CN106941151B - 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 PDFInfo
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- 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
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Abstract
The present invention provides a kind of graphene composite graphite negative electrode materials and its preparation method and application, which comprises a) graphene, graphite and auxiliary agent are added in supercritical fluid；It is uniformly mixing to obtain mixture；B) the obtained mixture of step a) is spray-dried, collection obtains powder；C) powder calcination for obtaining step b) obtains the graphene composite graphite negative electrode material.The present invention can effectively improve the chemical property of lithium ion battery negative material.To prepare there is the lithium ion battery of more preferable chemical property to provide ideal negative electrode material, is an important breakthrough in electrochemical applications field.
Description
Technical field
The present invention provides a kind of graphene composite graphite negative electrode materials and its preparation method and application, belong to energy technology
Field.
Background technique
A kind of carbon material of the graphene as New Two Dimensional structure is to be found for the first time by Novoselov et al. in 2004
(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, there is excellent conductive capability, be able to bear the current density of six orders of magnitude higher than copper, has and sets a record
The capacity of heat transmission, and at the same time have high rigidity and good ductility (Geim, A.K.Science 2009,324,1530-
4).In addition, if it is possible to which graphene, this typical two-dimension plane structure material is arbitrarily cut out, so that it may obtain different
The grapheme material of performance.A series of this excellent performance of graphene make it have potential application prospect in many fields,
Hot spot as recent research.
Lithium ion battery have many advantages, such as energy density is high, have extended cycle life and memory-less effect and be widely used in just
It takes in formula electronic equipment.In recent years, the development of electrical equipment proposed more the power density and energy density of lithium ion battery
High requirement, and electrode material is the deciding factor that performance of lithium ion battery improves.In terms of negative electrode material, it is commercialized at present
Graphite as anode material for lithium-ion battery theoretical capacity (372mAh g-1) relatively low, limit lithium ion battery chemical property
It improves, therefore designing and preparing high performance lithium ionic cell cathode material is the pass for meeting lithium ion battery and developing to electrical equipment
Key factor.New carbon graphene is due to electric conductivity, lower charge transfer resistance, the specific surface area of super large with superelevation
Various potential using values are shown with many characteristics such as interlamellar spacing, stable mechanical performance and lithium ion storage performances, are to work as
The hot spot of prescience area research is also considered as the potential ideal material of negative electrode of lithium ion battery.But simple graphene is negative
Pole material is same to limit because its irreversible capacity is larger, cyclical stability is poor and the reasons such as unstable voltage platform
Its application in terms of lithium-ion negative pole battery material.Therefore, a kind of cyclicity with high specific capacity, more stable is obtained
The lithium ion battery negative material of energy, high rate performance and stable voltage platform still requires study.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of graphene composite graphite negative electrode material；
Another object of the present invention is to provide the graphene composite graphite negative electrode materials that the preparation method is prepared
Material；
Another object of the present invention is to provide the battery cathode of the graphene composite graphite negative electrode material preparation；
A further object of the present invention is to provide the graphene composite graphite negative electrode materials in preparation battery cathode
Application.
In order to achieve the above object, on the one hand, the present invention provides a kind of preparation method of graphene composite graphite negative electrode material,
Wherein, which comprises
A) graphene, graphite and auxiliary agent are added in supercritical fluid, are uniformly mixing to obtain mixture；
B) the obtained mixture of step a) is spray-dried, collection obtains powder；
C) powder calcination for obtaining step b) obtains the graphene composite graphite negative electrode material.
Some specific embodiments according to the present invention, wherein the graphite is natural flake graphite (average grain diameter 15-20
Micron) or artificial graphite.
Some specific embodiments according to the present invention, wherein graphite purity is greater than 99%.
Some specific embodiments according to the present invention, wherein the mass ratio of graphene and graphite is 1:1-100.
Some specific embodiments according to the present invention, wherein the mass ratio of supercritical fluid and graphite is 0.1-100:1.
Still other specific embodiment according to the present invention, wherein the mass ratio of supercritical fluid and graphite is 1-10:1.
Other specific embodiment according to the present invention, wherein the mass ratio of supercritical fluid and graphite is 1:1.
Some specific embodiments according to the present invention, wherein the auxiliary agent quality dosage is the 0.1- of graphene quality
100%.
Some specific embodiments according to the present invention, wherein it is sweet that the auxiliary agent is selected from neopelex, fatty acid
Grease, N-methyl pyrrolidones, sulphur simple substance, red phosphorus, black phosphorus, ethyl alcohol, carbon disulfide, toluene, nickel nitrate, cobalt nitrate, manganese nitrate,
The mixing of one or more of nickelous carbonate, cobalt carbonate and manganese carbonate.
