CN109607515A - A kind of N doping hollow graphite alkene micro-sphere material and the preparation method and application thereof - Google Patents
A kind of N doping hollow graphite alkene micro-sphere material and the preparation method and application thereof Download PDFInfo
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- CN109607515A CN109607515A CN201811395620.4A CN201811395620A CN109607515A CN 109607515 A CN109607515 A CN 109607515A CN 201811395620 A CN201811395620 A CN 201811395620A CN 109607515 A CN109607515 A CN 109607515A
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- graphite alkene
- hollow graphite
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- doping
- doping hollow
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- -1 graphite alkene Chemical class 0.000 title claims abstract description 42
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 39
- 239000010439 graphite Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000004005 microsphere Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 46
- 239000004793 Polystyrene Substances 0.000 claims abstract description 31
- 229920002223 polystyrene Polymers 0.000 claims abstract description 28
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 27
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000009881 electrostatic interaction Effects 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001409 amidines Chemical class 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 9
- 239000011149 active material Substances 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 239000011859 microparticle Substances 0.000 abstract description 2
- 230000008602 contraction Effects 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004146 energy storage Methods 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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Abstract
The invention discloses a kind of N doping hollow graphite alkene micro-sphere materials and its preparation method and application；The preparation method includes using positively charged polystyrene microsphere as template, negatively charged graphene oxide is coated on positively charged Surfaces of Polystyrene Microparticles by electrostatic interaction and forms core-shell structure compound, adds the N doping hollow graphite alkene micro-sphere material that melamine has prepared better performances, structure-controllable by high-temperature calcination；N doping hollow graphite alkene micro-sphere structure, which is made, in grapheme material can increase its specific surface area, and high specific surface area can promote more active sites in absorption/desorption process to be exposed to outside, stored energy capacitance can be improved；Hollow structure can also promote sodium ion quickly to spread in active material, and provide cushion space in charge and discharge process for the volume expansion contraction of active material, improve the high rate performance of sodium-ion battery.
Description
Technical field
The invention belongs to new energy materials-sodium ion battery electrode material preparation technical fields, more specifically, the present invention
It is related to a kind of N doping hollow graphite alkene micro-sphere material and the preparation method and application thereof.
Background technique
Due to the increasingly increased fossil energy consumption of the mankind, the environmental problems such as haze, greenhouse effects are got worse.In order to slow
The status that current environment deteriorates is solved, needs to change existing unreasonable energy resource structure, energy utilization rate is improved, develops new energy,
Scale energy storage becomes very urgent problem.In the energy storage device currently researched and developed, lithium ion battery has small in size, weight
Gently, the advantages that energy density is high, in the traffic such as the portable equipments such as mobile phone, laptop and electric bicycle, electric car
Increasingly important role is just being played in tool.The dosage of lithium ion battery increases year by year, especially the development of support new energy
Energy-storage battery it is in great demand, the cost of such battery just becomes focus concerned by people.It is well known that lithium ion battery material
In the common heavy metal elements such as cobalt and nickel, not only resource is rare, expensive, but also also adversely affects to environment.Especially
It should be pointed out that synthesis positive electrode requires the presoma containing lithium of significant proportion, and the resource of lithium is extremely limited, with lithium
The Quick Extended of ion battery application range necessarily will appear the lithium salts situation that supply falls short of demand.Later period in 2015 is due to China's electricity
Electrical automobile yield rapid growth, leads to the promotion of lithium ion battery production capacity, to the situation of lithium carbonate rapid rise of price occur.It can be with
It is expected that the lithium ion battery cost of raw material is difficult to be greatly reduced, it is restricted its application in extensive energy storage.
