CN106784826A - Application of the fluorinated graphene in secondary sode cell - Google Patents
Application of the fluorinated graphene in secondary sode cell Download PDFInfo
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- CN106784826A CN106784826A CN201611001278.6A CN201611001278A CN106784826A CN 106784826 A CN106784826 A CN 106784826A CN 201611001278 A CN201611001278 A CN 201611001278A CN 106784826 A CN106784826 A CN 106784826A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses application of the fluorinated graphene in secondary sode cell, by fluorographite, chlorine atom causes part C F covalent bonds to be changed into the ionic bonds of C F half with halogen key is formed between fluorine atom after having the hot intercalation of chloroform；Ultrasound peels off fluorographite；The unreacted fluorographite raw material of centrifugation removal, fluorinated graphene is obtained by the upper solution suction filtration after centrifugation, adds conductive agent and adhesive that the fluorinated graphene positive pole of secondary sode cell is obtained in fluorinated graphene according to certain proportioning.Fluorinated graphene containing the ionic bonds of C F half obtained in technical solution of the present invention shows obvious charge and discharge platform for the secondary sode cell of positive pole, and, discharge platform steady advantage high with reversible specific capacity is a kind of new secondary sode cell positive electrode.
Description
The present patent application is the parent application " fluorinated graphene of the ionic bond of carbon containing fluorine half and using the secondary sodium that it is positive pole
The divisional application of battery ", the applying date of parent application is on May 13rd, 2014, Application No. 2014102017736.
Technical field
The invention belongs to energy storage material technical field, more particularly, it is related to a kind of fluorination of the ionic bond of carbon containing fluorine half
Graphene, preparation method and its utilization.
Background technology
The research and development of energy storage technology are always the direction that countries in the world are paid close attention to, and development capacity is big, volume
Small, energy storage and high conversion efficiency, long service life and high-performance energy-storage battery without geographical restrictions grind as the field
The important focus studied carefully, with great economic and social profit.In all of energy-storage battery positive electrode, fluorocarbons (CFx)
With highest specific discharge capacity, as x=1, its specific discharge capacity reaches 865mAh g-1.The seventies in last century, PANASONIC
Realize CFxIndustrialized production, and positive electrode as lithium primary cell is widely used.Traditional CFx
Be obtained by carbon and fluorine gas pyroreaction, it is used mainly as the positive pole of lithium primary battery, discharge voltage between 2-3V, and
High theoretical specific capacity and energy density is shown, but the insulation characterisitic and extremely low ion due to C-F covalent bonds are passed
Defeated characteristic, causes and there are many defects on its electrochemical properties, such as discharge generally along with battery volumetric expansion and heating,
And the poor inevitable shortcoming of grade of power characteristic [J.McBreen, et al.New approaches to the design
of polymer and liquid electrolytes for lithium batteries[J].J.Power Sources
89(2000)163-167].Fluorinated graphene (Fluorographene, FG), as a kind of new Graphene derivative nanometer two
Dimension material, the performance due to fluorinated graphene with numerous uniquenesses, than if not destroying the premise of Graphene two-dimensional structure
Under a certain amount of fluorine atom is connected on carbon atom, the electronic structure to Graphene carries out controllable regulation and control, simultaneously because FG is unique
Structure and performance it is had broad application prospects (O.Leenaerts, et al.First- in various fields
principles investigation of graphene fluoride and graphene[J].Physical Review
B,2010,82(19),195436)。
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided the fluorographite of the carbon containing ionic bond of fluorine (C-F) half
Alkene and using the secondary sode cell that it is positive pole, effective being effectively increased using C-F ionic bonds in fluorinated graphene can charge and discharge
Specific capacity and cycle efficieny, are suitable as energy storage device of future generation and are applied.
Technical purpose of the invention is achieved by following technical proposals：
The fluorinated graphene of the ionic bond of carbon containing fluorine half, by fluorographite after having the hot intercalation of chloroform chlorine atom with fluorine atom it
Between formed halogen key and cause part C-F covalent bonds to be changed into the ionic bonds of C-F half.Analyzed through x-ray photoelectron spectroscopy, the ionic bonds of C-F half
Shared ratio is 5-20%.