Some specific embodiments according to the present invention, wherein step c) is the powder that obtains step b) in inert gas
It is calcined in atmosphere.
Some specific embodiments according to the present invention, wherein the inert gas is nitrogen.
Some specific embodiments according to the present invention, wherein the temperature of the step c) calcining is 300-800 DEG C；Wherein
Preferred calcination temperature is 600 DEG C.
Some specific embodiments according to the present invention, wherein the time of the step c) calcining is 0.5-2h.
Some specific embodiments according to the present invention, wherein the graphene is doped graphene.
Some specific embodiments according to the present invention, wherein the doped graphene is to mix one of S, N and P or two
Kind or more mixing.
Some specific embodiments according to the present invention, wherein when the doped graphene contain one of S, N and P or
When a variety of, the respective doping of S, N and P is independently are as follows: S:0.5-5wt%, N:0.5-5wt%, P:0.1-2%.
That is, no matter adulterated in doped graphene be one or more of S, N and P mixing, as long as
Wherein contain S, then the doping of S is just 1.23-2.95wt%；As long as wherein containing N, then the doping of N is 1.95-
3.35wt%；As long as wherein containing P, then the doping of P is 0.21-1.34wt%.
Graphene of the present invention can be used existing conventional graphene, and some specific embodiment parties according to the present invention
Case, the graphene are the graphene that supercritical fluid method is prepared.
Some specific embodiments according to the present invention, wherein the preparation of the graphene includes:
(1) using graphite as raw material, after being mixed with additive, oxidant according to the ratio of mass ratio 0.1-20:0.1-50:1
It is reacted, heating reaction after treatment obtains expanded graphite；
(2) expanded graphite that step (1) obtains is sheared, obtains powdery solid；
(3) organic solvent is dispersed by the powdery solid that step (2) obtains, stirs 0.1-10h in 30-90 DEG C of laser heating
Re-ultrasonic dispersion 0.1-1h afterwards becomes uniform Dark grey to liquid；
(4) the Dark grey product that step (3) obtains is uniformly mixed in autoclave with Co 2 supercritical fluid
To mixture；
(5) mixture that step (4) obtains is sprayed onto non-pressure vessel by nozzle, obtains powdery graphite alkene.
Some specific embodiments according to the present invention, wherein step (1) is using graphite as raw material, with additive, oxidant
According to being reacted after the ratio mixing of mass ratio 2:10:1, heating reaction after treatment obtains expanded graphite；
Some specific embodiments according to the present invention, wherein the additive is selected from iron chloride, copper chloride, manganese chloride, three
Poly cyanamid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium polyphosphate, peroxophosphoric acid sodium, sodium nitrate, ammonium nitrate, ferric nitrate, nitric acid
Cobalt, nickel nitrate, copper nitrate, manganese nitrate, zinc nitrate, sodium thiosulfate, sodium peroxydisulfate, magnesium sulfate, cobaltous sulfate, ferric sulfate, sulfuric acid
The mixing of one or more of ferrous iron, nickel sulfate, manganese sulfate and lithium phosphate.
Some specific embodiments according to the present invention, wherein the oxidant is selected from sulfuric acid, nitric acid, phosphoric acid, acetic acid, second
The mixture of one or more of acid anhydrides, oxalic acid, potassium permanganate, hydrogen peroxide and potassium bichromate.
Some specific embodiments according to the present invention, wherein using graphite as raw material, mixed with additive and oxidant laggard
Row reaction 2-12h.
Other specific embodiments according to the present invention, wherein using graphite as raw material, after being mixed with additive and oxidant
Carry out reaction 12h.
Some specific embodiments according to the present invention, wherein using graphite as raw material, mixed with additive and oxidant laggard
Row reaction, is heated to 550-900 DEG C of reaction after treatment and obtains expanded graphite.
Some specific embodiments according to the present invention, wherein preferably be heated to 550-900 DEG C of reaction 0.5-2h obtain it is swollen
Swollen graphite.
Other specific embodiment according to the present invention, wherein being heated to 750 DEG C of reactions obtains expanded graphite.
Some specific embodiments according to the present invention, wherein step (1) is using graphite as raw material, with additive, oxidant
It is reacted after mixing, after treatment, is reacted after obtained product is mixed with additive, oxidant again, using
After processing, heating obtains expanded graphite.
Wherein, the additive being separately added into twice may be the same or different.