As can be seen that the core key technology as renewable energy utilization and smart grid, extensive energy storage technology is still
It is at an early stage of development, and cost is to influence a key factor of energy storage industrial economy.Compared with other energy storage technologies, sodium from
Sub- battery is in all many-sided presence such as resource reserve, cost, energy conversion efficiency, cycle life, security and stability, maintenance cost
Some superiority.Therefore, the sodium-ion battery technology for greatly developing extensive stored energy application has highly important strategic importance.So
And researching and developing sodium ion battery electrode material that is cheap and haveing excellent performance is that final realization sodium ion energy-storage battery is real
The key of border application.
The negative electrode material of sodium-ion battery must have excellent electric conductivity and big specific surface area, this is conducive to filling
Electric charge transfer is carried out in discharge process and sodium ion is stored by adsorption/desorption.The carbonaceous material of graphite-structure, because
Their excellent conductivity and the ability of sodium ion is stored with adsorption/desorption and by the concern of researcher.Graphite
Alkene is one kind of carbon material, it is by sp2Hydbridized carbon atoms composition, is arranged on hexagonal lattice.Much research shows that graphene has
There is high conductivity and store the ability of sodium ion, because it has very big specific surface area and high conjugated structure.It especially adulterates miscellaneous
When atom is to graphene, the big pi-conjugated interstructural collaboration coupling of hetero atom and graphene can increase hydrophily and sodium
The storage capacity of ion.In addition, heteroatomic mix the conductivity that grapheme material not only can be improved, multiplying power can also be improved
Performance.
Graphene and heterogeneous element doped graphene reversible capacity are high, can be with high current charge-discharge, and power-performance is good, but its
There are numerous defects:
(1) since during preparation and cycle charge-discharge, nano-graphene piece (GNS) is due to piece interlayer Van der Waals force
In the presence of, it can be gradually gathered into graphene paper-like structure, a large amount of sheet surfaces is caused to be difficult to be utilized, thus its specific surface is much
Lower than theoretical specific surface；
(2) aggregation of lamella causes the active surface of material persistently to reduce, while producing many discontinuous channels, resistance
Hinder ion in quick transmitting wherein；
(3) the complete graphene film in surface is transmitted by the ion of graphene film vulnerable to obstruction due to its surface compact；
Because while ion is very high in the conductivity being parallel on graphene surface direction, but it is perpendicular to graphene film plane side
Upward conductance efficiency is lower.Therefore the migration of ion can be concentrated mainly on the edge of graphene film, greatly hinder its ion
The raising of conductivity.
Since there are drawbacks described above to make answering for Heteroatom doping graphene for the Heteroatom doping graphene of prior art preparation
With being limited by very large.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of N doping hollow graphite alkene
The preparation method of micro-sphere material, and it is used as the negative electrode material of sodium-ion battery.The present invention is with positively charged polystyrene microsphere
Negatively charged graphene oxide is coated on positively charged Surfaces of Polystyrene Microparticles by electrostatic interaction and is formed by template
Core-shell structure compound, add melamine by high-temperature calcination prepared better performances, structure-controllable N doping in
Empty graphene micro-sphere material.
N doping hollow graphite alkene micro-sphere structure, which is made, in grapheme material can increase its specific surface area, high ratio table
Area can promote more active sites in absorption/desorption process to be exposed to outside, this has very big side to the raising of stored energy capacitance
It helps.It in addition, hollow structure can also promote sodium ion quickly to spread in active material, and is activity in charge and discharge process
The volume expansion of substance, which is shunk, provides cushion space, this is for the energy-storage property of sodium-ion battery and cyclical stability, it appears
It is extremely important.In addition, thin shell thickness ensures very short sodium ion diffusion length, this is conducive to improve sodium-ion battery
High rate performance.
