CN106229506B - A method of fluorocarbons discharge voltage is regulated and controled by graphene planes curvature - Google Patents
A method of fluorocarbons discharge voltage is regulated and controled by graphene planes curvature Download PDFInfo
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- CN106229506B CN106229506B CN201610685754.4A CN201610685754A CN106229506B CN 106229506 B CN106229506 B CN 106229506B CN 201610685754 A CN201610685754 A CN 201610685754A CN 106229506 B CN106229506 B CN 106229506B
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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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/12—Testing dielectric strength or breakdown voltage ; Testing or monitoring effectiveness or level of insulation, e.g. of a cable or of an apparatus, for example using partial discharge measurements; Electrostatic testing
- G01R31/1227—Testing dielectric strength or breakdown voltage ; Testing or monitoring effectiveness or level of insulation, e.g. of a cable or of an apparatus, for example using partial discharge measurements; Electrostatic testing of components, parts or materials
- G01R31/1263—Testing dielectric strength or breakdown voltage ; Testing or monitoring effectiveness or level of insulation, e.g. of a cable or of an apparatus, for example using partial discharge measurements; Electrostatic testing of components, parts or materials of solid or fluid materials, e.g. insulation films, bulk material; of semiconductors or LV electronic components or parts; of cable, line or wire insulation
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of methods regulating and controlling fluorocarbons discharge voltage by graphene planes curvature.It is first 0.3~1.5nm by curvature‑1Single-walled carbon nanotube or fullerene C60It is put into diamond heating area, install and checks tube furnace air-tightness, enough argon gas are passed through into pipe and exclude tubular type furnace air.The mixed gas of fluorine gas and hydrogen, volume ratio 1 are passed through after tube furnace is risen to 200 400 DEG C of arrival set temperatures from room temperature in 10 100 minutes into pipe:1‑1:4, mixed gas is by argon gas as carrier gas.It is taken out after burner hearth after reaction is cooled to room temperature, obtains product.The present invention is easy to operate, at low cost, and yield is high, and the fluorocarbons discharge voltage made from the smaller single-walled carbon nanotube of planar curvature is 2.8V~3.0V or so, and the curvature of single-walled carbon nanotube is bigger, and generating voltage is higher；And the fullerene C that curvature is larger60Fluorocarbons discharge voltage obtained is 3.5V or so.
Description
Technical field
It is specifically logical the present invention relates to a kind of method regulating and controlling fluorocarbons discharge voltage by graphene planes curvature
Overregulate the method for the different prepared fluorinated carbon material discharge voltages of control of the planar curvature of graphene.
Background technology
Fluorinated carbon material be now in the world high-tech, high-performance, high benefit one of novel carbon-based material research hotspot,
Especially fast development of fluorinated carbon material recent years in high energy lithium primary cell field further promotes its application
(Yazami R,Hamwi A,Guérin K,et al.Fluorinated carbon nanofibres for high
energy and high power densitiesprimary lithium batteries[J].Electrochemistry
communications,2007,9(7):1850-1855.).But it is used still as lithium primary cell anode many problems
It is badly in need of solving, wherein the too low and adjoint violent fever phenomenon of discharge voltage limits it and uses under certain extreme conditions
Major obstacle.Current commercialized fluorinated graphite material discharge voltage is generally 2.5~2.6V (vs.Li+/Li), far below reason
By calculated value.This is because sp3Fluorine carbon key shows covalency in the fluorographite of hydridization configuration, can only utilize its~55%
Chemical energy, remaining energy discharges in the form of thermal energy, cause a large amount of thermal energy release (Zhang Q, d ' Astorg S,
Xiao P,et al.Carbon-coated fluorinated graphite for high energy and highpower
densities primary lithium batteries[J].Journal of Power Sources,2010,195(9):
2914-2917.).Therefore how to regulate and control the bond type of the fluorine carbon key of fluorinated carbon material becomes raising fluorinated carbon material discharge voltage
It is crucial.