The fluorinated graphene of the ionic bond of carbon containing fluorine half, is prepared as steps described below：
By in fluorographite addition chloroform, stir so that fluorographite is dispersed；By finely dispersed fluorographite-
Chloroform system give it is closed, after fully reacting the sufficiently long time at 60 DEG C -180 DEG C, the centrifugation unreacted fluorination stone of removal
Mo Hou, by upper solution suction filtration, gained filter cake is the fluorinated graphene material containing the ionic bonds of C-F half.
In the above-mentioned technical solutions, reaction temperature is preferably at 100-180 DEG C, more preferred 120-150 DEG C；Reaction time
It is preferred that 6h-12h, preferably 8-10h.
In the above-mentioned technical solutions, selection stainless steel cauldron is used as reaction vessel.
In the above-mentioned technical solutions, Muffle furnace is selected as the supplier of reaction temperature.
In the above-mentioned technical solutions, after fully reaction, by resulting solution ultrasound 2h -12h.
In the above-mentioned technical solutions, fully reaction after, by solution under the rotating speed of 500r/min -4000r/min from
Heart 5min -30min, remove unreacted fluorographite raw material, by gained upper solution suction filtration, filter cake are obtained, by filter cake at 60 DEG C
Lower drying, obtains the fluorinated graphene material containing the ionic bonds of C-F half.
After the fluorinated graphene material containing the ionic bonds of C-F half is prepared, using transmission electron microscope, infrared spectrum and XPS
The structure of the fluorinated graphene material of analysis and explanation containing the ionic bonds of C-F half：
(1) by transmission electron microscope (TEM) to carrying out morphology analysis using obtained fluorinated graphene.TEM samples
Product preparation process is that fluorinated graphene dispersion is taken into a small amount of dilution with liquid-transfering gun afterwards in ethanol to be added drop-wise in micro-grid, treats ethanol
Naturally directly tested after volatilizing, the JEM-2100F of the model Jeol Ltd. of TEM.The TEM of fluorinated graphene
Photo is as shown in Figure 1, it can be seen that be all obvious fold lamellar structure using prepared fluorinated graphene, and its size is big
It is 1um × 2um to cause, and the number of plies is 5 layers or so, and obtained fluorinated graphene has the concave plane of fold, and is presented
Go out irregular non crystalline structure, this is the conjugated structure that graphite linings are destroyed due to the presence of C-F keys.
(2) examination of infrared spectrum method is first to mix a small amount of fluorinated graphene powder with KBr, and is fully ground using mortar
Mill is uniform, then using powder compressing machine constant pressure compressing tablet, is finally analyzed test, fluorine analysis using Fourier infrared spectrograph
The chemical constitution of graphite alkene.Infrared test instrument is that the TENSOR27 Fourier transformations of Brooker spectral instrument company production are red
External spectrum instrument.Fig. 2 is the FT-IR spectrum of prepared fluorinated graphene and protofluorine graphite, and fluorographite is in 1216cm-1Deposit at place
In an obvious strong absworption peak, corresponding to the stretching vibration of C-F covalent bonds；In 1342cm-1Locate exist absworption peak correspond to-
CF2The stretching vibration of group, this is due to that during being fluorinated to graphite, can form one at the edge of graphite flake layer
- CF a bit2Group.Fluorinated graphene is in 1143cm-1There is an acromion in place, corresponding to the ionic bonds of C-F half], illustrate using chlorine
Imitating during hot intercalation is carried out to fluorographite a part of C-F covalent bonds can be made to be changed into C-F ionic bonds, its survey with XPS
Test result is consistent.