In order to achieve the above-mentioned object of the invention, the present invention provides the preparation method of above-mentioned N doping hollow graphite alkene microballoon,
Specifically includes the following steps:
(1) preparation of positively charged polystyrene microsphere template: by styrene and polyvinylpyrrolidone be dissolved in from
In sub- water, then it is added in the reaction flask with stirring and condensing unit, being placed in oil bath and starting stirring makes its mixing
Uniformly, 10~20g/L, 2,2 '-azo diisobutyl amidine HCI solution is added, is continually fed into nitrogen, heats up after 40~90min
To 65~75 DEG C of 15~35h of reaction, dry acquisition polystyrene spheres in baking oven are moved to；Wherein, polyvinylpyrrolidone and benzene
The mass ratio of ethylene is 1:5~1:15, styrene and 2, the mass ratioes of 2 '-azo diisobutyl amidine HCI solutions for 50:1~
The mass ratio of 20:1, styrene and deionized water is 1:6~1:16；
(2) preparation of N doping hollow graphite alkene microballoon: by positively charged polystyrene spheres aqueous solution and graphite oxide
Alkene (GO) aqueous solution is uniformly mixed, and reaction 12~for 24 hours is stirred at room temperature, to promote negatively charged graphene oxide and band just
The polystyrene sphere of electricity is mutually coated by electrostatic interaction, melamine is added later, mixture is stirred for 12- at room temperature
For 24 hours, mixture is then put into baking oven dry 24-48h under the conditions of 60-80 DEG C；Obtained solid is put into silica crucible, logical
600-800 DEG C of calcining 1-3h in the tube furnace of nitrogen；Resulting product is N doping hollow graphite alkene micro-sphere material after cooling；
Wherein, the mass ratio of polystyrene spheres and graphene oxide is 50:1~10:1, the mass ratio of polystyrene spheres and melamine
For 4:1~1:6；
Preferably, the mass concentration of polystyrene spheres aqueous solution described in step (2) is 0.05-0.2g/mL；
Preferably, the mass concentration of graphene oxide water solution described in step (2) is 0.5-1.5mg/mL；
The N doping hollow graphite alkene micro-sphere material is prepared by above-mentioned preparation method；
Application of the N doping hollow graphite alkene micro-sphere material in large capacity, high magnification sodium-ion battery.
The invention has the following advantages and beneficial effects:
(1) N doping hollow graphite alkene microballoon prepared by the present invention has very unified size, by hollow sphere and very thin stone
Black alkene shell composition；Exist in the graphene shell of outer layer largely perpendicular to the mesoporous of spherome surface, can in different directions be sodium
Ion diffusion transport provides path；
(2) unique hollow structure can provide bigger specific surface and shorter diffusion in material prepared by the present invention
Distance is to promote transmission of the sodium ion in electrode material；The nano material of hollow structure can solve electrode material due to mistake
Big volume expansion and the too fast problem of capacity attenuation in the cyclic process that generates, in this case, the nanometer material of hollow structure
Material can hinder the reunion of active particle and provide sufficiently large space to alleviate volume expansion；
(3) N doping hollow graphite alkene microballoon prepared by the present invention can quickly filled as sodium ion battery electrode material
Large capacity, the high magnification electrode material used under discharging condition, the material significantly improve the electrical conductance and thermostabilization of electrode material
Property, provide more storage reversible active sites of sodium；
(4) present invention process process is simple, and operation is easy, and doping efficiency is fast, storage sodium performance is high, can be expected to mass production.
In short, the graphene oxide polystyrene spheres composite material with core-shell structure prepared by using template method
For raw material, N doping hollow graphite alkene microballoon is obtained using calcining reduction and doping, not only realizes nitrogen in hollow graphite alkene ball
The doping of lattice, and oxygen-containing functional group is further removed, the electrical conductance and thermal stability of graphene are improved, it is reversible to increase storage sodium
Active sites obtain a kind of large capacity, powerful Graphene electrodes material.
