then use molecular pump to be evacuated to 1 × 10 further -3pa, then at one end passes into shielding gas N 2and gaseous state Heteroatom doping source phosphorus trichloride is 10Pa (N to pressure 2be 0.5:1 with the volume ratio of phosphorus trichloride) (N 2and the flow that gaseous state Heteroatom doping source phosphorus trichloride passes into is respectively 5sccm and 10sccm), plasma high-temperature tubular reactor is heated to 500 DEG C with 5 DEG C/min temperature rise rate, then radio-frequency power supply is opened, be under the condition of 200W at radio frequency power, carry out plasma discharge 30min, then radio frequency and heating power supply is closed, stop passing into phosphorus trichloride, after being cooled to room temperature, the HF of products therefrom 10wt% is cleaned twice removing silicon-dioxide masterplate, with acetone-water mixture cleaning (volume ratio of acetone and water is 1:1), then washed with de-ionized water is used again until the electric conductivity of filtered liquid is lower than 10 μ S, filtrate solid material is the surface hollow sphere grapheme material with holes of phosphorus doping.Can be obtained by ultimate analysis, the phosphorus doping amount of the surface hollow sphere Graphene with holes of the phosphorus doping prepared is 5.1%, and oxygen level is 4.2%.
SEM and TEM is utilized to characterize to the surface of obtained phosphorus doping hollow sphere grapheme material with holes, result is similar to embodiment 1, and when being applied to the electrode materials of lithium ion battery (test condition is identical with embodiment 1), show good performance.At low current density 50mAg -1under, reversible specific capacity is 1705mAhg first -1; At high current density 20Ag -1under, reversible specific capacity is 196mAhg -1.
Embodiment 4
A preparation method for Heteroatom doping surface hollow ball grapheme material with holes, specifically comprises the following steps:
(1) synthesis of graphene oxide: identical with step (1) in embodiment 1;
(2) synthesis of surperficial graphene oxide with holes: identical with step (2) in embodiment 1;
(3) preparation of positively charged silicon-dioxide ball template: identical with step (3) in embodiment 1;
(4) there is the graphene oxide silica spheres mixture with holes of nucleocapsid structure: identical with step (4) in embodiment 1;
(5) graphene oxide silica spheres mixture 300mg with holes for the surface of above-mentioned preparation is placed in plasma high-temperature tubular reactor central position, mechanical pump is adopted to vacuumize removing impurity and water vapour, and be depressurized to 5Pa, then use molecular pump to be evacuated to 1 × 10 further -3pa, then at one end passes into shielding gas N 2and gaseous state Heteroatom doping source ammonia and phosphorus trichloride to pressure are 10Pa (volume ratio of nitrogen and phosphorus trichloride and ammonia is 0.5:1:1) (N 2and the flow that gaseous state Heteroatom doping source phosphorus trichloride and ammonia pass into is respectively 5sccm, 10sccm and 10sccm), plasma high-temperature tubular reactor is heated to 500 DEG C with 5 DEG C/min temperature rise rate, then radio-frequency power supply is opened, be under the condition of 200W at radio frequency power, carry out plasma discharge 30min, then radio frequency and heating power supply is closed, stop passing into ammonia and phosphorus trichloride, after being cooled to room temperature, the HF of products therefrom 10wt% is cleaned twice removing silicon-dioxide masterplate, clean with acetone-water mixture (volume ratio of acetone and water is 1:1), use washed with de-ionized water again until the electric conductivity of filtered liquid is lower than 10 μ S, filtrate solid material is phosphorus, nitrogen co-doped surface hollow ball grapheme material with holes.Can be obtained by ultimate analysis, the phosphorus doping amount of the phosphorus prepared, nitrogen co-doped surface hollow sphere Graphene with holes is 3.1%, and N doping amount is 8.3%, and oxygen level is 4.9%.
SEM and TEM is utilized to characterize to obtained phosphorus, nitrogen co-doped surface hollow sphere grapheme material with holes, result is similar to embodiment 1, and when being applied to the electrode materials of lithium ion battery (test condition is identical with embodiment 1), show good performance.At low current density 50mAg -1under, reversible specific capacity is 1987mAhg first -1; At high current density 20Ag -1under, reversible specific capacity is 229mAhg -1.