(3) chemical composition and chemical bond state of fluorinated graphene are characterized by x-ray photoelectron spectroscopy (XPS),
Fluorinated graphene is dried into water removal in 24 hours for 60 DEG C in vacuum drying oven first, XPS tests are then carried out.Test condition：Excitaton source
MgK α (1253.6eV), power 450W, vacuum 10-8~10-9Torr.The INSTRUMENT MODEL for being used is PERKIN ELMZR public
The PHI1600X photoelectron spectrographs of department.By XPS spectrum figure (Fig. 3-6 for contrasting fluorographite and fluorinated graphene C1s and F1s
It is shown), it can be seen that the fluorographite that remains of prepared fluorinated graphene corresponds to sp at 284.5eV2The C=of hydridization
C-structure peak, the sp at 285.3eV3The C-C structures peak of hydridization, and the C-F covalent bond structures peak at 290.0eV.But
A new peak is occurred in that at 288.44eV, the peak corresponds to half ionic state C-F keys.Equally, obtained fluorinated graphene
F 1s compose from 689.0eV slight shifts to 688.6eV, a new peak is occurred in that at 688.08eV, the peak is also corresponded to
Half ionic state C-F keys.This is because C-H groups in chloroform and three chlorine atoms are likely to and the fluorine original in fluorographite
Son forms halogen key so that the electron cloud on C-F keys shifts to F atom, so as to cause part C-F covalent bonds to be changed into the ions of C-F half
Key.
It is the secondary sode cell of positive pole using the fluorinated graphene of the ionic bond of carbon containing fluorine half, using the ionic bond of carbon containing fluorine half
Fluorinated graphene, acetylene black and Kynoar are according to mass ratio (75-85)：(5—15)：Positive electrode is prepared after 10 mixing.
In above-mentioned battery, the electrolyte composition for using is 1M NaPF6EC (ethylene carbonate)：DMC (carbonic acid diformazans
Ester), both volume ratios 1:1 mixed liquor, that is, the electrolyte composition for using is 1M NaPF6Solution, the solution be ethylene
The mixed solution of alkene ester and dimethyl carbonate, both volume ratios are 1:1.
During positive electrode is prepared, by fluorinated graphene, acetylene black, PVDF is placed in nitrogen-first according to mass ratio requirement
Wet grinding is carried out in base pyrrolidones (NMP) and be prepared into slurry, ground slurry is spread evenly across on aluminium foil, be positioned over
Dried 1~2 hour under 50-60 degrees Celsius in convection oven, the material that will be baked is placed in vacuum drying chamber and dries 24 hours.
The present invention because using chloroform as intercalation solution, using the halogen key interaction force between chlorine atom and fluorine atom,
Part C-F covalent bonds in fluorographite are transformed into the ionic bonds of C-F half, and can be by simply regulating and controlling hot intercalation
The percentage of the ionic bonds of C-F half in temperature-time regulation and control fluorinated graphene；By the prepared fluorographite containing the ionic bonds of C-F half
Alkene can effectively realize recycling for fluorinated graphene as sode cell positive pole, and show good cycle characteristics.
Brief description of the drawings
Fig. 1 is the TEM pictures of the fluorinated graphene of the ionic bond of carbon containing fluorine half prepared using technical solution of the present invention.
Fig. 2 is the fluorinated graphene and fluorinated graphene of the ionic bond of carbon containing fluorine half prepared using technical solution of the present invention
FT-IR spectrum spectrograms.
Fig. 3 is the XPS spectrum figure of the C1s of the fluorinated graphene of the ionic bond of carbon containing fluorine half prepared using technical solution of the present invention
Swarming figure, wherein the structure corresponding to different peak positions is respectively：The correspondence ions of C-F half of 1 corresponding C=C, 2 corresponding C-C, 3
Key, 4 corresponding C-F covalent bonds, 5 correspondence-CF2, 6 correspondence-CF3。
Fig. 4 is the XPS spectrum figure of the F1s of the fluorinated graphene of the ionic bond of carbon containing fluorine half prepared using technical solution of the present invention
Swarming figure, wherein the structure corresponding to different peak positions is respectively：The 1 correspondence ionic bonds of C-F half, 2 corresponding C-F covalent bonds.
Fig. 5 is the swarming figure of the XPS spectrum figure of the C1s of fluorographite raw material, wherein the structure point corresponding to different peak positions
It is not：The corresponding C-F covalent bonds of 1 corresponding C=C, 2 corresponding C-C, 3,4 correspondence-CF2, 5 correspondence-CF3。
Fig. 6 is the swarming figure of the XPS spectrum figure of the F1s of fluorographite raw material, wherein the structure corresponding to peak position 1 for C-F it is common
Valence link.
