CN108017050A - A kind of doped graphene and its preparation method and application - Google Patents
A kind of doped graphene and its preparation method and application Download PDFInfo
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- CN108017050A CN108017050A CN201610943741.2A CN201610943741A CN108017050A CN 108017050 A CN108017050 A CN 108017050A CN 201610943741 A CN201610943741 A CN 201610943741A CN 108017050 A CN108017050 A CN 108017050A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of doped graphene and its preparation method and application.The described method includes：(1) graphite is mixed with oxidant, dopant, intercalated graphite is prepared；It is preferred that the mass ratio of graphite, oxidant and dopant is 1：1‑20：0.1‑10；(2) intercalated graphite that step (1) obtains is calcined to obtain expanded graphite；(3) expanded graphite for obtaining step (2) is peeled off to obtain the doped graphene by solvent.The specific capacity of negative material greatly improved in this doped multi-layer graphene negative material；Material cost is not only efficiently controlled, but also improve the stable circulation performance of material using grapheme material as negative material compared to simple at the same time.
Description
Technical field
The present invention relates to energy technology field, is to be related to a kind of doped graphene and preparation method thereof and answer specifically
With.
Background technology
Graphene as a kind of carbon material of New Two Dimensional structure, was found first in 2004 by Novoselov et al.
(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, the current density of six orders of magnitude higher than copper can be born, has and sets a record
The 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 possible to obtain different
The grapheme material of performance.A series of this excellent performance of graphene make it have potential application prospect in many fields,
As the hot spot of recent research.The preparation method of graphene mainly includes micromechanics stripping method, chemical vapor deposition method, extension life
Regular way, electrochemical method, arc process, organic synthesis method, chemistry redox method and supercritical methanol technology etc..Wherein, adulterate public
Think effectively to improve the electrochemical energy storage performance of graphene.
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 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 material, commercialization at present
Graphite as anode material for lithium-ion battery theoretical capacity (372mAh g-1) relatively low, limit lithium ion battery chemical property
Improve, therefore it is to meet the pass that lithium ion battery develops to electrical equipment to design and prepare high performance lithium ionic cell cathode material
Key factor.New carbon graphene is due to the electric conductivity with superelevation, relatively low charge transfer resistance, the specific surface area of super large
Various potential using values are shown with many characteristics such as interlamellar spacing, the mechanical performance of stabilization 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 born
Pole material is because the reason such as larger, poor and without stabilization voltage platform of cyclical stability of its irreversible capacity, same limitation
Its application in terms of lithium-ion negative pole battery material.Therefore, a kind of cyclicity with high specific capacity, relatively stable is obtained
The lithium ion battery negative material of the voltage platform of energy, high rate performance and stabilization still requires study.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of doped graphene；
The doped graphene being prepared another object of the present invention is to provide the preparation method；
A further object of the present invention is the purposes for providing the doped graphene；
It is still another object of the present invention to provide battery cathode prepared by the doped graphene.
In order to achieve the above object, on the one hand, the present invention provides a kind of preparation method of doped graphene, wherein, the side
Method includes：
(1) graphite is mixed with oxidant, dopant, intercalated graphite is prepared；
(2) intercalated graphite that step (1) obtains is calcined to obtain expanded graphite；
(3) expanded graphite for obtaining step (2) is peeled off to obtain the doped graphene by solvent.
Some specific embodiments according to the present invention, wherein, the oxidant is selected from the concentrated sulfuric acid, concentrated nitric acid and permanganic acid
One or more mixing in potassium, potassium bichromate.
Some specific embodiments according to the present invention, wherein, the dopant is selected from the concentrated sulfuric acid, phosphoric acid, phosphate and sulphur
One or more mixing in hydrochlorate.
Some specific embodiments according to the present invention, wherein, the phosphate be selected from ammonium hydrogen phosphate, ammonium dihydrogen phosphate or
Sodium pyrophosphate.