Embodiment 5
A preparation method for Heteroatom doping surface hollow ball grapheme material with holes, specifically comprises the following steps:
(1) synthesis of graphene oxide
The Hummers method improved is adopted to prepare graphene oxide, its technical process is as follows: in ice-water bath, assemble reaction flask, under the condition stirred (rotating speed is 1000r/min), add the solid mixture of 5g expanded graphite powder and 5g SODIUMNITRATE successively, add the vitriol oil that 300mL massfraction is 95% again, in ice-water bath, react 60min; Subsequently, 60 times (every minor tick 2min) are divided to add 25g potassium permanganate, control temperature of reaction and be no more than 10 DEG C, continue reaction 24h, then add the dilution of 300mL deionized water, after stirring reaction 60min, be warming up to 98 DEG C with 20 DEG C/min temperature rise rate, insulation reaction 48h, solution colour becomes brown color from black transitions; Dropwise add the residual oxygenant (per minute drips 10) of hydrogen peroxide reduction that 100mL massfraction is 35%, drip off rear continuations and react 60min, solution becomes glassy yellow; Filtered while hot, and be 10%HCl solution and deionized water wash until sulfate radical-free is detected in filtrate with mass percent successively; Finally filter cake is placed in the abundant dry 12h of vacuum drying oven of 60 DEG C, obtains graphene oxide;
(2) synthesis of surperficial graphene oxide with holes
By the graphene oxide deionized water ultrasonic disperse 120min of above-mentioned preparation (frequency be 100KHz, power be 1000W), obtain the graphene oxide solution that mass percent concentration is 1.0%; Under agitation (rotating speed of stirring is 1000r/min), in the graphene oxide solution container that 50mL is housed, the dense HNO that 1000mL mass percent concentration is 65% is added 3sealed by container finish, (frequency is 100KHz to supersound process 10h, and power is 1000W, bath temperature is 60 DEG C), after leaving standstill 3h, pouring in the deionized water of 200mL, is centrifugal disacidify under the high speed of 13000rpm at rotating speed, purifying, after filtering, gained solid is placed in the abundant dry 12h of vacuum drying oven of 60 DEG C, obtains surperficial graphene oxide with holes;
(3) preparation of positively charged silicon-dioxide ball template
Cetyl trimethylammonium bromide (CTAB) 2g is joined 300g deionized water is housed, 100mL ethylene glycol and 25mL mass percent concentration are in the there-necked flask of the ammoniacal liquor of 25%, after stirring and dissolving (rotating speed of stirring is 1000r/min), temperature of reaction is risen to 70 DEG C, stir 60min, then 3mL tetraethoxysilane (TEOS) is dropwise added (rate of addition is 10/min), then the 3-aminopropyl triethoxysilane (APTES) of 300.0 μ L is once injected with liquid-transfering gun, then stirring reaction 4h under 70 DEG C of conditions, insulation is transferred in hydrothermal reaction kettle after leaving standstill 24h, and at 120 DEG C of Water Under thermal response 48h, the product deionized water of acquisition and ethanol are repeatedly cleaned until filtrate non-foam, then dry 12h under 80 DEG C of conditions, obtains positively charged silica spheres,
(4) there is the surface graphene oxide silica spheres with holes mixture of nucleocapsid structure
Graphene oxide with holes for surface is scattered in deionized water, is mixed with the surface graphene oxide solution with holes that concentration is 10mg/mL;
Positively charged for 2g silica spheres is scattered in 50mL deionized water, then 2.0mol/L salt acid for adjusting pH value to 2.5 is dripped, then 15mL surface graphene oxide solution with holes is added, magnetic agitation reaction 24h (rotating speed of magnetic agitation is the rotating speed stirred is 1000r/min) at ambient temperature, adopt freeze drier in-48 DEG C of lyophilize 12h, obtain having the surface graphene oxide silica spheres with holes matrix material of nucleocapsid structure;
(5) the plasma method preparation of Heteroatom doping surface hollow ball Graphene with holes
Graphene oxide silica spheres matrix material 1000mg with holes surperficial in step (4) is placed in plasma high-temperature tubular reactor, mechanical pump is adopted to vacuumize removing impurity and water vapour, and be depressurized to 10Pa, then use molecular pump to be evacuated to 1.0 × 10 further -2pa, then at one end passes into shielding gas N 2and gaseous state Heteroatom doping source NH 3(N 2and gaseous state Heteroatom doping source NH 3the flow passed into is respectively 50sccm and 5sccm), be 20Pa (N to pressure 2with NH 3volume ratio be 10:1), plasma high-temperature tubular reactor is heated to 600 DEG C with 10 DEG C/min temperature rise rate, then opens radio-frequency power supply, be under the condition of 600W at radio frequency power, carry out plasma discharge 60min, then close radio frequency and heating power supply, continue to pass into N 2, stop passing into NH 3after being cooled to room temperature, the HF of products therefrom 20wt% is cleaned twice removing silicon-dioxide masterplate, clean with acetone-water mixture (acetone and water volume ratio are 3:1), then use washed with de-ionized water again until the electric conductivity of filtered liquid is lower than 10 μ S, filtrate solid material is N doping surface hollow ball grapheme material with holes.