The oxidant being separately added into twice also may be the same or different.
Some specific embodiments according to the present invention, wherein step (1) processing is graphite and additive and oxidant
After reaction, the obtained product of reaction is washed with hydrochloric acid solution, be washed with water that wash to pH be 6-7.5, filtering obtains filter cake.
Some specific embodiments according to the present invention, wherein step (1) hydrochloric acid solution is the dense of volume ratio 1:1-10
Hydrochloric acid and water are prepared.
Wherein preferably preparing obtained hydrochloric acid solution mass concentration is 6wt%.
Some specific embodiments according to the present invention, wherein step (1) is using graphite as raw material, with additive and oxidation
It is reacted after agent mixing, the product that reaction obtains is washed with hydrochloric acid solution, be washed with water and wash three times, filtering, filtration cakes torrefaction
Heating reaction afterwards obtains expanded graphite.
Some specific embodiments according to the present invention, wherein step (1) is using graphite as raw material, with additive and oxidation
Reacted after agent mixing, the obtained product of reaction washed with hydrochloric acid solution, is washed with water and washs three times, filtering, filter cake again with
It is reacted after additive and oxidant mixing, the product that reaction obtains is washed with hydrochloric acid solution, is washed with water and washs three times, mistake
It filters, heating obtains expanded graphite after filtration cakes torrefaction.
Some specific embodiments according to the present invention, wherein step (2) shearing rotating speed is 5000-20000rpm.
Some specific embodiments according to the present invention, wherein step (3) is surpassed again after 70 DEG C of laser heatings stir 0.5h
Sound disperses 0.5h, becomes uniform Dark grey to liquid.
Some specific embodiments according to the present invention, wherein step (3) organic solvent is selected from ethyl alcohol, ether, N- first
The mixing of one or more of base pyrrolidones (NMP) and dimethylformamide (DMF).
Some specific embodiments according to the present invention, wherein step (3) consumption of organic solvent is every 1g powdery solid
It is scattered in 10-300ml organic solvent.
Other specific embodiments according to the present invention, wherein step (3) consumption of organic solvent is solid for every 1g powdery
Body is scattered in 30ml organic solvent.
Some specific embodiments according to the present invention, wherein step (4) is the Dark grey product that obtains (3) in 8-
It is uniformly mixed under 20MPa with Co 2 supercritical fluid.
Some specific embodiments according to the present invention, wherein step (4) is the product for obtaining step (3) and titanium dioxide
Carbon supercritical fluid 1:0.5-100 in mass ratio is uniformly mixed.
Other specific embodiments according to the present invention, wherein step (4) is the product and dioxy for obtaining step (3)
Change carbon supercritical fluid 1:1 in mass ratio to be uniformly mixed.
Some specific embodiments according to the present invention, wherein step (4) is the product at room temperature obtaining step (3)
It is uniformly mixed with Co 2 supercritical fluid.
Some specific embodiments according to the present invention, wherein the jet expansion internal diameter of step (5) is 1-20mm.
On the other hand, the present invention also provides the graphene composite graphite negative electrode materials that the preparation method is prepared
Material.
Another aspect, the present invention also provides the battery cathode of graphene composite graphite negative electrode material preparation.
Some specific embodiments according to the present invention, wherein the battery is lithium ion battery.
In another aspect, the present invention also provides provide the graphene composite graphite negative electrode material in preparation battery cathode
In application.
Some specific embodiments according to the present invention, wherein the battery is lithium ion battery.
In conclusion the present invention provides a kind of graphene composite graphite negative electrode materials and its preparation method and application.This
The graphene composite graphite negative electrode material of invention has the advantages that
Cost is relatively low for composite technology of the invention, is suitble to heavy industrialization application.
