CN109411752A - A method of carbon fluoride nano-tube is prepared by Fluorine source of fluorine gas - Google Patents
A method of carbon fluoride nano-tube is prepared by Fluorine source of fluorine gas Download PDFInfo
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- CN109411752A CN109411752A CN201710698631.9A CN201710698631A CN109411752A CN 109411752 A CN109411752 A CN 109411752A CN 201710698631 A CN201710698631 A CN 201710698631A CN 109411752 A CN109411752 A CN 109411752A
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- fluorine
- tube
- carbon nanotube
- fluorine gas
- fluoride nano
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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
- H01M10/052—Li-accumulators
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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 discloses a kind of method for preparing carbon fluoride nano-tube as Fluorine source using fluorine gas, carbon nanotube is put into after being dried in vacuum oven, carbon nanotube is put into reaction kettle, the mixed gas for being passed through fluorine gas and nitrogen is reacted, and being dried after reacting can be obtained carbon fluoride nano-tube.Technical solution of the present invention is simple and easy to do, easy to implement, and the carbon fluoride nano-tube of different fluorine carbon ratios can be obtained by adjusting parameter.
Description
Technical field
The present invention relates to a kind of methods for preparing fluorination single-walled carbon nanotube as Fluorine source using fluorine gas, specifically pass through fluorine
Gas is fluorinated to prepare the fluorination single-walled carbon nanotube of different fluorine carbon ratios.
Background technique
With the development of electronics technology, electronic product plays an important role in human lives, and battery performance
Quality directly affects the usage experience of people, therefore develops stabilization, safety, intelligence and sustainable battery and seem and especially close
Key.In all energy storage materials, fluorocarbons gets more and more people's extensive concerning as battery material specific energy with higher.Fluorine
Carbon nano tube, which compares the fluorographite studied in the past, has higher discharge voltage and high rate performance, and development prospect is wide.
Carbon nano tube structure stablize, high mechanical strength, large specific surface area, good conductivity, have excellent mechanics, optics,
Electricity and chemical property are constantly mined discovery using potentiality.By the way that multi-walled carbon nanotube is fluorinated and can greatly be changed
It is apt to its performance, there is important application on electrode material.But the fluorine carbon ratio of the single-walled carbon nanotube of hydro-thermal method preparation is too low, and not
It is easy to regulate and control.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, for the fluorine carbon ratio of carbon fluoride nano-tube in the prior art
It is not high and not easy-regulating the shortcomings that, a kind of method of carbon fluoride nano-tube preparing high fluorine carbon ratio is provided.
Technical purpose of the invention is achieved by following technical proposals:
A method of carbon fluoride nano-tube being prepared by Fluorine source of fluorine gas, is placed in reaction kettle with carbon nanotube, with fluorine gas
Air in reaction kettle is excluded with the mixed gas of nitrogen, 100-350 degrees Celsius is warming up to from 20-25 degrees Celsius of room temperature and keeps the temperature
It is reacted, so that carbon nanotube is fluorinated.
In the above-mentioned technical solutions, carbon nanotube is single-walled carbon nanotube or multi-walled carbon nanotube.
In the above-mentioned technical solutions, single-walled carbon nanotube is the carbon nanotube bundles purified.
In the above-mentioned technical solutions, carbon nanotube is handled by vacuum drying, and carbon nanotube is put into vacuum oven,
6-48h is dried under the conditions of 40-120 DEG C, is dried 12-24 hours under preferably 60-100 degrees Celsius.
In the above-mentioned technical solutions, the product after fluorination reaction is placed in a vacuum drying oven dry 6-48h, obtains fluorocarbons
Nanotube product.
In the above-mentioned technical solutions, the time for carrying out fluorination reaction is 4-48 hours, preferably 10-30 hours.
In the above-mentioned technical solutions, 150-250 degrees Celsius are warming up to from 20-25 degrees Celsius of room temperature, heating rate is every
1-5 degrees Celsius of minute.