Can be obtained by ultimate analysis, in the hollow ball grapheme material with holes of N doping surface, nitrogen-atoms number accounts for 13.7% of total atom number, and oxygen atomicity accounts for 2.4% of total atom number.
SEM and TEM is utilized to characterize to obtained N doping surface hollow ball grapheme material with holes, result is similar to embodiment 1, and when being applied to the electrode materials of lithium ion battery (test condition is identical with embodiment 1), show good performance.At low current density 50mAg -1under, reversible specific capacity is 1927mAhg first -1; At high current density 20Ag -1under, reversible specific capacity is 255mAhg -1.
Embodiment 6
A preparation method for Heteroatom doping surface hollow ball grapheme material with holes, specifically comprises the following steps:
(1) synthesis of graphene oxide
The Hummers method improved is adopted to prepare graphene oxide, its technical process is as follows: in ice-water bath, assemble reaction flask, (rotating speed of stirring is 200r/min) adds the mixture of 1g expanded graphite powder and 1g SODIUMNITRATE in reaction flask under agitation, add the vitriol oil that 90mL massfraction is 95% again, in ice-water bath, react 10min; Subsequently, 60 times (every minor tick 1min) are divided to add 5g potassium permanganate, control temperature of reaction and be no more than 5 DEG C, continue reaction 6h, then add the dilution of 50mL deionized water, after stirring reaction 30min, with 10 DEG C/min temperature rise rate, temperature of reaction is elevated to 98 DEG C fast, insulation reaction 12h, solution colour becomes brown color from black transitions; Then, dropwise add the residual oxygenant (per minute drips 5) of hydrogen peroxide reduction that 50mL massfraction is 35%, drip off rear continuations and react 30min, solution becomes glassy yellow; Filtered while hot, and be 5%HCl solution and deionized water wash until sulfate radical-free is detected in filtrate with mass percent successively; Finally filter cake is placed in the abundant dry 24h of vacuum drying oven of 40 DEG C, obtains graphene oxide;
(2) synthesis of surperficial graphene oxide with holes
By the graphene oxide deionized water ultrasonic disperse 30min of above-mentioned preparation (frequency be 20KHz, power be 40W), obtain the graphene oxide solution that mass percent concentration is 0.1%; Under agitation (rotating speed of stirring is 200r/min), in the graphene oxide solution container that 500mL is housed, the dense HNO that 500mL mass percent concentration is 65% is added 3sealed by container finish, (frequency is 20KHz to supersound process 0.5h, and power is 40W, temperature is 4 DEG C), after leaving standstill 1h, pouring in the deionized water of 100mL, is centrifugal disacidify under the high speed of 8000rpm at rotating speed, purifying, after filtering, gained solid is placed in the abundant dry 24h of vacuum drying oven of 40 DEG C, obtains surperficial graphene oxide with holes;
(3) preparation of positively charged silicon-dioxide ball template
Cetyl trimethylammonium bromide (CTAB) 0.5g is joined 100g deionized water is housed, 10mL ethylene glycol and 5mL mass percent concentration are in the three-necked flask of the ammoniacal liquor of 25%, after stirring and dissolving (rotating speed of stirring is 200r/min), temperature of reaction is risen to 40 DEG C, stir 20min, then 0.5mL tetraethoxysilane (TEOS) is dropwise added (rate of addition is 5/min), then the 3-aminopropyl triethoxysilane (APTES) of 100.0 μ L is once injected with liquid-transfering gun, then stirring reaction 2h under 40 DEG C of conditions, insulation is transferred in hydrothermal reaction kettle after leaving standstill 12h, and at 80 DEG C of Water Under thermal response 12h, by obtain product deionized water and ethanol purge until filtrate non-foam, then dry 24h under 60 DEG C of conditions, obtains positively charged silica spheres,
(4) there is the surface graphene oxide silica spheres with holes mixture of nucleocapsid structure
Graphene oxide with holes for surface is scattered in deionized water, is mixed with the surface graphene oxide solution with holes that concentration is 1mg/mL;
Positively charged for 0.1g silica spheres is scattered in 20mL deionized water, then 0.5mol/L salt acid for adjusting pH value to 2.5 is dripped, add 15mL surface graphene oxide solution with holes, magnetic agitation reaction 48h (rotating speed of magnetic agitation is the rotating speed stirred is 200r/min) at ambient temperature, adopt freeze drier in-28 DEG C of lyophilize 48h, obtain having the surface graphene oxide silica spheres with holes matrix material of nucleocapsid structure;
(5) the plasma method preparation of Heteroatom doping surface hollow ball Graphene with holes
Graphene oxide silica spheres matrix material 100mg with holes surperficial in step (4) is placed in plasma high-temperature tubular reactor, mechanical pump is adopted to vacuumize removing impurity and water vapour, and be depressurized to 1Pa, then use molecular pump to be evacuated to 1.0 × 10 further -3pa, then at one end passes into shielding gas N 2and gaseous state Heteroatom doping source NH 3(N 2and gaseous state Heteroatom doping source NH 3the flow passed into is respectively 5sccm and 50sccm), be 20Pa (N to pressure 2with NH 3volume ratio be 0.1:1), plasma high-temperature tubular reactor is heated to 300 DEG C with 5 DEG C/min temperature rise rate, then opens radio-frequency power supply, be under the condition of 100W at radio frequency power, plasma discharge 10min, then closes radio frequency and heating power supply, continues to pass into N 2, stop passing into NH 3after being cooled to room temperature, the HF of products therefrom 5wt% is cleaned twice removing silicon-dioxide masterplate, clean with acetone-water mixture (acetone and water volume ratio are 3:1), then use washed with de-ionized water again until the electric conductivity of filtered liquid is lower than 10 μ S, filtrate solid material is N doping surface hollow ball grapheme material with holes.