After Fig. 7 is the positive electrode assembling sode cell prepared in the embodiment of the present invention 1, in the discharge and recharge density of 50mA/g
Under, preceding 20 circle constant current charge-discharge curve, the direction of arrow is respectively the 1st to the 20th circulation along figure.
Specific embodiment
Technical scheme is further illustrated with reference to specific embodiment, the assembling process of secondary sode cell is：
The positive electrode that will be prepared is put into glove box.First stainless steel gasket is placed in the negative cover of battery, metal is then placed in
Sodium piece, is added dropwise appropriate electrolyte, and the composition of electrolyte is 1M NaPF6EC：DMC (volume ratios 1:1) mixed solution, stands
Barrier film is put into after a period of time, positive electrode is placed into and a few drop electrolyte is added dropwise again, finally sealed with sealing machine.Assemble
Battery first at room temperature stand 24 hours, allow electrolyte fully to infiltrate positive and negative pole material, related electrochemistry is then carried out again
The test of performance.
Embodiment 1
Weigh in 20mg fluorographites addition 100mL chloroforms, at the uniform velocity stir half an hour, make Graphite fluoride Composite Deposition in chloroform
In, it is subsequently adding in stainless steel cauldron, reactor is put into Muffle furnace, 12h is heated at 150 DEG C, after the heat time terminates,
By gained suspension ultrasound 6h, the suspension after ultrasound is then centrifuged 30min under the rotating speed of 500r/min, removal lower floor is not
The solid of reaction, by resulting solution suction filtration, obtains filter cake, and filter cake is dried at 60 DEG C, fluorinated graphene material is obtained, through X-ray
Ratio of the electron spectroscopy analysis wherein shared by the ionic bonds of C-F half (i.e. in XPS spectrum figure, corresponds to the ionic bonds of C-F half for 16.7%
The integral area at peak and the ionic bonds of corresponding C-F half, correspondence C-F covalent bonds, correspondence-CF2With correspondence-CF3Peak integral area it
The ratio of sum, as shown in Figure 3,3 integral area/(integration of the integral area+6 of the integral area+5 of 3 integral area+4
Area).It is 80 to weigh mass ratio:10:10 fluorinated graphene, acetylene black and PVDF, being placed in NMP carries out wet grinding
It is prepared into uniform slurry.Ground slurry is spread evenly across on aluminium foil, is positioned in convection oven and is dried under uniform temperature
1-2 hours.The material that will be baked is placed in vacuum drying chamber and dries 24 hours.Obtain fluorinated graphene electrode material.To prepare
Positive electrode be assembled into sode cell, under the discharge and recharge density of 50mA/g, the obtained fluorinated graphene containing the ionic bonds of C-F half
First time specific discharge capacity reaches 780mAh g-1, there is obvious charging platform, then goes out in 2.0V or so in 3.8V or so in it
Existing obvious discharge platform, reversible specific capacity reaches 380mAh g-1, circulate the specific capacity after 20 circles and drop to 120mAh g-1。
Embodiment 2
Weigh in 50mg fluorographites addition 100mL chloroforms, at the uniform velocity stir half an hour, make Graphite fluoride Composite Deposition in chloroform
In, it is subsequently adding in stainless steel cauldron, 10h is heated at 120 DEG C, after the heat time terminates, by gained suspension ultrasound 8h, so
The suspension after ultrasound is centrifuged 30min under the rotating speed of 1000r/min afterwards, unreacted solid is removed, resulting solution is taken out
Filter, obtain filter cake, filter cake dry at 60 DEG C, obtain fluorinated graphene material, by x-ray photoelectron spectroscopy sign wherein C-F from
Ratio shared by sub-key is 12.3%.It is 78 to weigh mass ratio:12:10 fluorinated graphene, acetylene black and PVDF, are placed on
Wet grinding is carried out in NMP and is prepared into uniform slurry.Ground slurry is spread evenly across on aluminium foil, air blast baking is positioned over
Dried 1-2 hours under uniform temperature in case.The material that will be baked is placed in vacuum drying chamber and dries 24 hours.Obtain fluorinated graphene electricity