The present invention can effectively improve the chemical property of lithium ion battery negative material.Relative to industrial commonly used
Graphite cathode material, the specific capacity of negative electrode material greatly improved in this graphene-graphite cathode material；While compared to
It is simple using grapheme material as negative electrode material, not only efficiently controlled material cost, but also improve the circulation of material
Stability, and material is made to present stable voltage platform during charge and discharge.In conclusion the invention is preparation
Lithium ion battery with more preferable chemical property provides ideal negative electrode material, is a Xiang Chong great in electrochemical applications field
It breaks through.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) picture of the untreated natural flake graphite of embodiment 1；
Fig. 2 is scanning electron microscope (SEM) picture of the expanded graphite of embodiment 1；
Fig. 3 is the transmission of the multi-layer graphene obtained after the supercritical fluid method described through the invention of embodiment 1 is handled
Electronic Speculum (TEM)；
Fig. 4 is that graphene-graphite composite material that embodiment 1 is prepared is used as active matter in ion cathode material lithium
The curve of double curvature of matter；
Fig. 5 is that graphene-graphite composite material that embodiment 1 is prepared is used as active matter in ion cathode material lithium
The charge-discharge test curve of matter；
Fig. 6 is that graphene-graphite composite material that embodiment 1 is prepared is used as active matter in ion cathode material lithium
100 circle cyclic curve (150mA g of matter-1)；
Fig. 7 is that graphene-graphite composite material that embodiment 3 is prepared is used as active matter in ion cathode material lithium
The curve of double curvature of matter；
Fig. 8 is that graphene-graphite composite material that embodiment 3 is prepared is used as active matter in ion cathode material lithium
The charge-discharge test curve of matter；
Fig. 9 is that graphene-graphite composite material that embodiment 3 is prepared is used as active matter in ion cathode material lithium
100 circle cyclic curve (150mA g of matter-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 substance；
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 substance；
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 substance-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 substance；
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 substance；
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 substance-1)；
Figure 16 is for graphite material in comparative example 1 as the curve of double curvature of active material in ion cathode material lithium；
Figure 17 is that graphite material is bent as the charge-discharge test of active material in ion cathode material lithium in comparative example 1
Line.
Specific embodiment
Below by way of the beneficial effect of the specific embodiment implementation process that the present invention will be described in detail and generation, it is intended to which help is read
Reader more fully understands essence and feature of the invention, does not limit the scope of the present invention.
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 uniformly mixed with 5g potassium permanganate powder, is added the 50g concentrated sulfuric acid (80wt%), uniform stirring,
12h is reacted at room temperature.
B. gained suspension is washed with dilute hydrochloric acid (6wt%), then is washed repeatedly three times with deionized water, filtering obtains
Filter cake.
C. products therefrom is reentered into reactor and is reacted, is added the 12.5g concentrated sulfuric acid (80wt%), 10g dioxygen
Water, uniform stirring react 3h at room temperature.
D. gained suspension is washed with dilute hydrochloric acid (6wt%), then is washed repeatedly three times with deionized water, measured pH value and exist
Between 6-7.5, filtering obtains filter cake.
E., products therefrom is heated to reaction 1h at 750 DEG C, because the presence of oxidation intercalation functional group, expanded by heating make stone
The distance between ink sheet layer significantly increases, and the scanning electron microscopic picture of former graphite flake is shown in Fig. 1, the Product scan Electronic Speculum after heat treatment
Picture is shown in Fig. 2.
F. obtained product is sheared with high-speed shearing machine (JRJ301-1H).
G. the sample after shear treatment is mixed with 100ml dimethylformamide (DMF), is ultrasonically treated 2h.
H. products therefrom is put into autoclave, is passed through Co 2 supercritical fluid, pressure 10Mpa, temperature is
Room temperature stirs evenly.The Co 2 supercritical fluid for being dispersed with expanded graphite is sprayed onto a normal pressure by autoclave nozzle
In bulk container, collect to obtain graphene powder in container bottom.Its transmission electron microscope picture is as shown in Figure 3.
2. the preparation of graphene-composite cathode material of silicon/carbon/graphite
The crystalline flake graphite of graphene obtained in step 1 and 80 mesh 1:1 in mass ratio is added to CO 2 supercritical
In fluid, the mass ratio of supercritical fluid and graphite is 1:1, toluene is also added in mixture simultaneously, wherein graphene: first
Benzene (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.It is compound to obtain graphene-graphite
Material.
Embodiment 2
It present embodiments provides and is born by graphene-graphite composite material that embodiment 1 is prepared as lithium ion battery
The application of pole material activity substance comprising following steps:
A. by the graphene-graphite composite material prepared in 0.4g embodiment 1 and 0.714g Kynoar solution
(PVDF, 7wt%) and 0.05g carbon black are mixed evenly and negative electrode material are made, wherein graphene-graphite composite material is made
For active material, Kynoar is as adhesive, and carbon black is as conductive agent.
B. by above-mentioned negative electrode material coater even spread on aluminium foil, lithium ion cell positive is made in drying；It is filling
Anode, lithium piece, diaphragm and electrolyte are assembled into lithium ion battery according to battery assembly technique in the glove box of full argon atmosphere；
Wherein, diaphragm uses U.S. celgard2400, and electrolyte is the 1mol/L solution of LiPF6, and solvent EC, EMC, DMC is according to body
Mixed liquor of the product than 1:1:1.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.Group installs
Lithium ion battery is placed 12h by Cheng Hou, and charge-discharge magnification performance test is carried out on charge-discharge test instrument.
