CN106531990A - Preparation method for graphene composite electrode material for lithium ion battery - Google Patents
Preparation method for graphene composite electrode material for lithium ion battery Download PDFInfo
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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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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- 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
Abstract
The invention discloses a preparation method for a graphene composite electrode material for a lithium ion battery, and belongs to the technical field of an electrode material of the lithium ion battery. The preparation method comprises the following steps of preparation of mixed raw materials: taking large-dimensional natural flake graphite as the raw material, and preparing a graphene oxide dispersion liquid by adopting a chemical oxidization method; addition of an additive: enabling the graphene oxide dispersion liquid to be mixed with a compounded active material dispersion liquid, then adding an anionic surfactant water solution, and performing ultrasonic processing in an auxiliary manner to enable the three parts to be mixed uniformly; drying and reducing of a composite material: heating the mixed solution of the three parts to 60 DEG C, quickly cooling in liquid nitrogen, and drying the obtained mixture by adopting an in-situ freezing and drying method after the solution is fully iced; and performing reduction on the dried composite material to obtain the graphene composite electrode material. The preparation method is controllable in process, simple in technology, short in preparation period, low in cost and is expected to further improve the specific capacity and the rate capability of the conventional lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, more particularly to a kind of silicon/carbon/graphite in lithium ion batteries alkene is combined
The preparation method of electrode material.
Background technology
At present, lithium ion battery is received more and more attention as a kind of conventional portable energy storage device.But how to carry
The specific capacity of high-lithium ion battery, high rate performance and cyclical stability, are the subject matter of urgent need to resolve.Electrode material is to change
The key of kind performance of lithium ion battery.At present the conventional positive electrode of lithium ion battery is LiFePO4, cobalt acid lithium, LiMn2O4 and
Ternary material negative material is graphite, metal-oxide etc..Graphene due to itself have high electron mobility and compared with
High specific surface area, it is compound with existing lithium ion battery electrode material, existing electrode material can be improved to a certain extent
Performance.The transmission in the material of lithium ion and electronics determines the high rate performance and cyclical stability of material.Graphene is due to tool
The electric conductivity having had, after being combined with existing lithium ion battery electrode material, can improve electrode material to a certain extent
Electric conductivity.The transmission of ion and electronics in graphene-based composite is divided into two parts, and a kind of is the transmission on Graphene,
A kind of be transmitted in Graphene and by the interface of active material.Therefore construct Graphene and by between composite
Combination interface is extremely important, directly affects the multiplying power property of electrode material.Moreover, Graphene due to its have it is well soft
Property, the structure of curling parcel can also be formed, the open design of the bright Graphene curling parcel of reasonable demonstration is more beneficial for other things
The intercalation and parcel of matter, therefore be more beneficial for carrying out chemical doping and hydrogen storage, at the same ultracapacitor, lithium ion battery and
Good application prospect (Nano.Lett.2009,9,2565) will be also had in terms of nanometer electronic device.
If Graphene can be constructed and by the combination interface between active material, accelerated by certain method
The transfer rate of lithium ion and electronics in composite between the two, and the curling package structure of Graphene and interface are constructed
Combine, it will improve the high rate performance and cyclical stability of combination electrode material to a great extent.If can invent
A kind of simple, quick, efficient method prepares the graphene-based combination electrode with combination interface and coiled structure of magnanimity
Material, it will the improvement to the performance of lithium ion battery produces very important meaning.
The content of the invention
The present invention provides a kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene combination electrode material, and the present invention is with simple, fast
Prompt, efficient method prepares the graphene-based combination electrode material with combination interface and coiled structure of magnanimity.
For solving above-mentioned technical problem, the technical scheme is that：
A kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene combination electrode material, comprises the following steps：
(1) prepared by mixed material：With large scale natural flake graphite as raw material, graphite oxide is prepared using chemical oxidization method
Alkene dispersion liquid, while will need to be disperseed in water by compound active substance；
(2) surfactant addition：Mixed by graphene oxide dispersion and by the dispersion liquid of active material,
Then add aqueous solution of anionic surfactant, assisting ultrasonic makes three's mix homogeneously；
(3) drying and reduction of composite：The mixed liquor of three is heated to into 60 DEG C, is cooled down in liquid nitrogen rapidly, with
Graphene oxide web-like package structure is prepared, after solution freezes completely, the method being dried using In-situ condensation is done
It is dry；Dried composite is reduced in noble gases by the way of heating or adding chemical reducing agent, finally
Obtain the graphene-based combination electrode material for lithium ion battery.
Wherein it is preferred to, the size of the natural flake graphite>100 μm, in step (1), chemical oxidization method is to adopt
Graphite is aoxidized with modified Hummers methods, the concentration of the graphene oxide dispersion of preparation is 0.5～7mg/ml, described
It is aqueous dispersions that concentration is 0.5～5mg/ml by active material.
Wherein it is preferred to, it is described by positive pole that active material is the metal-oxide or lithium ion battery that have capacity
Material；The metal-oxide is Fe3O4、Co3O4Or NiO；The positive electrode of lithium ion battery is lithium and cobalt oxides, lithium nickel oxygen
Compound or lithium manganese oxide.
Wherein, the Fe3O4It is made of using following preparation methoies：Using analytically pure Iron(III) chloride hexahydrate, with second two
Alcohol is disperse medium, adds sodium acetate and sodium citrate, and 200 DEG C of hydro-thermal in hydrothermal reaction kettle react 10h, are cooled to room temperature,
After precipitation ethanol and distilled water are cleaned repeatedly, dry in 25 DEG C of vacuum drying ovens, obtain final product.
Wherein, the Co3O4It is made of using following preparation methoies：Take cobalt nitrate, hexamethylenetetramine, trisodium citrate
It is dissolved in 30mL deionized waters, magnetic agitation under room temperature is until solution is changed into clarification；Then mixture is proceeded to into liner polytetrafluoro
In ethylene rustless steel autoclave, filling degree is 80%, sealing, 100 DEG C of constant temperature 24h；Reaction is completely cooled down to room temperature and can obtain
Aubergine is precipitated, and sucking filtration, the drip washing repeatedly of deionized water, dehydrated alcohol are vacuum dried 24h at 60 DEG C；The powder for obtaining is existed
200 DEG C in Muffle furnace heat treatment 3h obtain Co3O4Black powder.
Wherein, take nickel nitrate and hexamethylenetetramine is dissolved in 30mL deionized waters, be subsequently adding trisodium citrate, room temperature
Then mixture is proceeded in the rustless steel hydrothermal reaction kettle of inner liner polytetrafluoroethylene by lower magnetic agitation 10min, and filling degree is
80%, sealing, 100 DEG C of constant temperature 12h；Reaction is completely cooled down to room temperature and obtains green precipitate, sucking filtration, deionized water, anhydrous second
Alcohol is washed, and is vacuum dried 24h at 80 DEG C；By the powder for obtaining, the heat treatment 3h in Muffle furnace obtains NiO black powder at 300 DEG C
End.
Wherein it is preferred to, the anion surfactant is sodium citrate or dodecyl sodium sulfate, the anion
Aqueous surfactant solution concentration is 0.05～5mg/ml.
Wherein it is preferred to, graphene oxide dispersion described in step (2), the dividing by active material
The volume ratio of dispersion liquid and the aqueous solution of anionic surfactant is (1～2):(1～2):(0.1～0.2).
Wherein it is preferred to, the temperature heated described in step (3) is 300 DEG C～800 DEG C, the chemical reducing agent
For hydrazine hydrate solution or hydrazine hydrate steam, the time of electronation is 8～16h.
Beneficial effects of the present invention：
1. it is an object of the invention to improve high rate performance and the stable circulation performance of conventional lithium ion battery, i.e., by adding
Graphene and the combination interface by combination electrode material are constructed with anion surfactant, lithium ion are improved in charge and discharge process
In transfer rate；And by liquid nitrogen cold quenching preparing the coiled structure of Graphene.The material has higher specific capacitance and pole
Good high rate performance, and have preparation flow simple, cost relatively low (agents useful for same is cheap), it is easy to the advantages of preparing in a large number, because
This can be used as a kind of ideal material for changing lithium ion battery high rate performance.
2. the present invention is changed by the zeta current potentials of combination electrode material and surface activity using anion surfactant, and
By the graphene oxide dispersion ULTRASONIC COMPLEX which is prepared with modified Hummers methods, Graphene is constructed and by composite reactive thing
Combination interface between matter, and being combined with Graphene coiled structure, is obtained with high-rate characteristics and stable circulation performance
Electrode material.
3. preparation process of the present invention is controllable, process is simple, short preparation period, low cost, can be expected to further improve tradition
The specific capacity of lithium ion battery and high rate performance.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
To obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is not added with sodium citrate and prepares Graphene/Fe3O4The stereoscan photograph of composite；
Fig. 2 is not added with sodium citrate and prepares Graphene/Fe3O4The cyclical stability and high rate performance of composite；
Fig. 3 addition sodium citrates prepare Graphene/Fe3O4The stereoscan photograph of composite；
Fig. 4 addition sodium citrates prepare Graphene/Fe3O4The cyclical stability and high rate performance of web-like composite；
Fig. 5 addition sodium citrates prepare Graphene/Co3O4The lithium electricity Data Comparison of web-like composite；
Fig. 6 addition sodium citrates prepare the lithium electricity Data Comparison of Graphene/NiO web-like composites.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.It is based on
Embodiment in the present invention, it is all other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
The size of natural flake graphite used in following embodiments>100μm.
Embodiment 1
Using analytically pure 1.35g Iron(III) chloride hexahydrates, with 25mL ethylene glycol as disperse medium, add 2.7g sodium acetates
And 1g sodium citrates, 200 DEG C of hydro-thermal in hydrothermal reaction kettle, 10h is reacted, room temperature is cooled to, by precipitation ethanol and distilled water
After cleaning repeatedly, dry in 25 DEG C of vacuum drying ovens, be then configured to the Fe of 1mg/ml3O4Dispersion liquid.
With natural flake graphite as raw material, natural flake graphite is aoxidized using modified Hummers methods, the oxygen of preparation
Graphite alkene dispersion liquid concentration is 1mg/ml, is 1mg/ml's by graphene oxide dispersion and concentration that concentration is 1mg/ml
Fe3O4Dispersion liquid is combined, and adds the sodium citrate aqueous solution of 0.1mg/ml, graphene oxide dispersion, Fe3O4Dispersion liquid
Volume ratio with sodium citrate aqueous solution is 1:1:0.1, ultrasonic 15min, be heated to 60 DEG C insert in test tube after be put in liquid nitrogen
Cold quenching, until solution freezes completely, is then carried out In-situ condensation drying.Web-like graphene oxide composite wood is obtained after drying
Material, then 500 DEG C of reduction under Ar gas shieldeds by which, the time of electronation is 6h, prepares Graphene/Fe3O4Web-like composite wood
Material.
Electron microscopic observation result shows：Fe under such condition3O4Nano-particle is wrapped in Graphene coil structure,
Without significantly piling up and reuniting, the stable and electrically conductive property of graphene nano scroll looks is significantly improved.
Assembling lithium battery test result shows：The composite is made lithium cell negative pole material chemical property and is greatly changed
Kind, specific capacity is compared with Graphene/Fe3O4Nano-particle rises 40% without the material of special handling, cyclical stability and forthright again
Also can be obviously improved.
Embodiment 2
Fe3O4The preparation method of dispersion liquid and graphene oxide dispersion is with embodiment 1.
With natural flake graphite as raw material, natural flake graphite is aoxidized using modified Hummers methods, the oxygen of preparation
Graphite alkene dispersion liquid concentration is 0.5mg/ml, is 0.5mg/ by graphene oxide dispersion and concentration that concentration is 0.5mg/ml
The Fe of ml3O4Dispersion liquid is combined, and adds the sodium citrate aqueous solution of 0.05mg/ml, graphene oxide dispersion, Fe3O4Point
The volume ratio of dispersion liquid and sodium citrate aqueous solution is 1:2:0.2, be heated to 60 DEG C insert in test tube after be put into cold quenching in liquid nitrogen, directly
Frozen to solution completely, then carried out In-situ condensation drying.Web-like graphene oxide composite material is obtained after drying, then will
Its 300 DEG C of reduction under Ar gas shieldeds, the time of electronation is 5h, so as to obtain Graphene web-like composite.
Electron microscopic observation result shows：There is 30%Fe under such condition3O4Nano-particle occur from pile up with reunite, not with
Graphene occurs fully to combine, and graphene nano volume complex pattern is poor.
Assembling lithium battery test result shows：The composite specific capacitance has declined compared with embodiment 1, cyclical stability and
High rate performance is all not enough compared with 1 negative material of embodiment.
Embodiment 3
Fe3O4The preparation method of dispersion liquid and graphene oxide dispersion is with embodiment 1.
With natural flake graphite as raw material, natural flake graphite is aoxidized using modified Hummers methods, the oxygen of preparation
Graphite alkene dispersion liquid concentration is 7mg/ml, is 5mg/ml's by graphene oxide dispersion and concentration that concentration is 7mg/ml
Fe3O4Dispersion liquid is combined, and adds the sodium citrate aqueous solution of 0.1mg/ml, graphene oxide dispersion, Fe3O4Dispersion liquid
Volume ratio with sodium citrate aqueous solution is 2:1:0.1, be heated to 60 DEG C insert in test tube after be put into cold quenching in liquid nitrogen, until molten
Liquid freezes completely, is then carried out In-situ condensation drying.Obtain web-like graphene oxide composite material after drying, then by its
The lower 800 DEG C of reduction of Ar gas shieldeds, the time of electronation is 7h, so as to obtain Graphene web-like composite.
Electron microscopic observation result shows：Fe under such condition3O4Nano-particle has more than 90% to be wrapped into Graphene web-like
In structure, and the graphene nano volume amount of crimp for being formed is more sophisticated and be uniformly dispersed.
Assembling lithium battery test result shows：The composite specific capacitance has declined compared with embodiment 1, cyclical stability and
High rate performance is all not enough compared with 1 negative material of embodiment.
Embodiment 4
Fe3O4The preparation method of dispersion liquid and graphene oxide dispersion is with embodiment 1.
With natural flake graphite as raw material, natural flake graphite is aoxidized using modified Hummers methods, the oxygen of preparation
Graphite alkene dispersion liquid concentration is 2mg/ml, is 2mg/ml's by graphene oxide dispersion and concentration that concentration is 2mg/ml
Fe3O4Dispersion liquid is combined, and adds the anion surfactant dodecyl sodium sulfate of 5mg/ml, graphene oxide dispersion,
Fe3O4Dispersion liquid and sodium dodecyl sulfate aqueous solution volume ratio be 1:1:0.15, ultrasonic 15min, are heated to 60 DEG C and insert
Cold quenching in liquid nitrogen is put into after in test tube, until solution freezes completely, is then carried out In-situ condensation drying.Rolled up after drying
Shape graphene oxide composite material, then 400 DEG C of reduction under Ar gas shieldeds by which, the time of electronation is 10h, so as to obtain
Graphene web-like composite.
Electron microscopic observation result shows：80% Fe under such condition3O4Nano-particle is wrapped into Graphene coil structure
In, part occurs to pile up and reunites, and electric conductivity increases.
Assembling lithium battery test result shows：The composite is made lithium cell negative pole material chemical property and is greatly changed
Kind, specific capacity is compared with Graphene/Fe3O4Nano-particle rises 10% without the material of special handling, cyclical stability and forthright again
Also can be obviously improved.
Embodiment 5
Fe3O4The preparation method of dispersion liquid and graphene oxide dispersion is with embodiment 1.
With natural flake graphite as raw material, natural flake graphite is aoxidized using modified Hummers methods, the oxygen of preparation
Graphite alkene dispersion liquid concentration is 3mg/ml, is 3mg/ml's by graphene oxide dispersion and concentration that concentration is 3mg/ml
Fe3O4Dispersion liquid is combined, and adds the anion surfactant sodium citrate of 1mg/ml, graphene oxide dispersion, Fe3O4
The volume ratio of dispersion liquid and sodium citrate aqueous solution is 1:2:0.1, ultrasonic 15min, be heated to 60 DEG C insert in test tube after be put into
Cold quenching in liquid nitrogen, until solution freezes completely, is then carried out In-situ condensation drying.Web-like graphene oxide is obtained after drying
Composite, then 500 DEG C of reduction under Ar gas shieldeds by which, the time of electronation is 8h, multiple so as to obtain Graphene web-like
Condensation material.
Electron microscopic observation result shows：90% Fe under such condition3O4Nano-particle is wrapped into Graphene coil structure
In, to pile up and agglomeration is improved, electric conductivity increases.
Assembling lithium battery test result shows：The composite is made lithium cell negative pole material chemical property and is necessarily changed
Kind, specific capacity is compared with Graphene/Fe3O4Nano-particle rises 30% without the material of special handling, cyclical stability and forthright again
Also can be obviously improved.
Embodiment 6
Fe3O4The preparation method of dispersion liquid and graphene oxide dispersion is with embodiment 1.
With natural flake graphite as raw material, natural flake graphite is aoxidized using modified Hummers methods, the oxygen of preparation
Graphite alkene dispersion liquid concentration is 4mg/ml, is 4mg/ml's by graphene oxide dispersion and concentration that concentration is 4mg/ml
Fe3O4Dispersion liquid is combined, and adds the anion surfactant sodium citrate of 2mg/ml, graphene oxide dispersion, Fe3O4
The volume ratio of dispersion liquid and sodium citrate aqueous solution is 2:1:0.1, ultrasonic 15min, be heated to 60 DEG C insert in test tube after be put into
Cold quenching in liquid nitrogen, until solution freezes completely, is then carried out In-situ condensation drying.Web-like graphene oxide is obtained after drying
Composite, then 600 DEG C of reduction under Ar gas shieldeds by which, the time of electronation is 4h, multiple so as to obtain Graphene web-like
Condensation material.
Electron microscopic observation result shows：90% Fe under such condition3O4Nano-particle is wrapped into Graphene coil structure
In, without significantly building up and reuniting, electric conductivity increases.
Assembling lithium battery test result shows：The composite is made lithium cell negative pole material chemical property and is necessarily changed
Kind, specific capacity is compared with Graphene/Fe3O4Nano-particle rises 20% without the material of special handling, cyclical stability and forthright again
Also can be obviously improved.
Embodiment 7
3.16g cobalt nitrates are weighed, 2.12g hexamethylenetetramines and 1.23g trisodium citrates are dissolved in 30mL deionized waters,
Magnetic agitation under room temperature is until solution is changed into clarification.Then mixture is proceeded to into inner liner polytetrafluoroethylene rustless steel autoclave
In, filling degree is 80%, sealing, 100 DEG C of constant temperature 24h.Reaction is completely cooled down to room temperature and can obtain aubergine precipitation, and sucking filtration spends
The drip washing repeatedly of ionized water, dehydrated alcohol, is vacuum dried 24h at 60 DEG C.By the powder for obtaining in 200 DEG C of heat treatments in Muffle furnace
3h obtains Co3O4Black powder, is configured to the dispersion liquid of 3mg/mL.
With natural flake graphite as raw material, natural flake graphite is aoxidized using modified Hummers methods, the oxygen of preparation
Graphite alkene dispersion liquid concentration is 5mg/ml, by Co3O4Dispersion liquid is mixed, then adds the sodium citrate of 3mg/mL, oxidation
Graphene dispersing solution, Co3O4The volume ratio of dispersion liquid and sodium citrate aqueous solution is 2:1:0.1 ultrasound 15min, is heated to 60 DEG C
Cold quenching in liquid nitrogen is put into after inserting in test tube, until solution freezes completely, is then carried out In-situ condensation drying.After drying
To graphene oxide web-like composite, then by its under Ar gas shieldeds adopt hydrazine hydrate steam reduction, the time of electronation
For 8h.Prepare Graphene/Co3O4Web-like composite.
Electron microscopic observation result shows：Add the Co of sodium citrate modification under such condition3O4Nano-particle has more than 80%
It is wrapped in Graphene coil structure.
Assembling lithium battery test result shows：The composite of addition sodium citrate specific capacity Jing after 50 circulations adds compared with nothing
Sample-adding product are big by 50%.
Embodiment 8
4.36g nickel nitrates are weighed by a certain percentage and 1.56g hexamethylenetetramines are dissolved in 30mL deionized waters, Ran Houjia
Enter trisodium citrate, magnetic agitation 10min under room temperature, the rustless steel hydro-thermal that mixture is proceeded to inner liner polytetrafluoroethylene then are anti-
In answering kettle, filling degree is 80%, sealing, 100 DEG C of constant temperature 12h.Reaction is completely cooled down to room temperature and obtains green precipitate, and sucking filtration is used
Deionized water, absolute ethanol washing, are vacuum dried 24h at 80 DEG C.By the powder for obtaining at 300 DEG C the heat treatment in Muffle furnace
3h obtains NiO black powders.It is configured to the dispersion liquid of 3mg/mL.
With natural flake graphite as raw material, natural flake graphite is aoxidized using modified Hummers methods, the oxygen of preparation
Graphite alkene dispersion liquid concentration is 6mg/ml, will be NiO dispersion liquids mixed, and the sodium citrate for then adding 4mg/mL is water-soluble
Liquid, the volume ratio of graphene oxide dispersion, NiO dispersion liquids and sodium citrate aqueous solution is 2:1:0.1, ultrasonic 15min, heating
Cold quenching in liquid nitrogen is put into after inserting in test tube to after 60 DEG C, until solution freezes completely, In-situ condensation drying is then carried out.
Obtain graphene oxide web-like composite after drying, then be added into the reduction of 5mL80% hydrazine hydrate solutions, electronation when
Between be 16h.Prepare Graphene/NiO web-like composites.
Electron microscopic observation result shows：The NiO nano-particle for adding sodium citrate modification under such condition is wrapped degree
It is more sophisticated, and the graphene nano volume structure for being formed is stable and is uniformly dispersed.
Assembling lithium battery test result shows：The composite specific capacity of addition sodium citrate is big compared with no added sample
50%, and cyclical stability makes moderate progress.
As shown in figure 1,70% Fe under such condition3O4Nano-particle is wrapped in Graphene coil structure,
Fe3O4Nano particle portion occurs to pile up and reunites, and contacts with Graphene not exclusively, and graphene nano volume fracture is obvious, structure
Stability declines, and the diameter dimension of graphene nano volume concentrates on 300nm～400nm.
As shown in Fig. 2 assembled lithium battery test, under its 1C multiplying power, battery specific capacity is 812mAh g-1, Jing 100 times is electric
Pond specific capacity is 684mAh g-1, decay 20% or so.Its high rate performance (0.1C, 0.2C, 0.5C, 1C, 2C, 5C) is respectively
1185,1025,812,745,682,485mAh g-1。
As shown in figure 3,90% Fe under such condition3O4Nano-particle is wrapped in Graphene coil structure,
Fe3O4Nano-particle is without significantly building up and reunite, and contacts with Graphene completely, and Graphene web-like structure and morphology is perfect, electric conductivity
Increase, the diameter dimension of graphene nano volume concentrates on 200nm～300nm.
As shown in figure 4, assembling lithium battery test, under 1C multiplying powers, battery specific capacity is up to 1102mAh g-1, 100 primary cells of Jing
Specific capacity still has 1012mAh g-1.Its high rate performance (0.1C, 0.2C, 0.5C, 1C, 2C, 5C) is respectively 1610,1420,1210,
1135,825 and 624mAh g-1。
As shown in figure 5, Graphene/Co3O4The assembled lithium ion battery test of web-like composite, under 0.1C multiplying powers, addition
Sodium citrate sample specific capacity is 1200mAh/g, and Jing after 50 circulations, specific capacity is 1120mAh/g；And it is not added with sodium citrate
Sample specific capacity decay to 730mAh/g from 1150mAh/g, Jing 500 times circulation after the more additive-free sample of specific capacity it is big by 50%
Left and right.
As shown in fig. 6, the assembled lithium ion battery test of Graphene/NiO web-like composites, adds sodium citrate sample
Specific capacity 0.1C multiplying power (1200mAh/g) and 1C multiplying powers (820mAh/g), more additive-free sample specific capacity, 0.1C multiplying powers
(800mAh/g) and 1C multiplying powers (600mAh/g) have larger improvement.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene combination electrode material, it is characterised in that comprise the following steps：
(1) prepared by mixed material：With large scale natural flake graphite as raw material, graphene oxide point is prepared using chemical oxidization method
Dispersion liquid, while will need to be disperseed in water by compound active substance；
(2) surfactant addition：Mixed by graphene oxide dispersion and by the dispersion liquid of active material, then
Addition aqueous solution of anionic surfactant, assisting ultrasonic make three's mix homogeneously；
(3) drying and reduction of composite：The mixed liquor of three is heated to into 60 DEG C, is cooled down in liquid nitrogen rapidly, to prepare
Graphene oxide web-like package structure, after solution freezes completely, the method being dried using In-situ condensation is dried；Will
Dried composite is reduced in noble gases by the way of heating or adding chemical reducing agent, finally gives use
In the graphene-based combination electrode material of lithium ion battery.
2. the preparation method of a kind of silicon/carbon/graphite in lithium ion batteries alkene combination electrode material according to claim 1, its feature exist
In：The size of the natural flake graphite>100 μm, in step (1), chemical oxidization method is using modified Hummers methods pair
Graphite is aoxidized, and the concentration of the graphene oxide dispersion of preparation is 0.5～7mg/ml, and described is dense by active material
Spend the aqueous dispersions for 0.5～5mg/ml.
3. the preparation method of a kind of silicon/carbon/graphite in lithium ion batteries alkene combination electrode material according to claim 2, its feature exist
In：It is described by positive electrode that active material is the metal-oxide or lithium ion battery that have capacity.
4. the preparation method of a kind of silicon/carbon/graphite in lithium ion batteries alkene combination electrode material according to claim 3, its feature exist
In：The anion surfactant is sodium citrate or dodecyl sodium sulfate, the aqueous solution of anionic surfactant
Concentration is 0.05～5mg/ml.
5. the preparation method of a kind of silicon/carbon/graphite in lithium ion batteries alkene combination electrode material according to claim 1, its feature exist
In：It is graphene oxide dispersion described in step (2), described by the dispersion liquid of active material and the anion table
The volume ratio of face aqueous surfactant solutions is (1～2):(1～2):(0.1～0.2).
6. the preparation method of a kind of silicon/carbon/graphite in lithium ion batteries alkene combination electrode material according to claim 1, its feature exist
In：The temperature heated described in step (3) is 300 DEG C～800 DEG C, and the chemical reducing agent is hydrazine hydrate solution or hydration
Hydrazine steam, the time of electronation is 8～16h.
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