Detailed description of the invention
Fig. 1 is in the three-dimensional porous graphene of N doping (NG) and N doping that comparative example 1 and embodiment 1 are prepared respectively
The structural characterization figure of empty graphene microballoon (NGHMs) material；Wherein (a) is transmission electron microscope (TEM) photo of NGHMs,
(b) scanning electron microscope (SEM) photo for being NGHMs；(a) illustration is high resolution transmission electron microscopy (HRTEM) figure in；
(c) scheme for the TEM of NG；(d) scheme for the SEM of NG；
Fig. 2 is in the three-dimensional porous graphene of N doping (NG) and N doping that comparative example 1 and embodiment 1 are prepared respectively
The N of empty graphene microballoon (NGHMs) material2Adsorption/desorption isotherms figure；
Fig. 3 is that the three-dimensional porous graphene of N doping (NG) that comparative example 1 is prepared is used as sodium-ion battery cathode not
With the charge/discharge capacity under current density；
Fig. 4 is that N doping hollow graphite alkene microballoon (NGHMs) material that embodiment 1 is prepared is negative as sodium-ion battery
Charge/discharge capacity of the pole under different current densities；
Fig. 5 is that the current densities of ten circles before the three-dimensional porous graphene of N doping (NG) that comparative example 1 is prepared are 50mA/
G, subsequent current density are the cycle performance of 500mA/g；
Fig. 6 is the current density of ten circles before N doping hollow graphite alkene microballoon (NGHMs) material that embodiment 1 is prepared
For 50m/Ag, subsequent current density is the cycle performance of 500mA/g；
Fig. 7 is that the current densities of ten circles before the three-dimensional porous graphene of N doping (NG) that comparative example 1 is prepared are 50mA/
G, subsequent current density are the cycle performance of 1000mA/g；
Fig. 8 is the current density of ten circles before N doping hollow graphite alkene microballoon (NGHMs) material that embodiment 1 is prepared
For 50mA/g, subsequent current density is the cycle performance of 1000mA/g.
Specific embodiment
In order to be more clear the purpose of the present invention, technical solution and advantageous effects, with reference to the accompanying drawing and specifically
Embodiment, preparation method to N doping hollow graphite alkene micro-sphere material of the present invention and the material and as sodium-ion battery
The beneficial effect of negative electrode material be described in detail.It should be understood that embodiment described in this specification is only to be
Explain the present invention, be not intended to limit the present invention, parameter, ratio of embodiment etc. can adaptation to local conditions make a choice and to result
Have no substantial effect.
Comparative example 1: the three-dimensional porous graphene of N doping is synthesized according to the following steps:
(a) graphene oxide the synthesis of graphene oxide: is synthesized using improved Hummers method.Its synthesis process is such as
Under: 1000mL reaction flask is assembled in ice-water bath, is added with stirring the solid mixing of 2g expanded graphite powder and 2.5g sodium nitrate
Object and 98% concentrated sulfuric acid 180mL, and 30min is stirred to react in ice-water bath.Then control reaction temperature is no more than 10 DEG C,
Potassium permanganate 15g is slowly added under stirring, reaction stirring for 24 hours, is then slowly added into deionized water 180mL dilution, and at 98 DEG C
Lower reflux 24 hours makes color become golden yellow.It is after being then slowly added into 35% hydrogen peroxide of 80mL, reaction mixture is cold
But to room temperature.By graphene oxide obtained (GO) with 5%HCl and the multiple centrifuge washing of deionized water to neutrality, freezing is dry
Product is obtained after dry.
(b) 1.25mg/mL graphene oxide (GO) aqueous solution of 80mL is stirred at room temperature 12 hours, 3g is added later
Mixture is stirred for 12h by melamine at room temperature.Then under the conditions of mixture being put into 60 DEG C of baking oven, baking is for 24 hours.?
To solid be placed in silica crucible, 800 DEG C of calcining 1h in the tube furnace of logical nitrogen.It is three-dimensional porous that this just generates N doping
Graphene (NG).
The TEM and SEM that Fig. 1 (c) (d) is NG scheme.It can be seen that three-dimensional porous accumulation shape is presented in resulting NG.Make
It is 261m with the specific surface area that nitrogen adsorption-desorption isotherm measures NG2/ g is as shown in Figure 2.