Some specific embodiments according to the present invention, wherein, the sulfate is selected from sodium sulphate, potassium sulfate, ammonium hydrogen sulfate
Or lithium sulfate.
Some specific embodiments according to the present invention, wherein, the graphite flake is natural flake graphite (average grain diameter 15-
20 microns) or Delanium.
Some specific embodiments according to the present invention, wherein, graphite flake purity is more than 99%.
Some specific embodiments according to the present invention, wherein, graphite and oxidant, the mass ratio of dopant in step (1)
For 1：(1-20)：(0.1-10).
Some specific embodiments according to the present invention, wherein, step (2) is that the intercalated graphite that step (1) obtains exists
Calcining obtains expanded graphite at 500-1000 DEG C.
Some specific embodiments according to the present invention, wherein, step (2) is that calcining obtains expansion stone at 600-900 DEG C
Ink.
Some specific embodiments according to the present invention, wherein, step (2) is that calcining 0.5-30min obtains expanded graphite.
Some specific embodiments according to the present invention, wherein, step (2) is the intercalated graphite for obtaining step (1) lazy
Property atmosphere under calcining obtain expanded graphite.
Some specific embodiments according to the present invention, wherein, the inert gas of step (2) is argon gas.
It can be calciner commonly used in the art that calcining is reactor used in step (2), and according to the present invention one
A little specific embodiments, in step (2) calcining it is reactor used be in vertical CVD reactors and horizontal tube reactor one
Kind.
Some specific embodiments according to the present invention, wherein, step (3) is to pass through the expanded graphite that step (2) obtains
Hydro-thermal method, supercritical fluid method and ultrasonic method one or more kinds of combined method therein are peeled off to obtain the doped graphite
Alkene.
Some specific embodiments according to the present invention, wherein, the solvent in step (3), which is peeled off, obtains step (2)
Expanded graphite is peeled off to obtain the doping stone by the combined method of hydro-thermal method, supercritical fluid method and two kinds therein of ultrasonic method
Black alkene.
Some specific embodiments according to the present invention, wherein, the solvent in step (3), which is peeled off, obtains step (2)
Expanded graphite first passes through ultrasonic method, then peels off by hydro-thermal method or supercritical fluid method to obtain the doped graphene.
Some specific embodiments according to the present invention, wherein, the hydro-thermal method of step (3) includes：By expanded graphite point
It is scattered in water, hydro-thermal process 1-24h, is then cooled to room temperature at 100-300 DEG C, and doped graphene is obtained by processing.
Some specific embodiments according to the present invention, wherein, the temperature of the hydro-thermal method of step (3) is preferably 150 DEG C.
Some specific embodiments according to the present invention, wherein, step (3) after room temperature is cooled to, by filtering, rinse and
Drying obtains doped graphene.
Some specific embodiments according to the present invention, wherein, it with mass concentration is 5-10wt% that the rinsing of step (3), which is,
Aqueous hydrochloric acid solution is as purificant.
Some specific embodiments according to the present invention, wherein, the drying temperature of step (3) is 80-100 DEG C.
Some specific embodiments according to the present invention, wherein, the supercritical fluid method of step (3) includes：Will expansion
Graphite and carbon dioxide mix, under pressure 5-20MPa, at 10-200 DEG C of temperature, stir 0.5-10h, are then sprayed into normal pressure appearance
Device, obtains doped graphene.
Some specific embodiments according to the present invention, wherein, the matter of carbon dioxide and expanded graphite in supercritical fluid method
It is 10-1 to measure ratio:1.
Some specific embodiments according to the present invention, wherein, the supercritical fluid method of step (3) is sprayed into often by nozzle
Pressure vessel, obtains doped graphene.
Some specific embodiments according to the present invention, wherein, the jet expansion internal diameter of step (3) is 1-20mm.