Pole material.The positive electrode that will be prepared is assembled into sode cell, under the charge-discharge velocity of 50mA/g, it is obtained containing C-F half from
The fluorinated graphene first time specific discharge capacity of sub-key reaches 792mAh g-1, there is obvious charging platform in 3.8V or so in it,
Then there is obvious discharge platform in 2.0V or so, reversible specific capacity reaches 356mAh g-1, the specific capacity after the circle of circulation 20
Drop to 80mAh g-1。
Embodiment 3
Weigh in 60mg fluorographites addition 100mL chloroforms, at the uniform velocity stir half an hour, make Graphite fluoride Composite Deposition in chloroform
In, it is subsequently adding in stainless steel cauldron, reactor is put into Muffle furnace, 12h is heated at 90 DEG C, after the heat time terminates,
By gained suspension ultrasound 10h, the suspension after ultrasound is then centrifuged 20min under the rotating speed of 1500r/min, removal position is anti-
The solid answered, by resulting solution suction filtration, obtains filter cake, and filter cake is dried at 60 DEG C, fluorinated graphene material is obtained, by X-ray
Electron spectrum characterizes wherein C-F ionic bonds institute accounting and is classified as 8.9%.It is 82 to weigh mass ratio:8:10 fluorinated graphene, acetylene
Black and PVDF, being placed in NMP carries out wet grinding and is prepared into uniform slurry.Ground slurry is spread evenly across aluminium
On paper tinsel, it is positioned in convection oven and is dried 1-2 hours under uniform temperature.It is small that the material that will be baked is placed in vacuum drying chamber dry 24
When.Obtain fluorinated graphene electrode material.The positive electrode that will be prepared is assembled into sode cell, in the charge-discharge velocity of 50mA/g
Under, the obtained fluorinated graphene first time specific discharge capacity containing the ionic bonds of C-F half reaches 812mAh g-1, it is in 3.9V or so
There is obvious charging platform, then obvious discharge platform occur in 1.8V or so, reversible specific capacity reaches 226mAh g-1,
Circulate the specific capacity after 20 circles and drop to 48mAh g-1。
Embodiment 4
Weigh in 100mg fluorographites addition 100mL chloroforms, at the uniform velocity stir half an hour, make Graphite fluoride Composite Deposition in chloroform
In, it is subsequently adding in stainless steel cauldron, reactor is put into Muffle furnace, 8h is heated at 180 DEG C, after the heat time terminates,
By gained suspension ultrasound 9h, the suspension after ultrasound is then centrifuged 15min under the rotating speed of 2500r/min, removed not anti-
The solid answered, by resulting solution suction filtration, obtains filter cake, and filter cake is dried at 60 DEG C, fluorinated graphene material is obtained, by X-ray
Ratio of the electron spectroscopy analysis wherein shared by C-F ionic bonds is 18.8%.It is 85 to weigh mass ratio:5:10 fluorinated graphene,
Acetylene black and PVDF, being placed in NMP carries out wet grinding and is prepared into uniform slurry.By ground slurry even spread
Dried 1-2 hours on aluminium foil, being positioned in convection oven under uniform temperature.The material that will be baked is placed in and 24 is dried in vacuum drying chamber
Hour.Obtain fluorinated graphene electrode material.The positive electrode that will be prepared is assembled into sode cell, in the discharge and recharge speed of 50mA/g
Under rate, the obtained fluorinated graphene first time specific discharge capacity containing the ionic bonds of C-F half reaches 732mAh g-1, it is left in 3.8V
It is right obvious charging platform occur, then there is obvious discharge platform in 2.0V or so, reversible specific capacity reaches 388mAh g-1, circulate the specific capacity after 20 circles and drop to 128mAh g-1。
Embodiment 5
Weigh in 100mg fluorographites addition 100mL chloroforms, at the uniform velocity stir half an hour, make Graphite fluoride Composite Deposition in chloroform
In, it is subsequently adding in stainless steel cauldron, reactor is put into Muffle furnace, 12h is heated at 60 DEG C, after the heat time terminates,
By gained suspension ultrasound 9h, the suspension after ultrasound is then centrifuged 15min under the rotating speed of 2500r/min, removed not anti-
The solid answered, by resulting solution suction filtration, obtains filter cake, and filter cake is dried at 60 DEG C, fluorinated graphene material is obtained, by X-ray
Ratio of the electron spectroscopy analysis wherein shared by C-F ionic bonds is 6.8%.It is 75 to weigh mass ratio:15:10 fluorinated graphene,
Acetylene black and PVDF, being placed in NMP carries out wet grinding and is prepared into uniform slurry.By ground slurry even spread
Dried 1-2 hours on aluminium foil, being positioned in convection oven under uniform temperature.The material that will be baked is placed in and 24 is dried in vacuum drying chamber
Hour.Obtain fluorinated graphene electrode material.The positive electrode that will be prepared is assembled into sode cell, in the discharge and recharge speed of 50mA/g
Under rate, the obtained fluorinated graphene first time specific discharge capacity containing the ionic bonds of C-F half reaches 522mAh g-1, it is left in 3.8V
It is right obvious charging platform occur, then there is obvious discharge platform in 2.0V or so, reversible specific capacity reaches 288mAh g-1, circulate the specific capacity after 20 circles and drop to 128mAh g-1。
Embodiment 6
Weigh in 100mg fluorographites addition 100mL chloroforms, at the uniform velocity stir half an hour, make Graphite fluoride Composite Deposition in chloroform
In, it is subsequently adding in stainless steel cauldron, reactor is put into Muffle furnace, 6h is heated at 150 DEG C, after the heat time terminates,
By gained suspension ultrasound 9h, the suspension after ultrasound is then centrifuged 15min under the rotating speed of 2500r/min, removed not anti-
The solid answered, by resulting solution suction filtration, obtains filter cake, and filter cake is dried at 60 DEG C, fluorinated graphene material is obtained, by X-ray
Ratio of the electron spectroscopy analysis wherein shared by C-F ionic bonds is 19.8%.It is 80 to weigh mass ratio:10:10 fluorinated graphene,
Acetylene black and PVDF, being placed in NMP carries out wet grinding and is prepared into uniform slurry.By ground slurry even spread
Dried 1-2 hours on aluminium foil, being positioned in convection oven under uniform temperature.The material that will be baked is placed in and 24 is dried in vacuum drying chamber
Hour.Obtain fluorinated graphene electrode material.The positive electrode that will be prepared is assembled into sode cell, in the discharge and recharge speed of 50mA/g
Under rate, the obtained fluorinated graphene first time specific discharge capacity containing the ionic bonds of C-F half reaches 762mAh g-1, it is left in 3.8V
It is right obvious charging platform occur, then there is obvious discharge platform in 2.0V or so, reversible specific capacity reaches 408mAh g-1, circulate the specific capacity after 20 circles and drop to 148mAh g-1。
Exemplary description is done to the present invention above, it should explanation, do not departed from the situation of core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent of creative work equal
Fall into protection scope of the present invention.
Claims (8)
1. application of the fluorinated graphene in secondary sode cell, it is characterised in that the fluorinated graphene is the ion of carbon containing fluorine half
The fluorinated graphene of key, by fluorographite, chlorine atom causes part with halogen key is formed between fluorine atom after having the hot intercalation of chloroform
C-F covalent bonds are changed into the ionic bonds of C-F half, by the use of the ionic bond of carbon containing fluorine half fluorinated graphene as secondary sode cell positive pole
Materials'use.
2. application of the fluorinated graphene according to claim 1 in secondary sode cell, it is characterised in that through X-ray electronics
Energy spectrum analysis, the ratio shared by the ionic bonds of C-F half is 5-20%.
3. application of the fluorinated graphene according to claims 1 or 2 in secondary sode cell, it is characterised in that use
The fluorinated graphene of the ionic bond of carbon containing fluorine half, acetylene black and Kynoar are according to mass ratio (75-85)：(5—15)：10 mix
Positive electrode is prepared after conjunction.