Sode cell Performance Evaluation: electrode material obtained, conductive black and PVDF are made into slurry with mass ratio for 8:1:1
Coated in sodium-ion battery cathode is done on copper foil, sodium piece does anode, and electrolyte solute is 1MNaClO4, electrolyte solvent is carbonic acid
The mixed liquor of vinyl acetate (EC) and dimethyl carbonate (DMC), volume ratio 1:1.If Fig. 3 is NG as sodium-ion battery cathode
Charge/discharge capacity under different current densities.As shown in figure 3, the current density of NG is 0.1,0.2,1,2,5,10Ag-1When, it can
Inverse specific capacity is respectively 118.1,91.9,69.7,54.8,43.1,35.2 and 34.8mAhg-1.Especially when current density increases
To 20Ag-1When, NG reversible capacity is 29.3mAhg-1。
Fig. 5 and Fig. 7 is that the current density of ten circles before the three-dimensional porous graphene of N doping (NG) that comparative example 1 is prepared is
50mA/g, subsequent current density are the cycle performance of 500mA/g and 1000mA/g；As shown in Fig. 5 and Fig. 7, before NG 10 follow
Charging and discharging currents density is 50mA/g in the ring period, when subsequent cycle period current density is 500 or 1000mA/g, respectively
Stabilization reversible capacity be respectively 58.7 and 50.8mAh g-1。
Embodiment 1: N doping hollow graphite alkene microballoon (NGHMs) is synthesized according to the following steps:
Prior step (a) is identical as the method for comparative example 1.
(b) preparation of polystyrene (PS): 10g styrene (St) and 1.5g polyvinylpyrrolidone (PVP) are dissolved in
In 100mL deionized water, then it is added in the reaction flask with stirring and condensing unit, is placed in oil bath and starts stirring
It is uniformly mixed it, 20mL13g/L 2,2 '-azo diisobutyl amidine hydrochloride (AIBA) solution is added, is continually fed into nitrogen,
70 DEG C of reactions are warming up to after 60min for 24 hours, take 5mL be placed in baking oven it is dry after acquire the concentration of polystyrene solution and be
0.0754g/mL。
(c) preparation of N doping hollow graphite alkene microballoon: 26.5mL positively charged polystyrene microsphere aqueous solution
(0.0754g/mL) is uniformly mixed with 1.25mg/mL graphene oxide (GO) aqueous solution of 80mL, and obtained suspension is in room temperature
Lower stirring 12 hours is added again later with promoting negatively charged GO mutually to coat with positively charged PS bead by electrostatic interaction
Enter 3g melamine, mixture is stirred for 12h at room temperature.Then under the conditions of mixture being put into 60 DEG C of baking oven, baking is for 24 hours.
Obtained solid is placed on silica crucible, 800 DEG C of calcining 1h in the tube furnace of logical nitrogen.Resulting product is that nitrogen is mixed after cooling
Miscellaneous hollow graphite alkene micro-sphere material (NGHMs).
The TEM and SEM that Fig. 1 (a) (b) is NGHMs scheme.It can be seen that hollow microsphere shape is presented in resulting NGHMs.
It the use of the specific surface area that nitrogen adsorption-desorption isotherm measures NGHMs is 555m2/ g is as shown in Figure 2.
If Fig. 4 is charge/discharge capacity of the NGHMs as sodium-ion battery cathode under different current densities.Fig. 4 is shown
NGHMs is respectively 0.1,0.2,1,2,5,10Ag in current density-1When, reversible capacity is respectively 283.8,229.9,201.2,
186.8,229.9,201.2 and 85.8mAh g-1.Strikingly, even if in a very high current density 20Ag-1Item
Under part, it can also be observed that the stable reversible capacity of NGHMs is 66.7mAh g-1.Most it is interesting that when current density returns to 10,5,
2,1,0.5,0.2Ag-1When, reversible capacity can be restored to 83.2,108.1,142.2,182.2,201.1 and 214.8mAhg respectively-1.The high rate performance of NGHMs is higher by much than NG made from comparative example 1.