Can be obtained by ultimate analysis, in the hollow ball grapheme material with holes of N doping surface, nitrogen-atoms number accounts for 3.7% of total atom number, and oxygen atomicity accounts for 7.9% of total atom number.
SEM and TEM is utilized to characterize to obtained N doping surface hollow ball grapheme material with holes, result is similar to embodiment 1, and when being applied to the electrode materials of lithium ion battery (test condition is identical with embodiment 1), show good performance.At low current density 50mAg -1under, reversible specific capacity is 1427mAhg first -1; At high current density 20Ag -1under, reversible specific capacity is 155mAhg -1.
Embodiment result shows, the present invention is by carrying out doping and the reduction reaction of hetero atom to the surface with nucleocapsid structure of template synthesis graphene oxide silica composite with holes, reduced by plasma method and the adulterate electroconductibility and thermostability that improve Graphene, provide the reversible active sites of more storage lithiums, significantly improve the electrochemical lithium storage performance of Graphene, obtain Large Copacity, powerful Heteroatom doping surface hollow ball Graphene electrodes material with holes.The sharpest edges of Heteroatom doping surface hollow ball Graphene with holes are to improve the electrode stability of material under high current density condition, achieve Heteroatom doping surface hollow ball Graphene with holes and within a short period of time there is very high specific storage, and there is excellent cycling performance.Its chemical property is obviously better than graphene film and other Carbon Materials, and disclosing Heteroatom doping surface hollow ball Graphene with holes is the very promising electrode materials of one.
Finally also it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.

Claims (10)

1. a preparation method for Heteroatom doping surface hollow ball grapheme material with holes, is characterized in that: specifically comprise the following steps:
(1) synthesis of surperficial graphene oxide with holes
Water is added in graphene oxide, ultrasonic disperse, obtain graphene oxide solution; Then under agitation, in the container that graphene oxide solution is housed, dense HNO is added 3, container sealing, in 4 DEG C ~ 60 DEG C ultrasonic reaction 0.5 ~ 10h, after leaving standstill 1 ~ 3h, pours in deionized water, centrifugal disacidify, purifying, filters, dry, obtains surperficial graphene oxide with holes, for subsequent use;
(2) preparation of positively charged silicon-dioxide ball template
Cetyl trimethylammonium bromide is joined in the reaction vessel that deionized water, ethylene glycol and ammoniacal liquor are housed, stirring and dissolving, be warming up to 40 ~ 70 DEG C, insulated and stirred 20 ~ 60min, then dropwise add tetraethoxysilane, then add 3-aminopropyl triethoxysilane fast, in 40 ~ 70 DEG C of stirring reaction 2 ~ 4h, insulation leaves standstill 12 ~ 24h, carries out hydro-thermal reaction with being placed in hydrothermal reaction kettle; By the product cleaning of hydro-thermal reaction to filtrate non-foam, dry, obtain positively charged silica spheres;
(3) there is the preparation of the surface graphene oxide silica spheres with holes mixture of nucleocapsid structure
Positively charged silica spheres in step (2) is scattered in deionized water, obtains silica spheres dispersion liquid; Then dripping acid solution regulates pH to be 2 ~ 2.5, adds surperficial graphene oxide dispersion with holes, stirring reaction 24 ~ 48h, lyophilize, obtains having the surface graphene oxide silica spheres with holes matrix material of nucleocapsid structure; Wherein said surface graphene oxide dispersion with holes is scattered in water by surface graphene oxide with holes in step (1) to prepare;
(4) the plasma method preparation of Heteroatom doping surface hollow ball Graphene with holes
100mg ~ 1000mg surface graphene oxide silica spheres matrix material with holes is placed in plasma high-temperature tubular reactor, vacuumizes and be depressurized to 1 ~ 10Pa, be evacuated to 10 further -2~ 10 -3pa, pass into shielding gas and gaseous state Heteroatom doping source to pressure is 0.1 ~ 20Pa, plasma high-temperature tubular reactor is warming up to 300 ~ 600 DEG C, then radio-frequency power supply is opened, be under the condition of 100 ~ 600W at radio frequency power, plasma discharge 10 ~ 60min, then radio frequency and heating power supply is closed, stop passing into Heteroatom doping source, cooling, clean with HF solution, wash with acetone-water mixture again, finally with deionized water wash to the electric conductivity of filtrate lower than 10 μ S, filtrate solid material is Heteroatom doping surface hollow ball grapheme material with holes.