Multiplying power test result is as shown in figure 4, as can be seen from Figure 4 use graphene-graphite composite material as lithium
Ion battery cathode material active material is in 150mA g-1Its specific capacity reaches 429mAh g under electric current-1, it is apparently higher than common stone
The 372mAh g of ink material-1, show that the composite material makes the capacity of battery be significantly improved；Charging and discharging curve such as Fig. 5
It is shown, it can be seen that have stable voltage platform near 0.2-0.3V；Test results are shown in figure 6 for cyclical stability, is following
After ring 100 encloses, capacity is not decayed, and shows that the composite material has very good cyclical stability.According to the above test
As a result it can be concluded that, it is as lithium ion battery that this graphene-graphite composite material, which has very excellent chemical property,
The ideal material of negative electrode active material.
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 peroxydisulfate are uniformly mixed, the 50g concentrated sulfuric acid is added
(80wt%), uniform stirring react 12h at room temperature.
B. gained suspension is washed with hydrochloric acid (6wt%), then is washed repeatedly three times with deionized water, filtering is filtered
Cake.
C. products therefrom is reentered into reactor and is reacted, is added the 12.5g concentrated sulfuric acid (80wt%), 10g dioxygen
Water, uniform stirring react 3h at room temperature.
D. gained suspension is washed with hydrochloric acid (6wt%), then is washed repeatedly with deionized water and measures pH value three times in 6-
Between 7.5, filtering obtains filter cake.
E., products therefrom is heated to reaction 0.5h at 800 DEG C.
F. obtained product is sheared with high-speed shearing machine (JRJ301-1H).
G. the sample after shear treatment is mixed with 100ml dimethylformamide (DMF), is ultrasonically treated 2h.
Products therefrom is put into autoclave, Co 2 supercritical fluid, pressure 10Mpa are passed through, temperature is room
Temperature stirs evenly.It obtains product and mixes sulfur graphite alkene.
2. the preparation of graphene-composite cathode material of silicon/carbon/graphite
A. the crystalline flake graphite 1:100 in mass ratio of graphene obtained in step 1 and 80 mesh carbon dioxide is added to surpass
In critical fluids (mass ratio of carbon dioxide and graphite is 100:1), toluene and neopelex are also added 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.It is multiple to obtain graphene-graphite
Condensation material.
Embodiment 4
It present embodiments provides and is born by graphene-graphite composite material that embodiment 3 is prepared as lithium ion battery
The application of pole material activity substance comprising following steps:
A. by the graphene-graphite composite material prepared in 0.4g embodiment 3 and 0.714g Kynoar solution
(PVDF, 7wt%) and 0.05g carbon black are mixed evenly and negative electrode material are made, wherein graphene-graphite composite material is made
For active material, Kynoar is as adhesive, and carbon black is as conductive agent.
B. by above-mentioned negative electrode material coater even spread on aluminium foil, lithium ion cell positive is made in drying；It is filling
Anode, lithium piece, diaphragm and electrolyte are assembled into lithium ion battery according to battery assembly technique in the glove box of full argon atmosphere；
Wherein, diaphragm uses U.S. celgard2400, and electrolyte is the 1mol/L solution of LiPF6, and solvent EC, EMC, DMC is according to body
Mixed liquor of the product than 1:1:1.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.Group installs
Lithium ion battery is placed 12h by Cheng Hou, and charge-discharge magnification performance test is carried out on charge-discharge test instrument.
Multiplying power test result is as shown in fig. 7, as can be seen from Figure 7 use graphene-graphite composite material as lithium
Ion battery cathode material active material its specific capacity under 150mA g-1 electric current has reached 440mAh g-1, is apparently higher than general
The 372mAh g-1 of logical graphite material, shows that the composite material makes the capacity of battery be significantly improved；Charging and discharging curve
As shown in Figure 8, it can be seen that have stable voltage platform near 0.2-0.3V；Test results are shown in figure 9 for cyclical stability,
After the circle of circulation 100, capacity is not decayed, and shows that the composite material has very good cyclical stability.According to above
Test result it can be concluded that, this graphene-graphite composite material have very excellent chemical property, be as lithium ion
The ideal material of battery cathode active substance.
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 uniformly mixed, the 50g concentrated sulfuric acid is added
(80wt%), uniform stirring react 12h at room temperature.