It is vital that research finds that the curvature of graphene sheet layer has fluorine carbon key bond type in prepared fluorocarbons
Influence (Zhang W, Dubois M, Gu é rin K, et al.Effect of curvature on C-F bonding in
fluorinated carbons:from fullerene and derivatives to graphite[J].Physical
Chemistry Chemical Physics,2010,12(6):1388-1398.).The bending of graphene sheet layer causes carbon atom
Contain sp simultaneously2And sp3Hydridization ingredient, when it is converted into fluorocarbons, carbon atom is then maintained to the sp of part2Hydridization structure
Type will not be fully converted to the sp similar to fluorographite3Hydridization configuration reduces between fluorine atom and carbon atom hybridized orbit
Registration, eventually lead to the reduction of fluorine carbon key conjugated degree, improve fluorocarbons discharge voltage (Dubois M, Gu é rin K,
Zhang W,et al.Tuning the discharge potential offluorinated carbon used as
electrode in primary lithium battery[J].Electrochimica acta,2012,59:485-
491.).Meanwhile the different bending degree of graphene can lead to sp2And sp3The difference of hydridization component content, therefore graphene sheet layer
The variation of curvature can regulate and control discharge platform, effectively control the exothermic phenomenon of lithium-fluorination carbon battery.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind adjusting fluorination carbon materials by graphene curvature
Expect that the method for discharge voltage, this method are easy to operate effectively.The fluorinated carbon material of preparation has part sp2Hybrid structure is put
Piezoelectric voltage uses following technical scheme higher than commercialization fluorinated graphite material, the present invention：
A method of regulating and controlling fluorocarbons discharge voltage using graphene planes curvature, steps are as follows：
(1) it is 0.3~1.5nm by curvature-1Single-walled carbon nanotube or fullerene C60It is put into diamond heating area, installation is simultaneously
It checks tube furnace air-tightness, enough argon gas is passed through into pipe and exclude tubular type furnace air；
(2) at 10-100 minutes, tube furnace is risen to 200-400 DEG C by room temperature, fluorine gas and hydrogen are then passed through into pipe
Mixed gas, mixed gas is by argon gas as carrier gas；
(3) reaction time 0.5-24 hour is kept, is taken out after burner hearth after reaction is cooled to room temperature, obtains product.
The step (2) rises to 200-300 DEG C at 20-60 minutes, by tube furnace by room temperature, and volume is then passed through into pipe
Than being 1:1-1:The mixed gas of 4 fluorine gas and hydrogen, mixed gas is by argon gas as carrier gas.
The step (3) is kept for reaction time 8-16 hour.
The present invention is easy to operate, at low cost, and yield is high, and post-processes simply, and manufacturing cost is cheap.Raw material can be passed through
The hybrid structure of the planar curvature variation regulation and control fluorination carbon product of graphene, to regulate and control discharge voltage.According to selected stone
The difference of black alkene raw material planar curvature, the discharge voltage of the fluorinated carbon material of gained is also different, wherein by planar curvature compared with
Fluorocarbons discharge voltage made from small single-walled carbon nanotube is 2.8V~3.0V or so, and the curvature of single-walled carbon nanotube is got over
Greatly, discharge voltage is higher；And the fullerene C that curvature is larger60Fluorocarbons discharge voltage obtained is 3.5V or so.
Description of the drawings
Fig. 1 is the fluorocarbons discharge curve prepared by embodiment 1；
Fig. 2 is the fluorocarbons discharge curve prepared by embodiment 2；
Fig. 3 is the fluorocarbons discharge curve prepared by embodiment 3；
Fig. 4 is the fluorocarbons discharge curve prepared by embodiment 4；
Fig. 5 is the fluorocarbons discharge curve prepared by embodiment 5.
Specific implementation mode
Technical solution of the present invention is illustrated below by way of specific embodiment.
The various carbon sources used in embodiment are workable commercial product.
Embodiment 1
1) by a diameter of 1.5nm, curvature 1.33nm-1Single-walled carbon nanotube be put into diamond heating area, install and examine
Formula stove air-tightness is checked, enough argon gas are passed through into pipe and exclude tubular type furnace air.
2) tube furnace is risen to 200 DEG C by room temperature in 20 minutes, fluorine gas and hydrogen is passed through into pipe after reaching set temperature
The mixed gas of gas, volume ratio 1:1, mixed gas is by argon gas as carrier gas.
3) 8 hours reaction time is kept, is taken out after burner hearth after reaction is cooled to room temperature, obtains product.
4) discharge test is carried out to products therefrom, it is 3.129V to measure its discharge voltage.
Embodiment 2
1) by a diameter of 2.24nm, curvature 0.89nm-1Single-walled carbon nanotube be put into diamond heating area, install and examine
Formula stove air-tightness is checked, enough argon gas are passed through into pipe and exclude tubular type furnace air.
2) tube furnace is risen to 300 DEG C by room temperature in 60 minutes, fluorine gas and hydrogen is passed through into pipe after reaching set temperature
The mixed gas of gas, volume ratio 1:4, mixed gas is by argon gas as carrier gas.