2. according to claim 1 Heteroatom doping surface hollow ball grapheme material with holes preparation method, it is characterized in that: dense HNO described in step (1) 3be (1 ~ 20) with the volume ratio of graphene oxide solution: 1; The volume ratio of described deionized water and graphene oxide solution is (100 ~ 200) mL:(50 ~ 500) mL;
Described in step (1), the mass percent concentration of concentrated nitric acid is 60 ~ 65%; The mass percent concentration of described graphene oxide solution is 0.1 ~ 1.0%;
Cetyl trimethylammonium bromide described in step (2): deionized water: ethylene glycol: ammoniacal liquor: tetraethoxysilane: the amount ratio of 3-aminopropyl triethoxysilane 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 surperficial graphene oxide dispersion with holes described in step (3) is (1 ~ 10) mg/mL; The silica spheres of described positive charge and the mass volume ratio of deionized water are (0.1 ~ 2) g:(20 ~ 50) mL; The mass volume ratio of described positively charged silica spheres and surface graphene oxide dispersion with holes is (0.1 ~ 2) g:15mL.
3. according to claim 1 Heteroatom doping surface hollow ball grapheme material with holes preparation method, it is characterized in that: described in step (4), shielding gas is argon gas, helium or nitrogen; Described Heteroatom doping source is gaseous state heteroatomic compound, and described heteroatoms is more than one in boron, nitrogen, sulphur or phosphorus; The volume ratio in described shielding gas and Heteroatom doping source is (0.1 ~ 10): 1;
Described in step (2), the mass percent concentration of ammoniacal liquor is 25 ~ 28%; Described in step (2), the temperature of hydro-thermal reaction is 80 ~ 120 DEG C, and the time of hydro-thermal reaction is 12 ~ 48h.
4. according to claim 3 Heteroatom doping surface hollow ball grapheme material with holes preparation method, it is characterized in that: Heteroatom doping source described in step (4) is more than one in diborane, ammonia, hydrogen sulfide or phosphorus trichloride.
5. according to claim 1 Heteroatom doping surface hollow ball grapheme material with holes preparation method, it is characterized in that: described in step (1), graphene oxide is prepared from by the following method: under ice-water bath condition, by mass percent be 95 ~ 98% the vitriol oil add in SODIUMNITRATE and graphite mixture, stirring reaction 10 ~ 60min; Progressively add potassium permanganate, control temperature of reaction and be no more than 20 DEG C, after adding, continue reaction 6 ~ 24h, add deionized water dilution, stirring reaction 30 ~ 60min, be warming up to 20 ~ 98 DEG C, reaction 12-48h, dropwise adds the hydrogen peroxide that mass percent is 30 ~ 35%, drip rear continuation reaction 30 ~ 60min, filter, with mass percent be 5 ~ 10% HCl solution and deionized water wash, until sulfate radical-free is detected in filtrate; Finally by filter cake in 40 ~ 60 DEG C of drying 12 ~ 24h, obtain graphene oxide.