Some specific embodiments according to the present invention, wherein, the ultrasonic method of step (3) comprises the following steps：Will step
Suddenly the expanded graphite that (2) obtain is uniformly dispersed in organic solvent, is then ultrasonically treated, so as to fulfill the stripping of graphite flake layer,
Obtain doped graphene.
Some specific embodiments according to the present invention, wherein, the supersound process described in step (3) is ultrasound 1-2h.
Some specific embodiments according to the present invention, wherein, the supersound process described in step (3) is to be surpassed at 70 DEG C
Sonication.
Some specific embodiments according to the present invention, wherein, the organic solvent described in step (3) is selected from ethanol, ether, N-
One or more mixing in methyl pyrrolidone (NMP) and dimethylformamide (DMF)；Wherein it is preferably dimethyl formyl
Amine (DMF).
Some specific embodiments according to the present invention, wherein, the consumption of organic solvent of step (3) is will be per 1g expanded graphites
It is scattered in 10-100ml organic solvents.
Some specific embodiments according to the present invention, wherein, step (1) is to be mixed graphite and oxidant, dopant
Close, stir 1-48h, obtain intercalated graphite；
Some specific embodiments according to the present invention, wherein, step (1) is to stir 1-12h at 10-80 DEG C, is inserted
Layer graphite.
Some specific embodiments according to the present invention, wherein, step (1) further includes the production that will be obtained after stirring
Thing is washed, and is then filtered and is dried to obtain intercalated graphite.
Some specific embodiments according to the present invention, wherein, step (1) is will to obtain being washed with aqueous hydrochloric acid solution, then
Washed with ethanol, intercalated graphite is dried to obtain after then filtering.
Some specific embodiments according to the present invention, wherein, step (1) is to be washed repeatedly with aqueous hydrochloric acid solution 3 times, then is used
Ethanol washs 1 time.
Some specific embodiments according to the present invention, wherein, the aqueous hydrochloric acid solution concentration of step (1) is 3-30%.
Some specific embodiments according to the present invention, wherein, the drying of step (1) is the dry 2-24h at 80 DEG C.
On the other hand, present invention also offers the doped graphene that preparation method of the present invention is prepared.
Some specific embodiments according to the present invention, wherein, the doped chemical be sulphur, nitrogen, oxygen and phosphorus in one kind or
A variety of combinations.
Some specific embodiments according to the present invention, wherein, one kind or more in S and P is contained when the doped graphene
During kind, S and the respective dopings of P are each independently：S:0.5-5wt%, P:0.5-3%.
Some specific embodiments according to the present invention, wherein, the doped chemical is 3-10 layers.
The doped graphene of the present invention is very helpful for electrochemical energy storage, as lithium ion battery negative material, tool
There is a charge and discharge platform in stable 0-0.5V voltage ranges, lithium ion memory capacity is up to 450mAh g in platform-1。
Another aspect, present invention also offers application of the doped graphene in lithium ion battery is prepared.
Some specific embodiments according to the present invention, wherein, the doped graphene is used to prepare lithium ion battery
Anode.
Another further aspect, present invention also offers negative electrode of lithium ion battery prepared by the doped graphene.
Some specific embodiments according to the present invention, wherein, the used as negative electrode of Li-ion battery is in the discharge and recharge of 0-0.5V
Voltage platform.
The negative electrode of lithium ion battery can improve the memory capacity of lithium ion on the charging/discharging voltage platform of 0-0.5V,
The lithium ion memory capacity of doped graphene negative material is significantly higher than the theoretical capacity of graphite in the range of 0-0.5V
(372mAh/g)。
In conclusion the present invention provides a kind of doped graphene and its preparation method and application.The doping stone of the present invention
Black alkene 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.Relative to industrial commonly used
Graphite cathode material, the specific capacity of negative material greatly improved in this doped multi-layer graphene negative material；Compare at the same time
In simple using grapheme material as negative material, material cost has not only been efficiently controlled, but also has improved following for material
Ring stability, and there is the charge and discharge platform in stable 0-0.5V voltage ranges, lithium ion memory capacity can in platform
Up to 450mAh g-1.In conclusion the invention provides preferable bear to prepare the lithium ion battery with more preferable chemical property
Pole material, is an important breakthrough in electrochemical applications field.