3) 16 hours reaction time is kept, is taken out after burner hearth after reaction is cooled to room temperature, obtains product.
4) discharge test is carried out to products therefrom, it is 3.001V to measure its discharge voltage.
Embodiment 3
1) by a diameter of 3.23nm, curvature 0.62nm-1Single-walled carbon nanotube be put into diamond heating area, install and examine
Formula stove air-tightness is checked, enough argon gas are passed through into pipe and exclude tubular type furnace air.
2) tube furnace is risen to 250 DEG C by room temperature in 40 minutes, fluorine gas and hydrogen is passed through into pipe after reaching set temperature
The mixed gas of gas, volume ratio 1:2, mixed gas is by argon gas as carrier gas.
3) 12 hours reaction time is kept, is taken out after burner hearth after reaction is cooled to room temperature, obtains product.
4) discharge test is carried out to products therefrom, it is 2.906V to measure its discharge voltage.
Embodiment 4
1) by a diameter of 6.39nm, curvature 0.31nm-1Single-walled carbon nanotube be put into diamond heating area, install and examine
Formula stove air-tightness is checked, enough argon gas are passed through into pipe and exclude tubular type furnace air.
2) tube furnace is risen to 300 DEG C by room temperature in 45 minutes, fluorine gas and hydrogen is passed through into pipe after reaching set temperature
The mixed gas of gas, volume ratio 1:3, mixed gas is by argon gas as carrier gas.
3) 12 hours reaction time is kept, is taken out after burner hearth after reaction is cooled to room temperature, obtains product.
4) discharge test is carried out to products therefrom, it is 2.805V to measure its discharge voltage.
Embodiment 5
1) it is 2.94nm by curvature-1Fullerene C60It is put into diamond heating area, installs and check tube furnace air-tightness,
Xiang Guanzhong is passed through enough argon gas and excludes tubular type furnace air.
2) tube furnace is risen to 250 DEG C by room temperature in 30 minutes, fluorine gas and hydrogen is passed through into pipe after reaching set temperature
The mixed gas of gas, volume ratio 1:3, mixed gas is by argon gas as carrier gas.
3) 12 hours reaction time is kept, is taken out after burner hearth after reaction is cooled to room temperature, obtains product.
4) discharge test is carried out to products therefrom, it is 3.528V to measure its discharge voltage.
The present invention discloses and proposes a kind of method regulating and controlling fluorocarbons discharge voltage by graphene planes curvature, this field
Technical staff can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although the method for the present invention and preparation
Technology is described by preferred embodiment, related technical personnel obviously can not depart from the content of present invention, spirit and
Methods and techniques described herein route is modified or is reconfigured in range, to realize final technology of preparing.Especially
It should be pointed out that all similar replacements and change it is apparent to those skilled in the art, they all by
It is considered as and is included in spirit of that invention, range and content.
Claims (3)
1. a method of regulating and controlling fluorocarbons discharge voltage using graphene planes curvature, it is characterized in that steps are as follows：
(1) it is 0.3~1.5nm by curvature-1Single-walled carbon nanotube or fullerene C60It is put into diamond heating area, install and checks pipe
Formula stove air-tightness is passed through enough argon gas into pipe and excludes tubular type furnace air；
(2) at 10-100 minutes, tube furnace is risen to 200-400 DEG C by room temperature, the mixed of fluorine gas and hydrogen is then passed through into pipe
Gas is closed, mixed gas is by argon gas as carrier gas；
(3) reaction time 0.5-24 hour is kept, is taken out after burner hearth after reaction is cooled to room temperature, obtains product.
2. the method as described in claim 1, it is characterized in that the step (2) is risen at 20-60 minutes, by tube furnace by room temperature
200-300 DEG C, it is 1 that volume ratio is then passed through into pipe:1-1:The mixed gas of 4 fluorine gas and hydrogen, mixed gas are made by argon gas
For carrier gas.
3. the method as described in claim 1, it is characterized in that the step (3) is kept for reaction time 8-16 hour.
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| CN109411752A (en) * | 2017-08-15 | 2019-03-01 | 天津大学 | A method of carbon fluoride nano-tube is prepared by Fluorine source of fluorine gas |
| CN108726504A (en) * | 2018-05-18 | 2018-11-02 | 叶荣森 | A kind of high efficiency preparation method of fluorinated fullerene |
| CN112520723A (en) * | 2019-09-18 | 2021-03-19 | 天津大学 | Method for periodically improving carbon fluoride discharge voltage by destroying graphene |
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