4. application of the fluorinated graphene according to claims 1 or 2 or 3 in secondary sode cell, it is characterised in that
The electrolyte composition for using is 1M NaPF6Solution, the solution is the mixed solution of ethylene carbonate and dimethyl carbonate,
Both volume ratios are 1:1.
5. application of the fluorinated graphene according to claim 1 in secondary sode cell, it is characterised in that carbon containing fluorine half from
The fluorinated graphene of sub-key is prepared as steps described below：By in fluorographite addition chloroform, stir so that fluorographite is equal
Even dispersion；Finely dispersed fluorographite-chloroform system is given closed, fully react sufficiently long at 60 DEG C -180 DEG C
After time, after the unreacted fluorographite of centrifugation removal, by upper solution suction filtration, gained filter cake is containing the ionic bonds of C-F half
Fluorinated graphene material.
6. application of the fluorinated graphene according to claim 1 in secondary sode cell, it is characterised in that reaction temperature is excellent
It is selected in 100-180 DEG C, more preferred 120-150 DEG C；Reaction time preferred 6h-12h, preferably 8-10h.
7. application of the fluorinated graphene according to claim 1 in secondary sode cell, it is characterised in that fully reacting
Afterwards, by resulting solution ultrasound 2h -12h.
8. application of the fluorinated graphene according to claim 1 in secondary sode cell, it is characterised in that fully reacting
Afterwards, solution is centrifuged 5min -30min under the rotating speed of 500r/min -4000r/min, removes unreacted fluorographite former
Material, by gained upper solution suction filtration, obtains filter cake, and filter cake is dried at 60 DEG C, obtains the fluorinated graphene containing the ionic bonds of C-F half
Material.
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| CN201410201773.6A CN103985874A (en) | 2014-05-13 | 2014-05-13 | Fluorinated graphene containing semi-ionic C-F bonds and secondary sodium battery adopting the fluorinated graphene as the cathode |
| CN201611001278.6A CN106784826A (en) | 2014-05-13 | 2014-05-13 | Application of the fluorinated graphene in secondary sode cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107720730A (en) * | 2017-10-13 | 2018-02-23 | 厦门稀土材料研究所 | A kind of fluorinated graphene and anode material of lithium battery of the ionic bond of carbon containing fluorine half |
| CN108002367A (en) * | 2017-11-14 | 2018-05-08 | 科凯精细化工（上海）有限公司 | A kind of preparation method of water soluble fluoridized graphene |
| CN114975894A (en) * | 2022-06-15 | 2022-08-30 | 松山湖材料实验室 | Graphite fluoride positive electrode, preparation method thereof and battery |
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| KR20180034098A (en) * | 2016-09-27 | 2018-04-04 | 한국과학기술연구원 | Energy device including halogenated carbon materials and method for preparing the same |
| CN110877906B (en) * | 2018-09-06 | 2022-06-24 | 天津大学 | Preparation method of fluorine-doped graphene |
| CN109368633A (en) * | 2018-10-18 | 2019-02-22 | 山东理工大学 | A kind of lithium primary battery fluorographite positive electrode of modification and preparation method thereof |
| CN112080009B (en) * | 2020-09-11 | 2022-03-01 | 常州大学 | Boron-fluorine-containing hybrid adhesive with self-repairing and self-cleaning functions at room temperature and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720730A (en) * | 2017-10-13 | 2018-02-23 | 厦门稀土材料研究所 | A kind of fluorinated graphene and anode material of lithium battery of the ionic bond of carbon containing fluorine half |
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| CN108002367B (en) * | 2017-11-14 | 2020-01-21 | 科凯精细化工（上海）有限公司 | Preparation method of water-soluble fluorinated graphene |
| CN114975894A (en) * | 2022-06-15 | 2022-08-30 | 松山湖材料实验室 | Graphite fluoride positive electrode, preparation method thereof and battery |
| CN114975894B (en) * | 2022-06-15 | 2024-02-20 | 松山湖材料实验室 | Graphite fluoride anode, preparation method thereof and battery |
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