In the above-mentioned technical solutions, in the mixed gas of fluorine gas and nitrogen, the percentage by volume of fluorine gas is not more than 80%,
It is preferred that 15-30%.
Technical solution of the present invention is convenient and easy, and can pass through fluorine gas percentage by volume, fluorination reaction temperature and the tune of time
Degree of fluorination that is whole and then controlling carbon nanotube.It is characterized with being fluorinated the carbon nanotube of front and back, as shown in attached drawing 1-4, fluorination
Front and back, which does not change significantly, illustrates that structure is not destroyed, and is tested by EDS power spectrum it is found that fluorine element success and carbon nanometer
Pipe carries out compound.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of single-walled carbon nanotube used in the present invention.
Fig. 2 is the transmission electron microscope picture (1) of the fluorination single-walled carbon nanotube prepared using technical solution of the present invention.
Fig. 3 is the transmission electron microscope picture (2) of the fluorination single-walled carbon nanotube prepared using technical solution of the present invention.
Fig. 4 is the EDS power spectrum spectrogram of the fluorination single-walled carbon nanotube prepared using technical solution of the present invention.
Fig. 5 is to use the fluorination single-walled carbon nanotube of technical solution of the present invention preparation as the electricity of lithium primary cell positive electrode
Performance test figure.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.For single-walled carbon nanotube, from
20-25 degrees Celsius of room temperature heatings, heating rate are 1-5 degrees Celsius per minute.
Embodiment 1
30mg single-walled carbon nanotube is put into vacuum oven, dries 12h under the conditions of 120 DEG C；Then by the list of drying
Wall carbon nano tube is put into the reaction kettle of 5L, is passed through the mixed gas of F2/N2, the percentage by volume of fluorine gas is 20%, at 100 DEG C
Lower reaction 8h.Obtained product is finally placed in a vacuum drying oven dry 12h, obtains the fluorination single wall carbon that fluorine carbon ratio is 0.34
Nanotube.
Embodiment 2
28mg single-walled carbon nanotube is put into vacuum oven, is dried for 24 hours under the conditions of 80 DEG C；Then by the single wall of drying
Carbon nanotube is put into the reaction kettle of 5L, is passed through the mixed gas of F2/N2, the percentage by volume of fluorine gas is 60%, at 260 DEG C
React 20h.Obtained product is finally placed in a vacuum drying oven dry 20h, obtains the fluorination single wall carbon that fluorine carbon ratio is 0.85
Nanotube.
Embodiment 3
35mg single-walled carbon nanotube is put into vacuum oven, dries 12h under the conditions of 80 DEG C；Then by the single wall of drying
Carbon nanotube is put into the reaction kettle of 5L, is passed through the mixed gas of F2/N2, the percentage by volume of fluorine gas is 30%, at 200 DEG C
React 10h.Obtained product is finally placed in a vacuum drying oven dry 18h, obtains the fluorination single wall carbon that fluorine carbon ratio is 0.42
Nanotube.
Embodiment 4
26mg single-walled carbon nanotube is put into vacuum oven, dries 18h under the conditions of 100 DEG C；Then by the list of drying
Wall carbon nano tube is put into the reaction kettle of 5L, is passed through the mixed gas of F2/N2, the percentage by volume of fluorine gas is 5%, at 180 DEG C
Lower reaction 8h.Obtained product is finally placed in a vacuum drying oven drying for 24 hours, obtains the fluorination single wall carbon that fluorine carbon ratio is 0.45
Nanotube.
Embodiment 5
34mg single-walled carbon nanotube is put into vacuum oven, dries 12h under the conditions of 80 DEG C；Then by the single wall of drying
Carbon nanotube is put into the reaction kettle of 5L, is passed through the mixed gas of F2/N2, the percentage by volume of fluorine gas is 50%, at 220 DEG C
React 15h.Obtained product is finally placed in a vacuum drying oven dry 12h, obtains the fluorination single wall carbon that fluorine carbon ratio is 0.62
Nanotube.