Brief description of the drawings
Fig. 1 is scanning electron microscope (SEM) picture of undressed natural flake graphite used in embodiment 1；
Fig. 2 is scanning electron microscope (SEM) picture of the expanded graphite obtained in embodiment 1；
Fig. 3 is transmission electron microscope (TEM) picture of the obtained doped multi-layer graphene of embodiment 1；
Fig. 4 is that the doped multi-layer grapheme 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 the doped multi-layer grapheme material that embodiment 1 is prepared is used as active matter in ion cathode material lithium
The typical charging and discharging curve under 50mA/g electric currents of matter；
Fig. 6 is that the doped multi-layer grapheme material that embodiment 1 is prepared is used as active matter in ion cathode material lithium
The typical recycling curve under 150mA/g electric currents of matter；
Fig. 7 is that the doped multi-layer grapheme 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 the doped multi-layer grapheme 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 the doped multi-layer grapheme material that embodiment 5 is prepared is used as active matter in ion cathode material lithium
The curve of double curvature of matter；
Figure 10 is that the doped multi-layer grapheme material that embodiment 5 is prepared is used as active matter in ion cathode material lithium
The charge-discharge test curve of matter, two curves be respectively before circulating (Fresh cell) and after circulating (after cycle, 50 times
Circulation) charging and discharging curve；
Figure 11 is that multiplying power of the natural flake graphite material as active material in ion cathode material lithium is bent in comparative example 1
Line；
Figure 12 is discharge and recharge of the natural flake graphite material in ion cathode material lithium as active material in comparative example 1
Test curve.
Embodiment
Below by way of the specific embodiment implementation process that the present invention will be described in detail and the beneficial effect produced, 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 doped multi-layer grapheme material and preparation method thereof is present embodiments provided, including：
1. the preparation of intercalated graphite
(1) 10g graphite (pattern is as shown in Figure 1) is uniformly mixed with 5g potassium permanganate, 5g magnesium sulfate, adds the dense sulphur of 50g
Sour (80wt%) and 50g concentrated phosphoric acids, uniform stirring, under ice bath, magnetic agitation under the conditions of hybrid reaction 12h；
(2) obtained product is washed three times repeatedly with 6wt%HCl solution, then washed once with ethanol solution, filtered
12h is dried at 80 DEG C to filter cake, obtains intercalated graphite.
2. the preparation of expanded graphite
Intercalated graphite alkene is placed in vertical heater reactor, is sealed, leads to argon gas, 800 is warming up to the speed of 10 DEG C/min
DEG C, heated at constant temperature 10min, obtains expanded graphite；
3. the preparation of doped multi-layer graphene
(1) the preliminary stripping of graphite flake layer is realized using ultrasonic method first：By expanded graphite at 70 DEG C with dimethyl acyl
Amine mixes ultrasound 2h, expanded graphite alkene is more effectively disperseed；Dry 12h, collection obtain pulverulent solids at 80 DEG C,
Its scanning electron microscopic picture is as shown in Figure 2；
(2) and then using hydro-thermal method the stripping of graphite flake layer is further carried out：The product that step (1) obtains is dispersed in
In ionized water, it is put into water heating kettle, when hydro-thermal process 12 is small at 160 DEG C；By products therefrom filter and with deionized water repeatedly
After rinsing, drying 12h obtains mixing sulphur multi-layer graphene at 90 DEG C.