Fig. 6 illustrates NGHMs in preceding 10 cycle periods, is 50mAg with current density-1, 600 circulating cycles then
Phase is 500mAg with current density-1Reversible capacity and coulombic efficiency.It can clearly illustrate that NGHMs is in 10 circulating cycles
After phase, a stable reversible capacitance 205mAh g can be provided-1.Shown in Fig. 8, NGHMs charge and discharge electricity in preceding 10 cycle periods
Current density is 50mAg-1When, the current density of subsequent cycle period is 1000mAg-1, available one stable reversible appearance
Measure 172mAhg-1.The coulombic efficiency of both of these case NGHMs is all close to 100%.The reversible capacity of NGHMs is made than comparative example 1
NG be higher by very much.
Embodiment 2: N doping hollow graphite alkene microballoon (NGHMs) is synthesized according to the following steps:
Prior step (a) is identical as the method for comparative example 1.
(b) preparation of polystyrene (PS): 10g styrene (St) and 2g polyvinylpyrrolidone (PVP) are dissolved in
In 160mL deionized water, then it is added in the reaction flask with stirring and condensing unit, is placed in oil bath and starts stirring
It is uniformly mixed it, 20mL10g/L 2,2 '-azo diisobutyl amidine hydrochloride (AIBA) solution is added, is continually fed into nitrogen,
It is warming up to 65 DEG C of reaction 15h after 40min, takes 5mL to be placed in baking oven and acquires the concentration of polystyrene solution after drying as 0.2g/
mL。
(c) preparation of N doping hollow graphite alkene microballoon: 10mL positively charged polystyrene microsphere aqueous solution (0.2g/
ML it) is uniformly mixed with 0.5mg/mL graphene oxide (GO) aqueous solution of 80mL, it is small that obtained suspension is stirred at room temperature 24
When, to promote negatively charged GO mutually to coat with positively charged PS bead by electrostatic interaction, 0.5g trimerization is added later
Cyanamide, mixture are stirred for for 24 hours at room temperature.Then under the conditions of mixture being put into 80 DEG C of baking oven, baking is for 24 hours.What is obtained consolidates
Body is placed on silica crucible, 750 DEG C of calcining 2h in the tube furnace of logical nitrogen.Resulting product is the hollow stone of N doping after cooling
Black alkene micro-sphere material (NGHMs).
It the use of the specific surface area that nitrogen adsorption-desorption isotherm measures NGHMs is 598m2/g.10 circulations before NGHMs
Charging and discharging currents density is 50mAg in period-1, subsequent cycle period current density is 500 or 1000mAg-1When, respectively
Stabilization reversible capacity be respectively 228.4 and 178.3mAh g-1。
Embodiment 3: N doping hollow graphite alkene microballoon (NGHMs) is synthesized according to the following steps:
Prior step (a) is identical as the method for comparative example 1.
(b) preparation of polystyrene (PS): 10g styrene (St) and 0.67g polyvinylpyrrolidone (PVP) are dissolved in
In 60mL deionized water, then it is added in the reaction flask with stirring and condensing unit, is placed in oil bath and starts stirring
It is uniformly mixed it, 25mL20g/L 2,2 '-azo diisobutyl amidine hydrochloride (AIBA) solution is added, is continually fed into nitrogen,
It is warming up to 75 DEG C of reaction 35h after 90min, takes 5mL to be placed in baking oven and acquires the concentration of polystyrene solution after drying as 0.05g/
mL。
(c) preparation of N doping hollow graphite alkene microballoon: 30mL positively charged polystyrene microsphere aqueous solution (0.05g/
ML it) is uniformly mixed with 1.5mg/mL graphene oxide (GO) aqueous solution of 100mL, it is small that obtained suspension is stirred at room temperature 12
When, to promote negatively charged GO mutually to coat with positively charged PS bead by electrostatic interaction, 9g melamine is added later
Amine, mixture are stirred for 12h at room temperature.Then under the conditions of mixture being put into 60 DEG C of baking oven, 48h is toasted.Obtained solid
It is placed on silica crucible, 600 DEG C of calcining 3h in the tube furnace of logical nitrogen.Resulting product is N doping hollow graphite after cooling
Alkene micro-sphere material (NGHMs).