6. according to claim 5 Heteroatom doping surface hollow ball grapheme material with holes preparation method, it is characterized in that: the described potassium permanganate that progressively adds refers to that each add-on of potassium permanganate is 1/60 of potassium permanganate gross weight, every minor tick 1 ~ 2min; The rotating speed of described stirring is 200 ~ 1000r/min; The speed of described dropping is 5 ~ 10/min; Described temperature rise rate is 10 ~ 20 DEG C/min;
Described Graphite Powder 99: SODIUMNITRATE: the vitriol oil: potassium permanganate: the deionized water for diluting: 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. according to claim 1 Heteroatom doping surface hollow ball grapheme material with holes preparation method, it is characterized in that:
Described in step (1), the frequency of ultrasonic disperse is 20 ~ 100KHz, and the power of ultrasonic disperse is 40 ~ 1000W, and the time of ultrasonic disperse is 30 ~ 120min; The frequency of described ultrasonic reaction is 20 ~ 100KHz, and the power of ultrasonic reaction is 40 ~ 1000W, and the time of ultrasonic reaction is 0.5 ~ 10h; Centrifugal rotational speed is 8000 ~ 13000rpm; The temperature of described drying is 40 ~ 60 DEG C, and the dry time is 12 ~ 24h;
The rotating speed stirred described in step (2) is 200 ~ 1000r/min; Temperature dry described in step (2) is 60 ~ 80 DEG C, and the dry time is 12 ~ 24h; The speed dripped described in step (2) is 5 ~ 10/min; Described in step (2), cleaning adopts deionized water and ethanol to clean hydro-thermal reaction product successively;
Described in step (3), acid solution is hydrochloric acid, and the concentration of described acid solution is 0.5 ~ 2mol/L; The rotating speed of described stirring is 200 ~ 1000r/min, and the temperature of described reaction is room temperature; Described cryodesiccated temperature is-28 ~-48 DEG C, and the cryodesiccated time is 12 ~ 48h;
Described in step (4), the concentration of HF is 5 ~ 20wt%; The number of times of described cleaning is 2 ~ 3 times; In described acetone-water mixture, acetone and water volume ratio are (1 ~ 3): 1; Described temperature rise rate is 5 ~ 10 DEG C/min.
8. according to claim 1 Heteroatom doping surface hollow ball grapheme material with holes preparation method, it is characterized in that: described plasma high-temperature tubular reactor comprises plasma high-temperature quartz tube furnace, described plasma high-temperature quartz tube furnace one end is provided with shielding gas inlet pipe and Heteroatom doping source reactant gases inlet pipe, the described plasma high-temperature quartz tube furnace the other end is provided with 2 extraction pipes, one extraction pipe connects liquid nitrogen cold trap, another extraction pipe connects molecular pump, described liquid nitrogen cold trap is connected with mechanical pump by pipeline, described plasma high-temperature quartz tube furnace outside surface is wound with inductively coupled plasma coil, the two ends of described inductively coupled plasma coil connect radio frequency power source, described shielding gas inlet pipe is connected with digital display mass flowmeter and regulated valve, described Heteroatom doping source gas inlet pipe is connected with digital display mass flowmeter and regulated valve, the described extraction pipe being connected to liquid nitrogen cold trap is provided with the first by-pass valve control, the pipeline of described liquid nitrogen cold trap and mechanical pump is provided with the 3rd by-pass valve control, the pipeline that described 3rd by-pass valve control is communicated with liquid nitrogen cold trap is provided with vacuumometer, the bypass of described vacuumometer and pipeline communication is provided with the 4th by-pass valve control, the described extraction pipe being connected with molecular pump is provided with the second by-pass valve control, the described extraction pipe being connected to liquid nitrogen cold trap is provided with air intake duct, described air intake duct is provided with air control valve door.
9. the Heteroatom doping surface hollow ball grapheme material with holes prepared by preparation method described in any one of claim 1 ~ 8.
10. the application of Heteroatom doping surface hollow ball grapheme material with holes in lithium ion battery according to claim 9.
CN201510374574.XA 2015-06-30 2015-06-30 Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof Active CN105152161B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510374574.XA CN105152161B (en) 2015-06-30 2015-06-30 Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510374574.XA CN105152161B (en) 2015-06-30 2015-06-30 Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN105152161A true CN105152161A (en) 2015-12-16
CN105152161B CN105152161B (en) 2017-04-19

Family

ID=54793291

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510374574.XA Active CN105152161B (en) 2015-06-30 2015-06-30 Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN105152161B (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654212A (en) * 2016-12-29 2017-05-10 吉林大学 Preparation method and application of cobaltosic oxide/graphene composite material (Co<3>O<4>/N-RGO)