Characterized to mixing sulphur multi-layer graphene made from the above process, its transmission electron microscope picture is as shown in figure 3, black is real
The quantity of line lines corresponds to the graphene number of plies, and the graphene number of plies of the sample spot is 9 layers, belongs to multi-layer graphene.X-ray light
Electron Spectrum (XPS) measurement result is shown：Sample is mainly made of tetra- kinds of elements of C, S, P and O, and wherein the content of S elements is 1.8%
The content of (atomic percent), P element is 1.1% (atomic percent), S and P atoms are mainly by being covalently bound to carbon original
In the skeleton structure of son.Therefore, the product that the present embodiment obtains is the multi-layer graphene for mixing sulphur, phosphorus.
Embodiment 2
The doped multi-layer grapheme material being prepared by embodiment 1 is present embodiments provided as negative electrode of lithium ion battery
The application of material activity material, it comprises the following steps：
A. by the doped multi-layer grapheme material prepared in 0.4g embodiments 1 and 0.714g Kynoar solutions (PVDF,
7wt%) and 0.05g carbon blacks are mixed evenly and negative material are made, wherein, doped multi-layer grapheme material is as active matter
Matter, Kynoar is as adhesive, and carbon black is as conductive agent.
B. by above-mentioned negative material coater even spread on aluminium foil, drying, is made lithium ion cell positive；Filling
Cathode, lithium piece, membrane and electrolyte are dressed up into lithium ion battery according to battery assembling technique groups in the glove box of full argon gas atmosphere；
Wherein, membrane uses U.S. celgard2400, electrolyte LiPF61mol/L solution, solvent EC, EMC, DMC are according to body
Product ratio 1：1：1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.Assemble
Cheng Hou, 12h is placed by lithium ion battery, 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 doped multi-layer grapheme material as lithium ion
Cell negative electrode material active material is in 50mA g-1Its specific capacity is more than 500mAh g under electric current-1, apparently higher than common graphite material
The 372mAh g of material-1, show that the doped multi-layer grapheme material makes the capacity of battery be significantly improved, and in 0-1V
In the range of charge-discharge test result and 0-3V in the range of result approach, illustrate lithium ion storage voltage platform in 0-1V models
In enclosing.Charging and discharging curve is as shown in Figure 5, it can be seen that has stable voltage platform near 0.2-0.3V, in 0-0.5V scopes
Interior charge specific capacity (i.e. lithium ion abjection specific capacity) is significantly higher than the theoretical capacity of graphite more than 450mAh/g.Fig. 6 is provided
The material circulates under 150mA/g current densities the cycle performance figure of 100 times, it can be seen that the ratio of material after 100 circulations
Capacity does not decline not only, but also also certain increase, cyclical stability are very excellent.It can be obtained according to above test result
Go out, this doped graphene material has very excellent chemical property, is as lithium ion battery negative pole active materials
Ideal material.
Embodiment 3
This gives a kind of preparation process for mixing sulphur multi-layer graphene.
1. the preparation of intercalated graphite
(1) 10g graphite is uniformly mixed with 8g potassium bichromates, 5g magnesium sulfate, adds the 50g concentrated sulfuric acids (80wt%) and 50g
Concentrated nitric acid, uniform stirring, under ice bath, magnetic agitation under the conditions of hybrid reaction 12h；
(2) obtained product is washed three times repeatedly with 6wt%HCl solution, then washed once with ethanol solution, filtered
12h is dried at 80 DEG C to filter cake.
2. the preparation of expanded graphite
Intercalated graphite is placed in vertical heater reactor, is sealed, leads to argon gas, 750 DEG C is warming up to the speed of 10 DEG C/min,
Isothermal reaction 5min.
3. the preparation of doped multi-layer graphene
(1) expanded graphite is mixed ultrasound 1.5h with dimethylformamide and ethanol at 70 DEG C to be pre-processed；80
Dry 12h, collection obtain pulverulent solids at DEG C.
(2) expanded graphite is mixed with Co 2 supercritical fluid, be pressurized under 10MPa, temperature is 200 DEG C, stirring 2
Hour；Expanded graphite and carbon dioxide mixture are sprayed into non-pressure vessel by nozzle, collection obtains doped multi-layer graphene.