B. gained suspension is washed with hydrochloric acid (6wt%), then is washed repeatedly three times with deionized water, filtering is filtered
Cake.
C. products therefrom is reentered into reactor and is reacted, is added the 12.5g concentrated sulfuric acid (80wt%), 10g dioxygen
Water, uniform stirring react 3h at room temperature.
D. gained suspension is washed with hydrochloric acid (6wt%), then is washed repeatedly three times with deionized water, measure pH value in 6-
Between 7.5, filtering obtains filter cake.
E., products therefrom is heated to reaction 45min at 700 DEG C.
F. obtained product is sheared with high-speed shearing machine (JRJ301-1H).
G. the sample after shear treatment is mixed with 100ml dimethylformamide (DMF), is ultrasonically treated 2h.
Products therefrom is put into autoclave, Co 2 supercritical fluid, pressure 10Mpa are passed through, temperature is room
Temperature stirs evenly.Obtain p-doped graphene.
2. the preparation of graphene-composite cathode material of silicon/carbon/graphite
The crystalline flake graphite of graphene obtained in step 1 and 80 mesh 1:1 in mass ratio is added to CO 2 supercritical by a
In fluid (mass ratio of carbon dioxide and graphite is 10:1), toluene and ammonium polyphosphate are also added in mixture simultaneously, 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.It is multiple to obtain graphene-graphite
Condensation material.
Embodiment 6
It present embodiments provides and is born by graphene-graphite composite material that embodiment 5 is prepared as lithium ion battery
The application of pole material activity substance comprising following steps.
By the graphene-graphite composite material prepared in 0.4g embodiment 5 and 0.714g Kynoar solution (PVDF,
7wt%) and 0.05g carbon black is mixed evenly and negative electrode material is made, wherein graphene-graphite composite material is as activity
Substance, Kynoar is as adhesive, and carbon black is as conductive agent.
By above-mentioned negative electrode material coater even spread on aluminium foil, lithium ion cell positive is made in drying；It is being full of
Anode, lithium piece, diaphragm and electrolyte are assembled into lithium ion battery according to battery assembly technique in the glove box of argon atmosphere；Its
In, diaphragm uses U.S. celgard2400, and electrolyte is the 1mol/L solution of LiPF6, and solvent EC, EMC, DMC is according to volume
Mixed liquor than 1:1:1.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.It is completed
Afterwards, lithium ion battery is placed into 12h, charge-discharge magnification performance test is carried out on charge-discharge test instrument.
Test results are shown in figure 10 for multiplying power, as can be seen from Figure 10 uses graphene-graphite composite material as lithium
Ion battery cathode material active material its specific capacity under 150mA g-1 electric current has reached 439mAh g-1, it is apparently higher than common
The 372mAh g of graphite material-1, show that the composite material makes the capacity of battery be significantly improved；Charging and discharging curve is as schemed
Shown in 11, it can be seen that have stable voltage platform near 0.2-0.3V；Cyclical stability test result is as shown in figure 12,
After 100 circle of circulation, capacity is not decayed, and shows that the composite material has very good cyclical stability.It is surveyed according to above
Test result it can be concluded that, this graphene-graphite composite material have very excellent chemical property, be as lithium-ion electric
The ideal material of pond negative electrode active material.
Embodiment 7
1. the preparation of graphene
A. 10g graphite is mixed with 2.5g potassium permanganate, 2.5g potassium bichromate, is added the 50g concentrated sulfuric acid (80wt%), uniformly
Stirring, reacts 12h at room temperature.
B. gained suspension is washed three times repeatedly with hydrochloric acid (6wt%), then is washed repeatedly three times with deionized water, mistake
Filter, obtains filter cake.
C. 0.5h will be reacted in 800 DEG C of heating after products therefrom drying, obtains expanded graphite product.F. the product that will be obtained
It is sheared with high-speed shearing machine (JRJ301-1H).
D. the sample after shear treatment is mixed with 100ml dimethylformamide (DMF), is ultrasonically treated 2h.
E. products therefrom is put into autoclave, is passed through Co 2 supercritical fluid, pressure 10Mpa, temperature
For room temperature, stir evenly.The Co 2 supercritical fluid for being dispersed with expanded graphite is sprayed by autoclave nozzle
Into a normal pressure bulk container, collect to obtain graphene powder in container bottom.
2. the preparation of graphene-composite cathode material of silicon/carbon/graphite
The crystalline flake graphite of graphene obtained in step 1 and 80 mesh is added in Co 2 supercritical fluid, by rouge
Fatty acid glyceride is also added in mixture simultaneously, wherein graphene: graphite: supercritical fluid: fatty glyceride (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.It is compound to obtain graphene-graphite
Material.