CN106865494A (en) * 2017-04-10 2017-06-20 山西大学 A kind of preparation method of hollow nano silicon spheres/graphene composite negative pole
CN107176610A (en) * 2017-05-05 2017-09-19 浙江理工大学 A kind of silicon dioxide hollow microsphere and preparation method thereof
CN107934942A (en) * 2017-11-29 2018-04-20 湖南大学 A kind of modified 3 D graphene hydrogel and preparation method thereof
CN108232141A (en) * 2017-12-21 2018-06-29 中国科学院化学研究所 A kind of silicon-carbon composite cathode material of lithium ion battery of high-pressure solid and preparation method thereof
CN108545721A (en) * 2018-05-18 2018-09-18 南京师范大学 The preparation method and its resulting materials of a kind of three-dimensional grapheme hollow ball of high stable state and application
CN108598434A (en) * 2018-04-24 2018-09-28 盐城师范学院 A kind of electrostatic self-assembled preparation method of graphene/silicon electrode material
CN109461594A (en) * 2018-12-25 2019-03-12 重庆中科超容科技有限公司 A kind of three-dimensional porous graphene/active carbon electrode material of the doping of high voltage and preparation method thereof
CN109607515A (en) * 2018-11-22 2019-04-12 浙江理工大学 A kind of N doping hollow graphite alkene micro-sphere material and the preparation method and application thereof
CN110010911A (en) * 2019-03-14 2019-07-12 上海交通大学 A kind of codope porous graphene cathode non-platinum catalyst and preparation method thereof
CN110136967A (en) * 2018-02-02 2019-08-16 中国科学院苏州纳米技术与纳米仿生研究所 Three-dimensional ternary doping hollow graphene hydrogel and its preparation method and application
CN110240746A (en) * 2019-06-20 2019-09-17 福建宸琦新材料科技有限公司 A kind of anti-skidding heat-proof aging EVA, NR composite foam material and preparation method thereof
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
CN114773642A (en) * 2022-06-17 2022-07-22 中北大学 Preparation of graphene/natural rubber with simultaneously improved mechanics, heat conduction 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
CN117343096A (en) * 2023-12-04 2024-01-05 瑞浦兰钧能源股份有限公司 Ionized conductive agent and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2367595C2 (en) * 2007-11-28 2009-09-20 Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (статус государственного учреждения) Porous carbon nanomaterial and method thereof
KR20100090551A (en) * 2009-02-06 2010-08-16 에이비씨상사 주식회사 Method of maufacturing graphene hollow nanospheres
KR101006903B1 (en) * 2008-06-03 2011-01-13 연세대학교 산학협력단 Preparation process for hollow graphene multilayed nanospheres
US20120177995A1 (en) * 2011-01-06 2012-07-12 Springpower International, Inc. Secondary Lithium Batteries Having Novel Anodes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2367595C2 (en) * 2007-11-28 2009-09-20 Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (статус государственного учреждения) Porous carbon nanomaterial and method thereof
KR101006903B1 (en) * 2008-06-03 2011-01-13 연세대학교 산학협력단 Preparation process for hollow graphene multilayed nanospheres
KR20100090551A (en) * 2009-02-06 2010-08-16 에이비씨상사 주식회사 Method of maufacturing graphene hollow nanospheres
US20120177995A1 (en) * 2011-01-06 2012-07-12 Springpower International, Inc. Secondary Lithium Batteries Having Novel Anodes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LONGFEI WU ET AL.，: "Graphene-based hollow spheres as efficient electrocatalysts for oxygen reduction", 《NANOSCALE》 *
QINGGUO SHAO ET AL.，: "Synthesis and characterization of graphene hollow spheres for application in supercapacitors", 《J. MATER. CHEM. A》 *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654212A (en) * 2016-12-29 2017-05-10 吉林大学 Preparation method and application of cobaltosic oxide/graphene composite material (Co<3>O<4>/N-RGO)
CN106654212B (en) * 2016-12-29 2019-07-30 吉林大学 A kind of Co3O4The preparation method and application of/N-RGO/HSAs composite material
CN106865494B (en) * 2017-04-10 2019-07-23 山西大学 A kind of preparation method of hollow nano silicon spheres/graphene composite negative pole
CN106865494A (en) * 2017-04-10 2017-06-20 山西大学 A kind of preparation method of hollow nano silicon spheres/graphene composite negative pole
CN107176610A (en) * 2017-05-05 2017-09-19 浙江理工大学 A kind of silicon dioxide hollow microsphere and preparation method thereof
CN107176610B (en) * 2017-05-05 2019-03-01 浙江理工大学 A kind of silicon dioxide hollow microsphere and preparation method thereof
CN107934942A (en) * 2017-11-29 2018-04-20 湖南大学 A kind of modified 3 D graphene hydrogel and preparation method thereof
CN108232141A (en) * 2017-12-21 2018-06-29 中国科学院化学研究所 A kind of silicon-carbon composite cathode material of lithium ion battery of high-pressure solid and preparation method thereof
CN108232141B (en) * 2017-12-21 2020-08-21 中国科学院化学研究所 High-compaction lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof
CN110136967A (en) * 2018-02-02 2019-08-16 中国科学院苏州纳米技术与纳米仿生研究所 Three-dimensional ternary doping hollow graphene hydrogel and its preparation method and application