X-ray photoelectron spectroscopy (XPS) measurement result is shown：Sample is mainly made of tri- kinds of elements of C, S, O, wherein S elements
Content be 2.1% (atomic percent), S atom is mainly covalently bound in the skeleton structure of carbon atom by C-S-C.Cause
This, the product that the present embodiment obtains is the multi-layer graphene for mixing sulphur.
Embodiment 4
The doped multi-layer grapheme material being prepared by embodiment 3 is present embodiments provided as negative electrode of lithium ion battery
The application of material activity material, it comprises the following steps：
A. by the doped multi-layer grapheme material prepared in 0.4g embodiments 3 and 0.714g Kynoar solutions (PVDF,
7wt%) and 0.05g carbon blacks are mixed evenly and negative material are made, wherein, doped multi-layer grapheme material is as active matter
Matter, Kynoar is as adhesive, and carbon black is as conductive agent.
B. by above-mentioned negative material coater even spread on aluminium foil, drying, is made lithium ion cell positive；Filling
Cathode, lithium piece, membrane and electrolyte are dressed up into lithium ion battery according to battery assembling technique groups in the glove box of full argon gas atmosphere；
Wherein, membrane uses U.S. celgard2400, electrolyte LiPF61mol/L solution, solvent EC, EMC, DMC is according to body
Product ratio 1：1：1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.Assemble
Cheng Hou, 12h is placed by lithium ion battery, and charge-discharge magnification performance test is carried out on charge-discharge test instrument.
Multiplying power test result as shown in fig. 7, as can be seen from Figure 7 use doped multi-layer grapheme material as lithium from
Sub- cell negative electrode material active material is in 150mA g-1Its specific capacity reaches 440mAh g under electric current-1, apparently higher than common graphite
The 372mAh g of material-1, show that the composite material makes the capacity of battery be significantly improved；Charging and discharging curve such as Fig. 8 institutes
Show, it can be seen that have stable voltage platform near 0.2-0.3V.It can be drawn according to above test result, this doping stone
Black alkene material has very excellent chemical property, is the ideal material as lithium ion battery negative pole active materials.
Embodiment 5
This gives one kind using the concentrated sulfuric acid and potassium permanganate as oxidant, using magnesium sulfate and sodium phosphate as dopant
The method for preparing doped multi-layer graphene.
1. the preparation of intercalated graphite
(1) 10g graphite is uniformly mixed with 5g potassium permanganate, 5g magnesium sulfate and 5g sodium phosphates, adds the 50g concentrated sulfuric acids
(80wt%), uniform stirring, under ice bath, magnetic agitation under the conditions of hybrid reaction 12h；
(2) obtained product is washed three times repeatedly with 6wt%HCl solution, then washed once with ethanol solution, filtered
12h is dried at 80 DEG C to filter cake.
2. the preparation of expanded graphite
Intercalated graphite is placed in vertical heater reactor, is sealed, leads to argon gas, 700 DEG C is warming up to the speed of 10 DEG C/min,
Isothermal reaction 10min；
3. the preparation of doped multi-layer graphene
(1) expanded graphite is mixed to ultrasound 1.5h at 70 DEG C with dimethylformamide and ethanol；Then done at 80 DEG C
Dry 12h, collection obtain pulverulent solids.
(2) product for obtaining previous step is mixed with Co 2 supercritical fluid, is stirred under the conditions of 10MPa, 35 DEG C
Mix 2 it is small when；Products therefrom is sprayed into non-pressure vessel by nozzle when room temperature is down to, collection obtains doped multi-layer graphene.
Embodiment 6
The doped multi-layer grapheme material being prepared by embodiment 3 is present embodiments provided as negative electrode of lithium ion battery
The application of material activity material, it comprises the following steps：
A. by the doped multi-layer grapheme material prepared in 0.4g embodiments 3 and 0.714g Kynoar solutions (PVDF,
7wt%) and 0.05g carbon blacks are mixed evenly and negative material are made, wherein, doped multi-layer grapheme material is as active matter
Matter, Kynoar is as adhesive, and carbon black is as conductive agent.