Embodiment 8
It present embodiments provides and is born by graphene-graphite composite material that embodiment 7 is prepared as lithium ion battery
The application of pole material activity substance comprising following steps.
A. by the graphene-graphite composite material prepared in 0.4g embodiment 7 and 0.714g Kynoar solution
(PVDF, 7wt%) and 0.05g carbon black are mixed evenly and negative electrode material are made, wherein graphene-graphite composite material is made
For active material, Kynoar is as adhesive, and carbon black is as conductive agent.
B. by above-mentioned negative electrode material coater even spread on aluminium foil, lithium ion cell positive is made in drying；It is filling
Anode, lithium piece, diaphragm and electrolyte are assembled into lithium ion battery according to battery assembly technique in the glove box of full argon atmosphere；
Wherein, diaphragm uses U.S. celgard2400, and electrolyte is the 1mol/L solution of LiPF6, and solvent EC, EMC, DMC is according to body
Mixed liquor of the product than 1:1:1.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.Group installs
Lithium ion battery is placed 12h by Cheng Hou, and charge-discharge magnification performance test is carried out on charge-discharge test instrument.
Multiplying power test result is for example as shown in figure 13, as can be seen from Figure 13 use graphene-graphite composite material as
Lithium ion battery negative material active material is in 150mA g-1Its specific capacity reaches 429mAh g under electric current-1, it is apparently higher than common
The 372mAh g of graphite material-1, show that the composite material makes the capacity of battery be significantly improved；Charging and discharging curve is as schemed
Shown in 14, it can be seen that have stable voltage platform near 0.2-0.3V；Cyclical stability test result is as shown in figure 15,
After 100 circle of circulation, capacity is not decayed, and shows that the composite material has very good cyclical stability.It is surveyed according to above
Test result it can be concluded that, this graphene-graphite composite material have very excellent chemical property, be as lithium-ion electric
The ideal material of pond negative electrode active material.
Comparative example 1
This comparative example is using existing natural flake graphite material directly as lithium ion battery negative material.
0.4g natural flake graphite and 0.714g Kynoar solution (PVDF, 7wt%) and 0.05g carbon black are mixed
It stirs evenly and negative electrode material is made, wherein natural flake graphite is as active material, and Kynoar is as adhesive, carbon black
As conductive agent.
By above-mentioned negative electrode material coater even spread on aluminium foil, lithium ion cell positive is made in drying；It is being full of
Anode, lithium piece, diaphragm and electrolyte are assembled into lithium ion battery according to battery assembly technique in the glove box of argon atmosphere；Its
In, diaphragm uses U.S. celgard2400, and electrolyte is the 1mol/L solution of LiPF6, and solvent EC, EMC, DMC is according to volume
Mixed liquor than 1:1:1.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.It is completed
Afterwards, lithium ion battery is placed into 12h, charge-discharge magnification performance test is carried out on charge-discharge test instrument.
Curve of double curvature is as shown in figure 16, in 150mA g-1When its capacity be 355mAh g-1, it is lower than its theoretical capacity, and remote
Lower than graphene-graphite composite material of the present invention, charging and discharging curve such as Figure 17.It is proved by this comparative example, this hair
Bright graphene-the graphite composite material is the potential ideal optimization material of existing graphite cathode material.
Claims (20)
1. a kind of preparation method of graphene composite graphite negative electrode material, wherein the described method includes:
A) graphene, graphite and auxiliary agent are added in supercritical fluid, the mass ratio of supercritical fluid and graphite is 0.1-100:
1；It is uniformly mixing to obtain mixture；The mass ratio of graphene and graphite is 1:1-100；The auxiliary agent quality dosage is graphene matter
The 0.1-100% of amount；The graphene is the graphene that supercritical fluid method is prepared, comprising the following steps:
(1) it using graphite as raw material, is carried out after being mixed with additive, oxidant according to the ratio of mass ratio 0.1-20:0.1-50:1
Reaction, is heated to 550-900 DEG C of reaction after treatment and obtains expanded graphite；The oxidant be selected from sulfuric acid, nitric acid, phosphoric acid,
Acetic acid, acetic anhydride, oxalic acid, potassium permanganate and potassium bichromate one or more of mixture；
(2) expanded graphite that step (1) obtains is sheared, shearing rotating speed 5000-20000rpm obtains powdery solid；
(3) organic solvent is dispersed by the powdery solid that step (2) obtains, after 30-90 DEG C of laser heating stirs 0.1-10h again
Ultrasonic disperse 0.1-1h becomes uniform Dark grey to liquid；The organic solvent is selected from ethyl alcohol, ether, N-Methyl pyrrolidone
With the mixing of one or more of dimethylformamide；Consumption of organic solvent is that every 1g powdery solid is scattered in 10-
300ml organic solvent；
(4) the Dark grey product for obtaining step (3) in autoclave with Co 2 supercritical fluid 1:0.5- in mass ratio
100 be uniformly mixed obtain mixture；
(5) mixture that step (4) obtains is sprayed onto non-pressure vessel by nozzle, obtains powdery graphite alkene；
B) the obtained mixture of step a) is spray-dried, collection obtains powder；
C) powder calcination for obtaining step b) obtains the graphene composite graphite negative electrode material；The temperature of the calcining
It is 300-800 DEG C；Calcination time is 0.5-2h.
2. preparation method according to claim 1, wherein the graphite is natural flake graphite or artificial graphite.
3. preparation method according to claim 1, wherein the graphite purity is greater than 99%.
4. preparation method according to claim 1, wherein the mass ratio of supercritical fluid and graphite is 1-10:1.
5. preparation method according to claim 1, wherein the mass ratio of supercritical fluid and graphite is 1:1.
6. preparation method according to claim 1, wherein the graphene is doped graphene.
7. preparation method according to claim 6, wherein the doped graphene is to mix one or both of S, N and P
Above graphene.
8. preparation method according to claim 7, wherein when the doped graphene contains one of S, N and P or more
When kind, the respective doping of S, N and P is independently are as follows: S:0.5-5wt%, N:0.5-5wt%, P:0.1-2%.
9. preparation method according to claim 1, wherein it is sweet that the auxiliary agent is selected from neopelex, fatty acid
Grease, N-methyl pyrrolidones, sulphur simple substance, red phosphorus, black phosphorus, ethyl alcohol, carbon disulfide, toluene, nickel nitrate, cobalt nitrate, manganese nitrate,
The mixing of one or more of nickelous carbonate, cobalt carbonate and manganese carbonate.
10. preparation method according to claim 1, wherein (1) of step a) include using graphite as raw material, with additive,
Oxidant is heated to 550- according to reaction 2-12h is carried out after the ratio mixing of mass ratio 0.1-20:0.1-50:1 after treatment
900 DEG C of reactions obtain expanded graphite.
11. preparation method according to claim 1, wherein (1) of step a) is heated to 550-900 after treatment
DEG C keep 0.5-2h obtain expanded graphite.
12. preparation method according to claim 1, wherein (4) of step a) include that the product that step (3) obtains exists
It is uniformly mixed under 8-20MPa with Co 2 supercritical fluid.
13. preparation method according to claim 1, wherein (4) of step a) include at room temperature obtaining step (3)
Product be uniformly mixed with Co 2 supercritical fluid.
14. preparation method according to claim 1, wherein step c) includes the powder that obtains step b) in indifferent gas
It is calcined in body atmosphere.
15. preparation method according to claim 1, wherein the additive is selected from iron chloride, copper chloride, manganese chloride, three
Poly cyanamid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium polyphosphate, peroxophosphoric acid sodium, sodium nitrate, ammonium nitrate, ferric nitrate, nitric acid
Cobalt, nickel nitrate, copper nitrate, manganese nitrate, zinc nitrate, sodium thiosulfate, sodium peroxydisulfate, magnesium sulfate, cobaltous sulfate, ferric sulfate, sulfuric acid
The mixing of one or more of ferrous iron, nickel sulfate, manganese sulfate, lithium phosphate and hydrogen peroxide.
16. the graphene composite graphite negative electrode material that preparation method described in claim 1~15 any one is prepared.
17. the battery cathode of the preparation of graphene composite graphite negative electrode material described in claim 16.
18. battery cathode according to claim 17, wherein the battery is lithium ion battery.
19. application of the graphene composite graphite negative electrode material described in claim 16 in preparation battery cathode.
20. application according to claim 19, wherein the battery is lithium ion battery.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN110931782B (en) * | 2019-11-15 | 2021-01-15 | 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 |
| 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 |
| CN114975925B (en) * | 2022-05-24 | 2024-06-07 | 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 |
| CN117923483B (en) * | 2023-12-14 | 2024-11-08 | 云南中晟新材料有限责任公司 | Graphite material and preparation method and application thereof |
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