It the use of the specific surface area that nitrogen adsorption-desorption isotherm measures NGHMs is 578m2/g.10 circulations before NGHMs
Charging and discharging currents density is 50mAg in period-1, subsequent cycle period current density is 500 or 1000mAg-1When, respectively
Stabilization reversible capacity be respectively 218.7 and 175.8mAh g-1。
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (6)
1. a kind of N doping hollow graphite alkene micro-sphere material, which is characterized in that its structural unit has very unified size, by sky
Bulbus cordis and very thin graphene shell composition；Exist in the graphene shell of outer layer largely perpendicular to the mesoporous of spherome surface, Neng Gou
Path is provided on different directions for sodium ion diffusion transport.
2. a kind of preparation method of N doping hollow graphite alkene micro-sphere material as described in claim 1, it is characterised in that: specific
The following steps are included:
(1) preparation of positively charged polystyrene microsphere template
Styrene and polyvinylpyrrolidone are dissolved in deionized water, the reaction with stirring and condensing unit is then added
In bottle, it is placed in oil bath and starting stirring is uniformly mixed it, 10~20g/L, 2,2 '-azo diisobutyl amidine salt is added
Acid salt solution is continually fed into nitrogen, and 65~75 DEG C of 15~35h of reaction are warming up to after 40~90min, moves to dry acquisition in baking oven
Polystyrene spheres；Wherein, the mass ratio of polyvinylpyrrolidone and styrene is 1:5~1:15, styrene and 2,2 '-azos
The mass ratio of diisobutyl amidine HCI solution is 50:1~20:1, and the mass ratio of styrene and deionized water is 1:6~1:16；
(2) preparation of N doping hollow graphite alkene microballoon
Positively charged polystyrene spheres aqueous solution is uniformly mixed with graphene oxide (GO) aqueous solution, is stirred at room temperature anti-
Answer 12~for 24 hours, to promote negatively charged graphene oxide mutually to wrap with positively charged polystyrene sphere by electrostatic interaction
It covers, melamine is added later, mixture is stirred for 12-24h at room temperature, and mixture is then put into baking oven at 60-80 DEG C
Under the conditions of dry 24-48h, obtained solid is put into silica crucible, the 600-800 DEG C of calcining 1-3h in the tube furnace of logical nitrogen,
Resulting product is N doping hollow graphite alkene micro-sphere material after cooling；Wherein, the matter of polystyrene spheres and graphene oxide
Ratio is measured as 50:1~10:1, the mass ratio of polystyrene spheres and melamine is 4:1~1:6.
3. a kind of preparation method of N doping hollow graphite alkene micro-sphere material according to claim 2, which is characterized in that step
(2) mass concentration of polystyrene spheres aqueous solution described in is 0.05-0.2g/mL.
4. a kind of preparation method of N doping hollow graphite alkene micro-sphere material according to claim 2, which is characterized in that step
(2) mass concentration of graphene oxide water solution described in is 0.5-1.5mg/mL.
5. a kind of N doping hollow graphite alkene micro-sphere material according to claim 1 is as anode material of lithium-ion battery
Using.
6. a kind of N doping hollow graphite alkene micro-sphere material according to claim 1 is as large capacity, high magnification sodium ion
The application of cell negative electrode material.
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