B. by above-mentioned negative material coater even spread on aluminium foil, drying, is made lithium ion cell positive；Filling
Cathode, lithium piece, membrane and electrolyte are dressed up into lithium ion battery according to battery assembling technique groups in the glove box of full argon gas atmosphere；
Wherein, membrane uses U.S. celgard2400, electrolyte LiPF61mol/L solution, solvent EC, EMC, DMC is according to body
Product ratio 1：1：1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.Assemble
Cheng Hou, 12h is placed by lithium ion battery, and charge-discharge magnification performance test is carried out on charge-discharge test instrument.
Multiplying power test result as shown in figure 9, as can be seen from the figure use doped multi-layer grapheme material as lithium from
Sub- cell negative electrode material active material is in 150mA g-1Its specific capacity reaches 439mAh g under electric current-1, hence it is evident that higher than common graphite
The 372mAh g of material-1, show that the composite material makes the capacity of battery be significantly improved；Charging and discharging curve such as Figure 10 institutes
Show, it can be seen that initial material has stable voltage platform, specific capacity about 400mAh g near 0.2-0.3V-1, and circulate
After 50 weeks, specific capacity increases to about 450mAh g-1.It can be drawn according to above test result, this doped graphene material tool
There is very excellent chemical property, be the ideal material as lithium ion battery negative pole active materials.
Comparative example 1
With existing natural flake graphite material directly as lithium ion battery negative material, it includes following this comparative example
Step：
0.4g natural flake graphites and 0.714g Kynoar solutions (PVDF, 7wt%) and 0.05g carbon blacks are mixed
Stir evenly and negative 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 material coater even spread on aluminium foil, drying, is made lithium ion cell positive；Full of
Cathode, lithium piece, membrane and electrolyte are dressed up into lithium ion battery according to battery assembling technique groups in the glove box of argon gas atmosphere；Its
In, membrane uses U.S. celgard2400, and electrolyte is the 1mol/L solution of LiPF6, and solvent EC, EMC and DMC are according to body
Product ratio 1：1：1 mixed liquor.Wherein EC, EMC, DMC are respectively ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.Assemble
Cheng Hou, 12h is placed by lithium ion battery, and charge-discharge magnification performance test is carried out on charge-discharge test instrument.
Curve of double curvature is as shown in figure 11, in 150mA g-1When its capacity be 355mAh g-1, less than its theoretical capacity, and far
Less than doped multi-layer grapheme material of the present invention.Its charging and discharging curve such as Figure 12, although in the voltage range of 0-3V
The charge specific capacity of crystalline flake graphite is more than 500mAh g-1, but the specific capacity in 0-0.5V sections only has~300mAh g-1,
Quite a few specific capacity (account for overall specific capacity 40%) is distributed in 1-3V voltage ranges, can not be effective in full battery
Utilize.In contrast, specific capacity of the sample of embodiment 2 in the voltage range of 0-0.5V is more than 450mAh g-1, show bright
Aobvious advantage.Proved by this comparative example, doped graphene material of the present invention is the potential of existing graphite cathode material
Ideal optimization material.
Claims (10)
1. a kind of preparation method of doped graphene, wherein, the described method includes：
(1) graphite is mixed with oxidant, dopant, intercalated graphite is prepared；It is preferred that graphite, oxidant and dopant
Mass ratio be 1：1-20：0.1-10
(2) intercalated graphite that step (1) obtains is calcined to obtain expanded graphite；
(3) expanded graphite for obtaining step (2) is peeled off to obtain the doped graphene by solvent.
2. preparation method according to claim 1, wherein, the oxidant be selected from the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate,
One or more mixing in potassium bichromate；It (is preferably phosphoric acid hydrogen that the dopant, which is selected from the concentrated sulfuric acid, phosphoric acid, phosphate sodium,
Ammonium, ammonium dihydrogen phosphate or sodium pyrophosphate) and sulfate (be preferably sodium sulphate, potassium sulfate, ammonium hydrogen sulfate or lithium sulfate) one
Kind or a variety of mixing.