CN108598434A (en) * 2018-04-24 2018-09-28 盐城师范学院 A kind of electrostatic self-assembled preparation method of graphene/silicon electrode material
CN108545721A (en) * 2018-05-18 2018-09-18 南京师范大学 The preparation method and its resulting materials of a kind of three-dimensional grapheme hollow ball of high stable state and application
CN109607515A (en) * 2018-11-22 2019-04-12 浙江理工大学 A kind of N doping hollow graphite alkene micro-sphere material and the preparation method and application thereof
CN109461594B (en) * 2018-12-25 2023-02-28 重庆中科超容科技有限公司 High-voltage-resistance doped three-dimensional porous graphene/activated carbon electrode material and preparation method thereof
CN109461594A (en) * 2018-12-25 2019-03-12 重庆中科超容科技有限公司 A kind of three-dimensional porous graphene/active carbon electrode material of the doping of high voltage and preparation method thereof
CN110010911A (en) * 2019-03-14 2019-07-12 上海交通大学 A kind of codope porous graphene cathode non-platinum catalyst and preparation method thereof
CN110240746A (en) * 2019-06-20 2019-09-17 福建宸琦新材料科技有限公司 A kind of anti-skidding heat-proof aging EVA, NR composite foam material and preparation method thereof
CN110240746B (en) * 2019-06-20 2022-04-05 福建宸琦新材料科技有限公司 Anti-slip thermal-aging-resistant EVA (ethylene-vinyl acetate copolymer) and NR (NR) composite foaming material and preparation method thereof
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
CN114773642A (en) * 2022-06-17 2022-07-22 中北大学 Preparation of graphene/natural rubber with simultaneously improved mechanics, heat conduction and wear resistance
WO2023241196A1 (en) * 2022-06-17 2023-12-21 中北大学 Preparation of graphene/natural rubber with simultaneously improved mechanical property, heat conduction 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
CN117343096A (en) * 2023-12-04 2024-01-05 瑞浦兰钧能源股份有限公司 Ionized conductive agent and preparation method and application thereof
CN117343096B (en) * 2023-12-04 2024-04-02 瑞浦兰钧能源股份有限公司 Ionized conductive agent and preparation method and application thereof

Also Published As

Publication number Publication date
CN105152161B (en) 2017-04-19

Similar Documents

Publication Publication Date Title
CN105152161A (en) Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof
US20220376235A1 (en) Composite Negative Electrode Material and Method for Preparing Composite Negative Electrode Material, Negative Electrode Plate of Lithium Ion Secondary Battery, and Lithium Ion Secondary Battery
CN106876689B (en) Nitrogen-doped graphene-silicon composite negative electrode material, preparation method thereof and lithium ion battery
CN103715430B (en) Three-dimensional grapheme network structure load carbon covered stannum rice material and preparation and application
CN103165862B (en) A kind of high performance lithium ionic cell cathode material and preparation method thereof
CN110212183A (en) A kind of powder prelithiation silicon based anode material and its preparation method and application
CN103165894B (en) Graphene-hydroxyl lithium composite and its preparation method and application
Yang et al. Ionic liquid as the C and N sources to prepare yolk-shell Fe3O4@ N-doped carbon nanoparticles and its high performance in lithium-ion battery
Guo et al. TiN-coated micron-sized tantalum-doped Li4Ti5O12 with enhanced anodic performance for lithium-ion batteries
Sun et al. Fe2O3/CNTs composites as anode materials for lithium-ion batteries
CN103682266A (en) Li and Mn codoped manganese phosphate/carbon composite material and preparation method thereof
CN109244378A (en) A kind of preparation method of porous nano Si-C composite material
CN109860526B (en) Preparation method of graphite material doped with metal oxalate lithium battery composite negative electrode material
Su et al. Synthesis and electrochemical performance of nano-sized Li4Ti5O12 coated with boron-doped carbon
CN104269536A (en) Graphene-loaded spherical carbon-cladded iron oxide composite material and preparation method of composite material
CN105826524A (en) Synthesis method of lithium iron phosphate of graphene in-situ nucleation
CN105428618A (en) Preparation method for shell-core type carbon-coated metal sulfide nano-composite particles and application of particles
CN103367718A (en) Method for preparing carbon-coated Fe3O4 nanometer microspheres
CN106816590A (en) A kind of preparation method of high-capacity lithium ion cell composite negative pole material
CN103107309B (en) A kind of lithium ion cell positive and preparation method thereof
CN114695894A (en) High-capacity hard carbon fast-charging negative electrode material and preparation method and application thereof
CN104393275A (en) Preparation method of carbon-coated lithium titanate battery material
CN105161690A (en) Method for improving charge-discharge cycling capacity of molybdenum disulfide by doping graphene and titanium dioxide
CN104638248A (en) Method for preparing graphene/lead compound composite material
CN109037645B (en) Method for preparing metal oxide @ chlorine-doped graphene lithium ion battery anode material in one step

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant