CN106941151A - A kind of graphene composite graphite negative electrode material and its preparation method and application - Google Patents

A kind of graphene composite graphite negative electrode material and its preparation method and application Download PDF

Info

Publication number
CN106941151A
CN106941151A CN201610004810.3A CN201610004810A CN106941151A CN 106941151 A CN106941151 A CN 106941151A CN 201610004810 A CN201610004810 A CN 201610004810A CN 106941151 A CN106941151 A CN 106941151A
Authority
CN
China
Prior art keywords
graphene
graphite
preferred
preparation
nitrate
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
CN201610004810.3A
Other languages
Chinese (zh)
Other versions
CN106941151B (en
Inventor
宁国庆
陈兵
马新龙
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.)
China University of Petroleum Beijing
Original Assignee
China University of Petroleum Beijing
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 China University of Petroleum Beijing filed Critical China University of Petroleum Beijing
Priority to CN201610004810.3A priority Critical patent/CN106941151B/en
Publication of CN106941151A publication Critical patent/CN106941151A/en
Application granted granted Critical
Publication of CN106941151B publication Critical patent/CN106941151B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a kind of graphene composite graphite negative electrode material and its preparation method and application, methods described includes:A) graphene, graphite and auxiliary agent are added in supercritical fluid;It is uniformly mixing to obtain mixture;B) the obtained mixtures of step a) are spray-dried, collection obtains powder;C) powder calcination for obtaining step b), obtains described graphene composite graphite negative electrode material.The present invention can effectively improve the chemical property of lithium ion battery negative material.Preferable negative material is provided to prepare the lithium ion battery with more preferable chemical property, is an important breakthrough in electrochemical applications field.

Description

A kind of graphene composite graphite negative electrode material and its preparation method and application
Technical field
The invention provides a kind of graphene composite graphite negative electrode material and its preparation method and application, belong to energy technology Field.
Background technology
Graphene, as a kind of carbon material of New Two Dimensional structure, was sent out first in 2004 by Novoselov et al. Existing (Novoselov, K.S.;Geim,A.K.;Morozov,S.V.;Jiang,D.;Zhang,Y.;Dubonos,S.V.; Grigorieva,I.V.;Firsov,A.A.Science 2004,306,666-9).Graphene is known today most thin, strong Maximum material is spent, with excellent conductive capability, the current density of six orders of magnitude higher than copper can be born, had The record-breaking capacity of heat transmission, while with high rigidity and good ductility (Geim, A.K.Science 2009, 324,1530-4).In addition, if graphene can be arbitrarily cut out this typical two-dimension plane structure material, It is obtained with the grapheme material of different performance.A series of this excellent performance of graphene make it in many fields all There is potential application prospect, the focus as recent research.
Lithium ion battery have the advantages that energy density is high, have extended cycle life and memory-less effect and be widely used in just Take in formula electronic equipment.In recent years, the development of electrical equipment was proposed to the power density and energy density of lithium ion battery Higher requirement, and electrode material is the deciding factor that performance of lithium ion battery is improved.In terms of negative material, Current commercialized graphite as anode material for lithium-ion battery theoretical capacity (372mAh g-1) relatively low, limit lithium-ion electric The raising of pond chemical property, therefore it is to meet lithium ion battery to design and prepare high performance lithium ionic cell cathode material The key factor developed to electrical equipment.New carbon graphene is due to the electric conductivity with superelevation, relatively low electric charge Many characteristics such as transfer resistance, the specific surface area of super large and interlamellar spacing, stable mechanical performance and lithium ion storage performance Various potential using values are shown, is the focus of contemporary scientific area research, is also considered as lithium ion battery negative Potential ideal material.But simple graphene negative material is because its irreversible capacity is larger, cyclical stability is poor With the reason such as the voltage platform without stabilization, its application in terms of lithium-ion negative pole battery material is equally limited.Cause This, obtains a kind of cycle performance with high specific capacity, relatively stablized, high rate performance and stable voltage platform Lithium ion battery negative material still requires study.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of graphene composite graphite negative electrode material;
Another object of the present invention is to provide the graphene composite graphite negative electrode material that described preparation method is prepared Material;
A further object of the present invention is GND prepared by the graphene composite graphite negative electrode material described in offer;
It is still another object of the present invention to provide described graphene composite graphite negative electrode material in GND is prepared Application.
For up to above-mentioned purpose, on the one hand, the invention provides a kind of preparation method of graphene composite graphite negative electrode material, Wherein, methods described includes:
A) graphene, graphite and auxiliary agent are added in supercritical fluid, is uniformly mixing to obtain mixture;
B) the obtained mixtures of step a) are spray-dried, collection obtains powder;
C) powder calcination for obtaining step b), obtains described graphene composite graphite negative electrode material.
According to some specific embodiments of the invention, wherein, the graphite is natural flake graphite (average grain diameter 15-20 Micron) or Delanium.
According to some specific embodiments of the invention, wherein, graphite purity is more than 99%.
According to some specific embodiments of the invention, wherein, the mass ratio of graphene and graphite is 1:1-100.
According to some specific embodiments of the invention, wherein, the mass ratio of supercritical fluid and graphite is 0.1-100:1.
According to still other specific embodiment of the invention, wherein, the mass ratio of supercritical fluid and graphite is 1-10:1.
According to other specific embodiment of the invention, wherein, the mass ratio of supercritical fluid and graphite is 1:1.
According to some specific embodiments of the invention, wherein, the auxiliary agent quality consumption is graphene quality 0.1-100%.
According to some specific embodiments of the invention, wherein, the auxiliary agent is selected from neopelex, aliphatic acid Glyceride, N-methyl pyrrolidones, sulphur simple substance, red phosphorus, black phosphorus, ethanol, carbon disulfide, toluene, nickel nitrate, One or more kinds of mixing in cobalt nitrate, manganese nitrate, nickelous carbonate, cobalt carbonate and manganese carbonate.
According to some specific embodiments of the invention, wherein, step c) is the powder for obtaining step b) in inertia Calcined in gas atmosphere.
According to some specific embodiments of the invention, wherein, the inert gas is nitrogen.
According to some specific embodiments of the invention, wherein, the temperature of the step c) calcinings is 300-800 DEG C; Wherein preferred calcination temperature is 600 DEG C.
According to some specific embodiments of the invention, wherein, the time of the step c) calcinings is 0.5-2h.
According to some specific embodiments of the invention, wherein, the graphene is doped graphene.
According to some specific embodiments of the invention, wherein, the doped graphene is to mix one kind in S, N and P Or two or more mixing.
According to some specific embodiments of the invention, wherein, when the doped graphene contains one in S, N and P When planting or be a variety of, the respective doping of S, N and P is each independently:S:0.5-5wt%, N:0.5-5wt%, P:0.1-2%.
That is, it is one or more kinds of mixing in S, N and P no matter to adulterate in doped graphene, As long as wherein containing S, then S doping is just 1.23-2.95wt%;As long as wherein containing N, then N's Doping is just 1.95-3.35wt%;As long as wherein containing P, then P doping is just 0.21-1.34wt%.
Graphene of the present invention can use existing conventional graphene, and according to some specific embodiment parties of the invention Case, the graphene that the graphene prepares for supercritical fluid method.
According to some specific embodiments of the invention, wherein, the preparation of the graphene includes:
(1) using graphite as raw material, with additive, oxidant according to mass ratio 0.1-20:0.1-50:1 ratio mixing Reacted afterwards, heating response obtains expanded graphite after treatment;
(2) expanded graphite for obtaining step (1) is sheared, and obtains powdery solid;
(3) powdery solid for obtaining step (2) is scattered in organic solvent, in 30-90 DEG C of laser heating stirring Ultrasonic disperse 0.1-1h again after 0.1-10h, treats that liquid is changed into uniform Dark grey;
(4) the Dark grey product for obtaining step (3) is well mixed in autoclave with Co 2 supercritical fluid Obtain mixture;
(5) mixture for obtaining step (4) is sprayed onto in non-pressure vessel by nozzle, obtains powdery graphite alkene.
According to some of the invention specific embodiments, wherein, step (1) be using graphite as raw material, with additive, Oxidant is according to mass ratio 2:10:Reacted after 1 ratio mixing, heating response obtains expanding stone after treatment Ink;
According to some of the invention specific embodiments, wherein, the additive be selected from iron chloride, copper chloride, manganese chloride, Melamine, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, APP, peroxophosphoric acid sodium, sodium nitrate, ammonium nitrate, Ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, manganese nitrate, zinc nitrate, sodium thiosulfate, sodium peroxydisulfate, sulfuric acid It is one or more kinds of mixed in magnesium, cobaltous sulfate, ferric sulfate, ferrous sulfate, nickel sulfate, manganese sulfate and lithium phosphate Close.
According to some of the invention specific embodiments, wherein, the oxidant be selected from sulfuric acid, nitric acid, phosphoric acid, acetic acid, One or more kinds of mixtures in acetic anhydride, oxalic acid, potassium permanganate, hydrogen peroxide and potassium bichromate.
According to some specific embodiments of the invention, wherein, using graphite as raw material, after being mixed with additive and oxidant Carry out reaction 2-12h.
According to other specific embodiments of the invention, wherein, using graphite as raw material, mixed with additive and oxidant Reaction 12h is carried out afterwards.
According to some specific embodiments of the invention, wherein, using graphite as raw material, after being mixed with additive and oxidant Reacted, 550-900 DEG C of reaction is heated to after treatment and obtains expanded graphite.
According to some specific embodiments of the invention, wherein, preferably it is heated to 550-900 DEG C of reaction 0.5-2h and obtains Expanded graphite.
According to other specific embodiment of the invention, wherein being heated to 750 DEG C of reactions obtains expanded graphite.
According to some of the invention specific embodiments, wherein, step (1) be using graphite as raw material, with additive, Reacted, after treatment, carried out after obtained product is mixed with additive, oxidant again after oxidant mixing Reaction, then after treatment, heating obtains expanded graphite.
Wherein, the additive being separately added into twice can be with identical, can also be different.
The oxidant being separately added into twice can also be identical, can also be different.
According to some specific embodiments of the invention, wherein, step (1) processing is graphite and additive and oxygen After agent reaction, obtained product will be reacted and washed with hydrochloric acid solution, be washed with water that to wash to pH be 6-7.5, filtering, Obtain filter cake.
According to some specific embodiments of the invention, wherein, step (1) described hydrochloric acid solution is volume ratio 1:1-10 Concentrated hydrochloric acid and water prepare.
It is 6wt% wherein preferably to prepare obtained hydrochloric acid solution mass concentration.
According to some of the invention specific embodiments, wherein, step (1) be using graphite as raw material, with additive and Reacted, the product that reaction is obtained is washed with hydrochloric acid solution, is washed with water and is washed three times, filtered after oxidant mixing, Heating response obtains expanded graphite after filtration cakes torrefaction.
According to some of the invention specific embodiments, wherein, step (1) be using graphite as raw material, with additive and Reacted, the product that reaction is obtained is washed with hydrochloric acid solution, is washed with water and is washed three times, filtered after oxidant mixing, Filter cake is reacted after being mixed again with additive and oxidant, and the product that reaction is obtained is washed with hydrochloric acid solution, then is used Heating obtains expanded graphite after water washing three times, filtering, filtration cakes torrefaction.
According to some specific embodiments of the invention, wherein, step (2) shearing rotating speed is 5000-20000rpm.
According to some specific embodiments of the invention, wherein, step (3) is in 70 DEG C of laser heating stirring 0.5h Ultrasonic disperse 0.5h again, treats that liquid is changed into uniform Dark grey afterwards.
According to some of the invention specific embodiments, wherein, step (3) described organic solvent be selected from ethanol, ether, One or more kinds of mixing in 1-METHYLPYRROLIDONE (NMP) and dimethylformamide (DMF).
According to some specific embodiments of the invention, wherein, step (3) described consumption of organic solvent is per 1g powder Shape solid is scattered in 10-300ml organic solvents.
According to other specific embodiments of the invention, wherein, step (3) described consumption of organic solvent is per 1g powder Shape solid is scattered in 30ml organic solvents.
According to some specific embodiments of the invention, wherein, step (4) is that the Dark grey product for obtaining (3) exists It is well mixed under 8-20MPa with Co 2 supercritical fluid.
According to some specific embodiments of the invention, wherein, step (4) is the product and two for obtaining step (3) Carbonoxide supercritical fluid in mass ratio 1:0.5-100 is well mixed.
According to other of the invention specific embodiments, wherein, step (4) be the product that obtains step (3) with Co 2 supercritical fluid in mass ratio 1:1 is well mixed.
According to some specific embodiments of the invention, wherein, step (4) at room temperature obtains step (3) Product is well mixed with Co 2 supercritical fluid.
According to some specific embodiments of the invention, wherein, the jet expansion internal diameter of step (5) is 1-20mm.
On the other hand, present invention also offers the graphene composite graphite negative electrode material that described preparation method is prepared Material.
Another aspect, present invention also offers GND prepared by described graphene composite graphite negative electrode material.
According to some specific embodiments of the invention, wherein, the battery is lithium ion battery.
Another further aspect, GND is being prepared present invention also offers the graphene composite graphite negative electrode material described in offer In application.
According to some specific embodiments of the invention, wherein, the battery is lithium ion battery.
In summary, the invention provides a kind of graphene composite graphite negative electrode material and its preparation method and application.This The graphene composite graphite negative electrode material of invention has the following advantages that:
The composite technology cost of the present invention is relatively low, is adapted to heavy industrialization application.
The present invention can effectively improve the chemical property of lithium ion battery negative material.It is commonly used relative to industrial Graphite cathode material, the specific capacity of negative material greatly improved in this graphene-graphite cathode material;Same phase Compared with simple using grapheme material as negative material, material cost is not only efficiently controlled, and improve material The stable circulation performance of material, and material is presented stable voltage platform during discharge and recharge.In summary, This invention provides preferable negative material to prepare the lithium ion battery with more preferable chemical property, is that electrochemistry should With an important breakthrough in field.
Brief description of the drawings
Fig. 1 is ESEM (SEM) picture of the undressed natural flake graphite of embodiment 1;
Fig. 2 is ESEM (SEM) picture of the expanded graphite of embodiment 1;
Fig. 3 passes through the transmission of the multi-layer graphene obtained after supercritical fluid method of the present invention processing for embodiment 1 Electronic Speculum (TEM);
Fig. 4 is that graphene-graphite composite material that embodiment 1 is prepared is used as activity in ion cathode material lithium The curve of double curvature of material;
Fig. 5 is that graphene-graphite composite material that embodiment 1 is prepared is used as activity in ion cathode material lithium The charge-discharge test curve of material;
Fig. 6 is that graphene-graphite composite material that embodiment 1 is prepared is used as activity in ion cathode material lithium 100 circle cyclic curve (150mA g of material-1);
Fig. 7 is that graphene-graphite composite material that embodiment 3 is prepared is used as activity in ion cathode material lithium The curve of double curvature of material;
Fig. 8 is that graphene-graphite composite material that embodiment 3 is prepared is used as activity in ion cathode material lithium The charge-discharge test curve of material;
Fig. 9 is that graphene-graphite composite material that embodiment 3 is prepared is used as activity in ion cathode material lithium 100 circle cyclic curve (150mA g of material-1);
Figure 10 is that graphene-graphite composite material that embodiment 5 is prepared is used as activity in ion cathode material lithium The curve of double curvature of material;
Figure 11 is that graphene-graphite composite material that embodiment 5 is prepared is used as activity in ion cathode material lithium The charge-discharge test curve of material;
Figure 12 is that graphene-graphite composite material that embodiment 5 is prepared is used as activity in ion cathode material lithium 100 circle cyclic curve (150mA g of material-1);
Figure 13 is that graphene-graphite composite material that embodiment 7 is prepared is used as activity in ion cathode material lithium The curve of double curvature of material;
Figure 14 is that graphene-graphite composite material that embodiment 7 is prepared is used as activity in ion cathode material lithium The charge-discharge test curve of material;
Figure 15 is that graphene-graphite composite material that embodiment 7 is prepared is used as activity in ion cathode material lithium 100 circle cyclic curve (150mA g of material-1);
Curve of double curvature of the Figure 16 for graphite material in comparative example 1 in ion cathode material lithium as active material;
Charge-discharge test songs of the Figure 17 for graphite material in comparative example 1 in ion cathode material lithium as active material Line.
Embodiment
The beneficial effect for describing the implementation process of the present invention in detail below by way of specific embodiment and producing, it is intended to which help is read Reader more fully understand the present invention essence and feature, not as to this case can practical range restriction.
Embodiment 1
A kind of graphene-graphite composite material and preparation method thereof is present embodiments provided, including:
1. the preparation of graphene
A. 10g graphite is well mixed with 5g potassium permanganate powders, adds the 50g concentrated sulfuric acids (80wt%), uniformly stir Mix, 12h is reacted at room temperature.
B. gained suspension is washed with watery hydrochloric acid (6wt%), then with deionized water cyclic washing three times, filtering, Obtain filter cake.
C. products therefrom is reentered into reactor and reacted, add the 12.5g concentrated sulfuric acids (80wt%), 10g Hydrogen peroxide, uniform stirring reacts 3h at room temperature.
D. gained suspension is washed with watery hydrochloric acid (6wt%), then with deionized water cyclic washing three times, measures pH Value is between 6-7.5, and filtering obtains filter cake.
E. by products therefrom at 750 DEG C heating response 1h because the presence of oxidation intercalation functional group, expanded by heating makes stone The distance between ink sheet layer is significantly increased, and the scanning electron microscopic picture of former graphite flake is shown in Fig. 1, and the product after heating is swept Retouch electron microscopic picture and see Fig. 2.
F. obtained product is sheared with high-speed shearing machine (JRJ301-1H).
G. the sample after shear treatment is mixed with 100ml dimethylformamides (DMF), ultrasonically treated 2h.
H. products therefrom is put into autoclave, is passed through Co 2 supercritical fluid, pressure 10Mpa, temperature For room temperature, stir.The Co 2 supercritical fluid of expanded graphite will be dispersed with and be sprayed onto one by autoclave nozzle In individual normal pressure bulk container, collected in container bottom and obtain graphene powder.Its transmission electron microscope picture is as shown in Figure 3.
2. the preparation of graphene-composite cathode material of silicon/carbon/graphite
By the crystalline flake graphite of the graphene obtained in step 1 and 80 mesh in mass ratio 1:1 is added to that carbon dioxide is super to be faced In boundary's fluid, the mass ratio of supercritical fluid and graphite is 1:1, toluene is also added in mixture simultaneously, wherein, Graphene:Toluene (wt)=1:1.
Obtained mixture is spray-dried, collection obtains powder.
Obtained powder is calcined in a nitrogen atmosphere, 600 DEG C, normal pressure, 0.5h.Obtain graphene-graphite multiple Condensation material.
Embodiment 2
Graphene-the graphite composite material prepared by embodiment 1 is present embodiments provided to bear as lithium ion battery The application of pole material activity material, it comprises the following steps:
A. by the graphene-graphite composite material prepared in 0.4g embodiments 1 and 0.714g Kynoar solutions Negative material is made in (PVDF, 7wt%) and 0.05g carbon black mixing and stirrings, wherein, graphene-graphite is combined Material is used as conductive agent as active material, Kynoar as adhesive, carbon black.
B. by above-mentioned negative material coater even spread on aluminium foil, lithium ion cell positive is made in drying; In glove box full of argon gas atmosphere by positive pole, lithium piece, barrier film and electrolyte according to battery assembling technique groups dress up lithium from Sub- battery;Wherein, barrier film uses U.S. celgard2400, and electrolyte is LiPF6 1mol/L solution, and solvent is EC, EMC, DMC are according to volume ratio 1:1:1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate Ester, methyl ethyl carbonate, dimethyl carbonate.After being completed, lithium ion battery is placed into 12h, in charge-discharge test Charge-discharge magnification performance test is carried out on instrument.
Multiplying power test result is as shown in figure 4, as can be seen from Figure 4 use graphene-graphite composite material conduct Lithium ion battery negative material active material is in 150mA g-1Its specific capacity reaches 429mAh g under electric current-1, it is substantially high In the 372mAh g of common graphite-1, show that the composite makes the capacity of battery be significantly improved;Fill Discharge curve is as shown in Figure 5, it can be seen that have stable voltage platform near 0.2-0.3V;Cyclical stability is tested As a result as shown in fig. 6, after the circle of circulation 100, capacity is not decayed, show that the composite has very good Cyclical stability.It can be drawn according to above test result, this graphene-graphite composite material has very excellent Different chemical property, is the ideal material as lithium ion battery negative pole active materials.
Embodiment 3
A kind of graphene-graphite composite material and preparation method thereof is present embodiments provided, including:
1. the preparation of graphene
A. 10g graphite, 5g potassium permanganate, 5g magnesium sulfate and 5g sodium peroxydisulfates are well mixed, add 50g dense Sulfuric acid (80wt%), uniform stirring reacts 12h at room temperature.
B. gained suspension is washed with hydrochloric acid (6wt%), then with deionized water cyclic washing three times, filtering is obtained To filter cake.
C. products therefrom is reentered into reactor and reacted, add the 12.5g concentrated sulfuric acids (80wt%), 10g Hydrogen peroxide, uniform stirring reacts 3h at room temperature.
D. gained suspension is washed with hydrochloric acid (6wt%), then pH value is measured three times with deionized water cyclic washing and existed Between 6-7.5, filtering obtains filter cake.
E. by products therefrom at 800 DEG C heating response 0.5h.
F. obtained product is sheared with high-speed shearing machine (JRJ301-1H).
G. the sample after shear treatment is mixed with 100ml dimethylformamides (DMF), ultrasonically treated 2h.
Products therefrom is put into autoclave, Co 2 supercritical fluid, pressure 10Mpa is passed through, temperature is Room temperature, stirs.Obtain product and mix sulfur graphite alkene.
2. the preparation of graphene-composite cathode material of silicon/carbon/graphite
A. by the crystalline flake graphite of the graphene obtained in step 1 and 80 mesh in mass ratio 1:100, which are added to carbon dioxide, surpasses (mass ratio of carbon dioxide and graphite is 100 to critical fluids:1) in, by toluene and neopelex Add simultaneously in mixture, wherein, graphene:Toluene (wt)=1:0.5.
B. obtained mixture is spray-dried, collection obtains powder.
C. obtained powder is calcined in a nitrogen atmosphere, 600 DEG C, normal pressure, 0.5h.Obtain graphene-graphite Composite.
Embodiment 4
Graphene-the graphite composite material prepared by embodiment 3 is present embodiments provided to bear as lithium ion battery The application of pole material activity material, it comprises the following steps:
A. by the graphene-graphite composite material prepared in 0.4g embodiments 3 and 0.714g Kynoar solutions Negative material is made in (PVDF, 7wt%) and 0.05g carbon black mixing and stirrings, wherein, graphene-graphite is combined Material is used as conductive agent as active material, Kynoar as adhesive, carbon black.
B. by above-mentioned negative material coater even spread on aluminium foil, lithium ion cell positive is made in drying; In glove box full of argon gas atmosphere by positive pole, lithium piece, barrier film and electrolyte according to battery assembling technique groups dress up lithium from Sub- battery;Wherein, barrier film uses U.S. celgard2400, and electrolyte is LiPF6 1mol/L solution, and solvent is EC, EMC, DMC are according to volume ratio 1:1:1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate Ester, methyl ethyl carbonate, dimethyl carbonate.After being completed, lithium ion battery is placed into 12h, in charge-discharge test Charge-discharge magnification performance test is carried out on instrument.
Multiplying power test result is as shown in fig. 7, as can be seen from Figure 7 use graphene-graphite composite material conduct Lithium ion battery negative material active material its specific capacity under 150mA g-1 electric currents has reached 440mAh g-1, bright The aobvious 372mAh g-1 higher than common graphite, show that the composite makes the capacity of battery obtain significantly carrying It is high;Charging and discharging curve is as shown in Figure 8, it can be seen that have stable voltage platform near 0.2-0.3V;Stable circulation Property test result as shown in figure 9, circulation 100 circle after, capacity is not decayed, and shows that the composite has Very good cyclical stability.It can be drawn according to above test result, this graphene-graphite composite material has Very excellent chemical property, is the ideal material as lithium ion battery negative pole active materials.
Embodiment 5
A kind of graphene-graphite composite material and preparation method thereof is present embodiments provided, including:
1. the preparation of graphene
A. 10g graphite, 5g potassium permanganate, 10g ammonium phosphate and 5g peroxophosphoric acid sodium are well mixed, add 50g The concentrated sulfuric acid (80wt%), uniform stirring reacts 12h at room temperature.
B. gained suspension is washed with hydrochloric acid (6wt%), then with deionized water cyclic washing three times, filtering is obtained To filter cake.
C. products therefrom is reentered into reactor and reacted, add the 12.5g concentrated sulfuric acids (80wt%), 10g Hydrogen peroxide, uniform stirring reacts 3h at room temperature.
D. gained suspension is washed with hydrochloric acid (6wt%), then with deionized water cyclic washing three times, measures pH value Between 6-7.5, filtering obtains filter cake.
E. by products therefrom at 700 DEG C heating response 45min.
F. obtained product is sheared with high-speed shearing machine (JRJ301-1H).
G. the sample after shear treatment is mixed with 100ml dimethylformamides (DMF), ultrasonically treated 2h.
Products therefrom is put into autoclave, Co 2 supercritical fluid, pressure 10Mpa is passed through, temperature is Room temperature, stirs.Obtain p-doped graphene.
2. the preparation of graphene-composite cathode material of silicon/carbon/graphite
A is by the crystalline flake graphite of the graphene obtained in step 1 and 80 mesh in mass ratio 1:1 is added to that carbon dioxide is super to be faced (mass ratio of carbon dioxide and graphite is 10 in boundary's fluid:1), toluene and APP are also added simultaneously and mixed In thing, wherein, graphene:Toluene (wt)=1:0.5.
B. obtained mixture is spray-dried, collection obtains powder.
C. obtained powder is calcined in a nitrogen atmosphere, 600 DEG C, normal pressure, 0.5h.Obtain graphene-graphite Composite.
Embodiment 6
Graphene-the graphite composite material prepared by embodiment 5 is present embodiments provided to bear as lithium ion battery The application of pole material activity material, it comprises the following steps.
By the graphene-graphite composite material prepared in 0.4g embodiments 5 and 0.714g Kynoar solutions Negative material is made in (PVDF, 7wt%) and 0.05g carbon black mixing and stirrings, wherein, graphene-graphite is combined Material is used as conductive agent as active material, Kynoar as adhesive, carbon black.
By above-mentioned negative material coater even spread on aluminium foil, lithium ion cell positive is made in drying;Filling Positive pole, lithium piece, barrier film and electrolyte are dressed up into lithium ion according to battery assembling technique groups in the glove box of full argon gas atmosphere Battery;Wherein, barrier film uses U.S. celgard2400, and electrolyte is LiPF6 1mol/L solution, and solvent is EC, EMC, DMC are according to volume ratio 1:1:1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate Ester, methyl ethyl carbonate, dimethyl carbonate.After being completed, lithium ion battery is placed into 12h, in charge-discharge test Charge-discharge magnification performance test is carried out on instrument.
Multiplying power test result as shown in Figure 10, as can be seen from Figure 10 using graphene-graphite composite material as Lithium ion battery negative material active material its specific capacity under 150mA g-1 electric currents has reached 439mAh g-1, it is bright The aobvious 372mAh g higher than common graphite-1, show that the composite makes the capacity of battery obtain significantly carrying It is high;Charging and discharging curve is as shown in figure 11, it can be seen that have stable voltage platform near 0.2-0.3V;Circulation is steady Qualitative test result as shown in figure 12, after the circle of circulation 100, do not decay, and shows the composite by capacity With very good cyclical stability.It can be drawn according to above test result, this graphene-graphite composite material It is the ideal material as lithium ion battery negative pole active materials with very excellent chemical property.
Embodiment 7
1. the preparation of graphene
A. 10g graphite is mixed with 2.5g potassium permanganate, 2.5g potassium bichromates, adds the 50g concentrated sulfuric acids (80wt%), Uniform stirring, reacts 12h at room temperature.
B. by gained suspension with hydrochloric acid (6wt%) cyclic washing three times, then with deionized water cyclic washing three times, Filtering, obtains filter cake.
C. in 800 DEG C of heating response 0.5h after products therefrom is dried, expanded graphite product is obtained.F. by obtained production Thing is sheared with high-speed shearing machine (JRJ301-1H).
D. the sample after shear treatment is mixed with 100ml dimethylformamides (DMF), ultrasonically treated 2h.
E. products therefrom is put into autoclave, is passed through Co 2 supercritical fluid, pressure 10Mpa, temperature
For room temperature, stir.The Co 2 supercritical fluid for being dispersed with expanded graphite is sprayed by autoclave nozzle
Into a normal pressure bulk container, collected in container bottom and obtain graphene powder.
2. the preparation of graphene-composite cathode material of silicon/carbon/graphite
The crystalline flake graphite of the graphene obtained in step 1 and 80 mesh is added in Co 2 supercritical fluid, will Fatty glyceride is also added in mixture simultaneously, wherein, graphene:Graphite:Supercritical fluid:Fatty acid glycerine Ester (wt)=100:100:100:0.1.
Obtained mixture is spray-dried, collection obtains powder.
Obtained powder is calcined in a nitrogen atmosphere, 600 DEG C, normal pressure, 0.5h.Obtain graphene-graphite multiple Condensation material.
Embodiment 8
Graphene-the graphite composite material prepared by embodiment 7 is present embodiments provided to bear as lithium ion battery The application of pole material activity material, it comprises the following steps.
A. by the graphene-graphite composite material prepared in 0.4g embodiments 7 and 0.714g Kynoar solutions Negative material is made in (PVDF, 7wt%) and 0.05g carbon black mixing and stirrings, wherein, graphene-graphite is combined Material is used as conductive agent as active material, Kynoar as adhesive, carbon black.
B. by above-mentioned negative material coater even spread on aluminium foil, lithium ion cell positive is made in drying; In glove box full of argon gas atmosphere by positive pole, lithium piece, barrier film and electrolyte according to battery assembling technique groups dress up lithium from Sub- battery;Wherein, barrier film uses U.S. celgard2400, and electrolyte is LiPF6 1mol/L solution, and solvent is EC, EMC, DMC are according to volume ratio 1:1:1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate Ester, methyl ethyl carbonate, dimethyl carbonate.After being completed, lithium ion battery is placed into 12h, in charge-discharge test Charge-discharge magnification performance test is carried out on instrument.
Multiplying power test result is as can be seen from Figure 13 made as shown in figure 13 using graphene-graphite composite material It is lithium ion battery negative material active material in 150mA g-1Its specific capacity reaches 429mAh g under electric current-1, substantially Higher than the 372mAh g of common graphite-1, show that the composite makes the capacity of battery be significantly improved; Charging and discharging curve is as shown in figure 14, it can be seen that have stable voltage platform near 0.2-0.3V;Cyclical stability Test result as shown in figure 15, after the circle of circulation 100, do not decay, and shows that the composite has by capacity Very good cyclical stability.It can be drawn according to above test result, this graphene-graphite composite material has Very excellent chemical property, is the ideal material as lithium ion battery negative pole active materials.
Comparative example 1
This comparative example is using existing natural flake graphite material directly as lithium ion battery negative material.
By 0.4g natural flake graphites and 0.714g Kynoar solutions (PVDF, 7wt%) and 0.05g carbon blacks Negative material is made in mixing and stirring, wherein, natural flake graphite is as active material, and Kynoar is as viscous Mixture, carbon black is used as conductive agent.
By above-mentioned negative material coater even spread on aluminium foil, lithium ion cell positive is made in drying;Filling Positive pole, lithium piece, barrier film and electrolyte are dressed up into lithium ion according to battery assembling technique groups in the glove box of full argon gas atmosphere Battery;Wherein, barrier film uses U.S. celgard2400, and electrolyte is LiPF6 1mol/L solution, and solvent is EC, EMC, DMC are according to volume ratio 1:1:1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate Ester, methyl ethyl carbonate, dimethyl carbonate.After being completed, lithium ion battery is placed into 12h, in charge-discharge test Charge-discharge magnification performance test is carried out on instrument.
Curve of double curvature is as shown in figure 16, in 150mA g-1When its capacity be 355mAh g-1, less than its theoretical capacity, And far below graphene-graphite composite material of the present invention, its charging and discharging curve such as Figure 17.Pass through this comparative example Prove, graphene-graphite composite material of the present invention is the potential preferable optimization material of existing graphite cathode material.

Claims (10)

1. a kind of preparation method of graphene composite graphite negative electrode material, wherein, methods described includes:
A) graphene, graphite and auxiliary agent are added in supercritical fluid, the mass ratio of preferred supercritical fluid and graphite For 0.1-100:1, more preferably 1-10:1, most preferably 1:1;It is uniformly mixing to obtain mixture;It is preferred that graphene Mass ratio with graphite is 1:1-100;It is preferred that the auxiliary agent quality consumption is the 0.1-100% of graphene quality;It is preferred that The graphene is doped graphene;Wherein the preferably doped graphene is to mix the one or two in S, N and P Graphene above;Wherein further preferably when the doped graphene contains the one or more in S, N and P, S, The respective dopings of N and P are each independently:S:0.5-5wt%, N:0.5-5wt%, P:0.1-2%;Further preferably institute State the graphene that graphene prepares for supercritical fluid method;
B) the obtained mixtures of step a) are spray-dried, collection obtains powder;
C) powder calcination for obtaining step b), obtains described graphene composite graphite negative electrode material;It is wherein excellent Choosing is that the powder for obtaining step b) is calcined in inert gas atmosphere;It is also preferred that the temperature of calcining is 300-800℃;It is preferred that calcination time is 0.5-2h.
2. preparation method according to claim 1, wherein, the graphite is natural flake graphite or artificial stone Ink;It is preferred that graphite purity is more than 99%.
3. preparation method according to claim 1, wherein, the auxiliary agent be selected from neopelex, Fatty glyceride, N-methyl pyrrolidones, sulphur simple substance, red phosphorus, black phosphorus, ethanol, carbon disulfide, toluene, nitre One or more kinds of mixing in sour nickel, cobalt nitrate, manganese nitrate, nickelous carbonate, cobalt carbonate and manganese carbonate.
4. preparation method according to claim 1, wherein, the preparation of the graphene comprises the following steps:
(1) using graphite as raw material, with additive, oxidant according to mass ratio 0.1-20:0.1-50:1 ratio mixing Reacted afterwards, heating response obtains expanded graphite after treatment;It is preferred that the oxidant be selected from sulfuric acid, nitric acid, One or more kinds of mixtures among phosphoric acid, acetic acid, acetic anhydride, oxalic acid, potassium permanganate and potassium bichromate; It is preferred that reacting 2-12h;Expanded graphite is obtained preferably through being heated to 550-900 DEG C after processing;More preferably it is heated to 550-900 DEG C keeps 0.5-2h to obtain expanded graphite;
(2) expanded graphite for obtaining step (1) is sheared, preferably shearing rotating speed 5000-20000rpm, is obtained To powdery solid;
(3) powdery solid for obtaining step (2) is scattered in organic solvent, in 30-90 DEG C of laser heating stirring Ultrasonic disperse 0.1-1h again after 0.1-10h, treats that liquid is changed into uniform Dark grey;It is preferred that the organic solvent be selected from ethanol, One or more kinds of mixing in ether, 1-METHYLPYRROLIDONE and dimethylformamide;Further preferably organic solvent Consumption is to be scattered in 10-300ml organic solvents per 1g powdery solids;
(4) the Dark grey product for obtaining step (3) is well mixed in autoclave with Co 2 supercritical fluid Obtain mixture;The product that preferred steps (3) are obtained is mixed under 8-20MPa with Co 2 supercritical fluid It is even;The product that further preferably step (3) is obtained and Co 2 supercritical fluid in mass ratio 1:0.5-100 is mixed Uniformly;It is preferred that the product that step (3) is obtained at room temperature is well mixed with Co 2 supercritical fluid;
(5) mixture for obtaining step (4) is sprayed onto in non-pressure vessel by nozzle, obtains powdery graphite alkene.
5. preparation method according to claim 4, wherein, the additive be selected from iron chloride, copper chloride, Manganese chloride, melamine, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, APP, peroxophosphoric acid sodium, sodium nitrate, Ammonium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, manganese nitrate, zinc nitrate, sodium thiosulfate, persulfuric acid One in sodium, magnesium sulfate, cobaltous sulfate, ferric sulfate, ferrous sulfate, nickel sulfate, manganese sulfate, lithium phosphate and hydrogen peroxide Plant or two or more mixing.
6. the graphene composite graphite negative electrode material that the preparation method described in Claims 1 to 5 any one is prepared.
7. GND prepared by the graphene composite graphite negative electrode material described in claim 6.
8. GND according to claim 7, wherein, the battery is lithium ion battery.
9. application of the graphene composite graphite negative electrode material in GND is prepared described in claim 6.
10. application according to claim 9, wherein, the battery is lithium ion battery.
CN201610004810.3A 2016-01-05 2016-01-05 A kind of graphene composite graphite negative electrode material and its preparation method and application Expired - Fee Related CN106941151B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610004810.3A CN106941151B (en) 2016-01-05 2016-01-05 A kind of graphene composite graphite negative electrode material and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610004810.3A CN106941151B (en) 2016-01-05 2016-01-05 A kind of graphene composite graphite negative electrode material and its preparation method and application

Publications (2)

Publication Number Publication Date
CN106941151A true CN106941151A (en) 2017-07-11
CN106941151B CN106941151B (en) 2019-07-12

Family

ID=59468515

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610004810.3A Expired - Fee Related CN106941151B (en) 2016-01-05 2016-01-05 A kind of graphene composite graphite negative electrode material and its preparation method and application

Country Status (1)

Country Link
CN (1) CN106941151B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107611445A (en) * 2017-09-18 2018-01-19 华南师范大学 A kind of preparation method of lithium ion battery graphite cathode material
CN109065878A (en) * 2018-08-15 2018-12-21 南通百川新材料有限公司 A kind of preparation method of modified graphene composite graphite negative electrode material
CN109216669A (en) * 2018-08-03 2019-01-15 深圳市山木新能源科技股份有限公司 A kind of preparation method of lithium cell cathode material
CN109467926A (en) * 2018-10-31 2019-03-15 江苏立新材料科技有限公司 Wear-resisting slurry is preparing the application in abrasion-resistant bearing materials
CN109585820A (en) * 2018-11-23 2019-04-05 四川大学 Si-C composite material, preparation method, application and negative electrode of lithium ion battery
CN109585821A (en) * 2018-11-23 2019-04-05 四川大学 Graphite composite material, preparation method, application and negative electrode of lithium ion battery
CN109752433A (en) * 2019-03-04 2019-05-14 四川轻化工大学 A kind of nickel phosphate/Co-MOFs composite material and preparation method and application
CN110668433A (en) * 2019-11-25 2020-01-10 陕西师范大学 Method for preparing graphite/graphene composite material by supercritical carbon dioxide fluid and application
CN110931782A (en) * 2019-11-15 2020-03-27 中南大学 Preparation method and application of hollow sphere cobalt sulfide/graphene composite material
CN114094106A (en) * 2021-11-23 2022-02-25 山东大学 Ammonium polyphosphate modified graphite negative electrode material and preparation method and application thereof
CN114975925A (en) * 2022-05-24 2022-08-30 广东凯金新能源科技股份有限公司 Phosphorus-graphene doped composite graphite negative electrode material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090090640A1 (en) * 2007-10-05 2009-04-09 Jang Bor Z Process for producing carbon anode compositions for lithium ion batteries
CN102569810A (en) * 2011-12-30 2012-07-11 常州第六元素材料科技股份有限公司 Graphene modified lithium ion battery anode material and preparation method thereof
CN104240964A (en) * 2014-09-18 2014-12-24 上海交通大学 Method for achieving in situ composition of graphene and activated carbon through supercutical fluid
CN104934603A (en) * 2015-05-22 2015-09-23 田东 Preparation method of graphene-dopedand carbon-coated modified graphite anode material
CN105016331A (en) * 2015-08-05 2015-11-04 清华大学 Synthetic method of graphene microchip-diamond compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090090640A1 (en) * 2007-10-05 2009-04-09 Jang Bor Z Process for producing carbon anode compositions for lithium ion batteries
CN102569810A (en) * 2011-12-30 2012-07-11 常州第六元素材料科技股份有限公司 Graphene modified lithium ion battery anode material and preparation method thereof
CN104240964A (en) * 2014-09-18 2014-12-24 上海交通大学 Method for achieving in situ composition of graphene and activated carbon through supercutical fluid
CN104934603A (en) * 2015-05-22 2015-09-23 田东 Preparation method of graphene-dopedand carbon-coated modified graphite anode material
CN105016331A (en) * 2015-08-05 2015-11-04 清华大学 Synthetic method of graphene microchip-diamond compound

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107611445A (en) * 2017-09-18 2018-01-19 华南师范大学 A kind of preparation method of lithium ion battery graphite cathode material
CN109216669A (en) * 2018-08-03 2019-01-15 深圳市山木新能源科技股份有限公司 A kind of preparation method of lithium cell cathode material
CN109065878B (en) * 2018-08-15 2021-10-26 南通百川新材料有限公司 Preparation method of modified graphene composite graphite negative electrode material
CN109065878A (en) * 2018-08-15 2018-12-21 南通百川新材料有限公司 A kind of preparation method of modified graphene composite graphite negative electrode material
CN109467926A (en) * 2018-10-31 2019-03-15 江苏立新材料科技有限公司 Wear-resisting slurry is preparing the application in abrasion-resistant bearing materials
CN109585820A (en) * 2018-11-23 2019-04-05 四川大学 Si-C composite material, preparation method, application and negative electrode of lithium ion battery
CN109585821A (en) * 2018-11-23 2019-04-05 四川大学 Graphite composite material, preparation method, application and negative electrode of lithium ion battery
CN109752433A (en) * 2019-03-04 2019-05-14 四川轻化工大学 A kind of nickel phosphate/Co-MOFs composite material and preparation method and application
CN109752433B (en) * 2019-03-04 2021-03-16 四川轻化工大学 Nickel phosphate/Co-MOFs composite material and preparation method and application thereof
CN110931782A (en) * 2019-11-15 2020-03-27 中南大学 Preparation method and application of hollow sphere cobalt sulfide/graphene composite material
CN110668433A (en) * 2019-11-25 2020-01-10 陕西师范大学 Method for preparing graphite/graphene composite material by supercritical carbon dioxide fluid and application
CN114094106A (en) * 2021-11-23 2022-02-25 山东大学 Ammonium polyphosphate modified graphite negative electrode material and preparation method and application thereof
CN114094106B (en) * 2021-11-23 2023-08-11 山东大学 Ammonium polyphosphate modified graphite negative electrode material and preparation method and application thereof
CN114975925A (en) * 2022-05-24 2022-08-30 广东凯金新能源科技股份有限公司 Phosphorus-graphene doped composite graphite negative electrode material and preparation method thereof

Also Published As

Publication number Publication date
CN106941151B (en) 2019-07-12

Similar Documents

Publication Publication Date Title
CN106941151A (en) A kind of graphene composite graphite negative electrode material and its preparation method and application
CN105895886B (en) A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof
CN104603060B (en) The preparation method of lithium iron phosphate nano powder
CN104659359B (en) A kind of lithium ion cell nano piece is overlapped piles up cube Mn(3‑x)CoxO4The preparation method of negative material
CN108017050A (en) A kind of doped graphene and its preparation method and application
CN106549155A (en) A kind of potassium sodium ferromanganese base prussian blue electrode material and its preparation method and application
CN106229503B (en) A kind of preparation method of nickel oxide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery
CN106252628B (en) A kind of preparation method of manganese oxide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery
CN105355866A (en) Preparation method of cobaltosic oxide composite graphene three-dimensional aerogel
CN108461739A (en) A kind of high performance lithium ionic cell cathode material Fe7S8The preparation method of/C
CN106129377A (en) The preparation method of a kind of sesquioxide/graphene composite material, lithium ion battery negative, lithium ion battery
CN106450193A (en) Nickel sulfide/graphene composite material and preparation method and application thereof
CN107275571A (en) A kind of full battery of lithium sulfide/nano-silicone wire/carbon and preparation method and application
CN104192810A (en) Preparation method of layered double hydroxide with large interlayer spacing
CN106848192A (en) Layered porous iron oxide electrode material and preparation method thereof, lithium ion cell electrode piece and preparation method thereof and lithium ion battery
CN108117103A (en) A kind of vanadic acid cobalt compound and preparation method and application
CN109065874A (en) A kind of MoO3/ rGO-N nanocomposite and its preparation method and application
CN106340400B (en) A kind of carbon coating rhombic system nano bar-shape Nb2O5Material and preparation method thereof
CN109904395A (en) A kind of molybdenum disulfide-graphene composite material
CN105870440B (en) A kind of preparation method and applications of bowknot shape cobaltosic oxide
CN106409520A (en) Method for preparing electrode material of lithium-ion-mixed capacitor and application thereof
CN103531809A (en) Preparation method and application of core-shell structural particle and graphene composite material
CN104617290B (en) Homogenous precipitation method for preparing Fe2O3 nanobelt and Fe2O3 nanobelt-carbon composite material
CN109534401B (en) Preparation method of copper vanadate, copper vanadate prepared by method and application of copper vanadate in lithium ion battery
CN107834045A (en) A kind of preparation method of bar-shaped carbon coating cobalt molybdate and its application in lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190712

Termination date: 20220105