3. preparation method according to claim 1, wherein, step (2) is the intercalated graphite for obtaining step (1) in 500-
Calcining obtains expanded graphite at 1000 DEG C；Wherein preferably calcining obtains expanded graphite at 600-900 DEG C；Further preferably calcine
0.5-30min obtains expanded graphite；The intercalated graphite that preferred steps (1) obtain is calcined under atmosphere of inert gases obtains expansion stone
Ink.
4. preparation method according to claim 1, wherein, the solvent in step (3) peel off be step (2) is obtained it is swollen
Swollen graphite is peeled off to obtain institute by hydro-thermal method, supercritical fluid method and ultrasonic method one or more kinds of combined method therein
State doped graphene (solvent in preferred steps (3) peel off be by the expanded graphite that step (2) obtains by hydro-thermal method, super face
The combined method of boundary's flow process and two kinds therein of ultrasonic method is peeled off to obtain the doped graphene；More preferably in step (3)
It is that the expanded graphite that step (2) obtains is first passed through ultrasonic method that solvent, which is peeled off, then is peeled off by hydro-thermal method or supercritical fluid method
Obtain the doped graphene).
5. preparation method according to claim 4, wherein, the hydro-thermal method comprises the following steps：Expanded graphite is disperseed
Into water, hydro-thermal process 1-24h, is then cooled to room temperature at 100-300 DEG C, and doped graphene is obtained by processing；Wherein
It is preferred that after being cooled to room temperature, by filtering, rinsing and drying obtains doped graphene；
The supercritical fluid method comprises the following steps：By expanded graphite and the carbon dioxide (matter of carbon dioxide and expanded graphite
It is 10-1 to measure ratio:1) mix, under pressure 5-20MPa, at 10-200 DEG C of temperature, stir 0.5-10h, be then sprayed into normal pressure appearance
Device, obtains doped graphene；
The ultrasonic method comprises the following steps：The expanded graphite that step (2) obtains is uniformly dispersed in organic solvent, Ran Houchao
Sonication, so as to fulfill the stripping of graphite flake layer, obtains doped graphene；Wherein preferably ultrasound 1-2h；It is preferred that at 70 DEG C into
Row is ultrasonically treated；It is preferred that the organic solvent in ethanol, ether, 1-methyl-2-pyrrolidinone and dimethylformamide one
Kind or a variety of mixing；Preferable organic solvent dosage is that will be scattered in 10-100ml organic solvents per 1g expanded graphites.
6. preparation method according to claim 1, wherein, step (1) is to be mixed graphite and oxidant, dopant
Close, stir 1-48h, obtain intercalated graphite；1-12h preferably wherein is stirred at 10-80 DEG C, obtains intercalated graphite；It is preferred that walk
Suddenly (1) further includes the product that will be obtained and is washed after stirring, then filters and is dried to obtain intercalated graphite.
7. the doped graphene that the preparation method described in claim 1~6 any one is prepared；The wherein preferably doping
Element is one or more combinations in sulphur, nitrogen, oxygen and phosphorus；Wherein, preferably when the doped graphene contains in S and P
When one or more, S and the respective dopings of P are each independently：S:0.5-5wt%, P:0.5-3%；It is preferred that the doping member
Element is 3-10 layers.
8. application of the doped graphene described in claim 7 in lithium ion battery is prepared；The wherein preferred doped graphite
Alkene is the anode for being used to prepare lithium ion battery.
9. negative electrode of lithium ion battery prepared by the doped graphene described in claim 7.
10. negative electrode of lithium ion battery according to claim 9, it is characterised in that can be put down in the charging/discharging voltage of 0-0.5V
The memory capacity of lithium ion is improved on platform.
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