The fluorination single-walled carbon nanotube for using technical solution of the present invention to prepare as the application of lithium primary cell positive electrode,
Electric performance test is as follows:
(1) preparation of electrode
It weighs PVDF to be added in NMP, is configured to the solution that concentration is 50mg/ml.It is measured respectively for 8:1:1 in mass ratio
FC sample, acetylene black, PVDF prepare battery.NMP ultrasonic disperse is added dropwise thereto into uniform sizing material solution.Aluminium is cleaned using ethyl alcohol
Paillon is placed in baking oven and dries, and by scattered pulp solution even application on aluminium foil, is placed in convection oven 60 DEG C
12h is dried, 60 DEG C of vacuum drying 12h in vacuum oven are subsequently placed at.It takes out, the amount of active material is determined using mass difference method,
Carry out battery assembly.
(2) lithium battery assembly technology
The electrode slice prepared is put into glove box.Choose the 1M for being dissolved in the PC/DME mixed solvent that volume ratio is 1:1
LiBF4As liquid electrolyte, using the polyethylene film with microcellular structure as diaphragm.Stainless steel elastic slice is first placed on battery
In negative cover, gasket is placed, is then placed in metal lithium sheet, electrolyte is added dropwise, diaphragm is put into after standing 1-2 hours, places into
Simultaneously 5-10ml electrolyte are added dropwise in electrode slice again, are finally sealed with sealing machine.The battery assembled is taken the photograph in room temperature 20-25 first
Family name's degree is stood for 24 hours, is allowed electrolyte sufficiently to infiltrate positive and negative pole material, is then carried out the test of related chemical property again.
(3) constant-current discharge is tested
Battery is connected on LAND battery test system, after standing 10min, carries out constant current discharge performance test,
The discharge current of test is 10mAg-1, final discharging voltage 1.5V, test directly measures using button cell and being obtained data,
As shown in Fig. 5, stable electric property and good specific capacity are shown.
Content carries out the adjustment of preparation technology parameter according to the present invention, and the fluorination of carbon nanotube can be achieved, and can pass through
Fluorine gas percentage by volume, fluorination reaction temperature and the adjustment of time changed to realize degree of fluorination.The present invention is done above
Exemplary description, it should explanation, in the case where not departing from core of the invention, it is any it is simple deformation, modification or
Other skilled in the art can not spend the equivalent replacement of creative work to each fall within protection scope of the present invention.
Claims (7)
1. a kind of method for preparing carbon fluoride nano-tube as Fluorine source using fluorine gas, which is characterized in that be placed in reaction kettle with carbon nanotube
In, air in reaction kettle is excluded with the mixed gas of fluorine gas and nitrogen, 100-350 is warming up to from 20-25 degrees Celsius of room temperature and takes the photograph
Family name's degree and keep the temperature react so that carbon nanotube is fluorinated.
2. a kind of method for preparing carbon fluoride nano-tube as Fluorine source using fluorine gas according to claim 1, which is characterized in that carbon
Nanotube is single-walled carbon nanotube or multi-walled carbon nanotube.
3. a kind of method for preparing carbon fluoride nano-tube as Fluorine source using fluorine gas according to claim 1, which is characterized in that into
The time of row fluorination reaction is 4-48 hours, preferably 10-30 hours.
4. a kind of method for preparing carbon fluoride nano-tube as Fluorine source using fluorine gas according to claim 1, which is characterized in that from
20-25 degrees Celsius of room temperature are warming up to 150-250 degrees Celsius, and heating rate is 1-5 degrees Celsius per minute.
5. a kind of method for preparing carbon fluoride nano-tube as Fluorine source using fluorine gas according to claim 1, which is characterized in that with
In the mixed gas of fluorine gas and nitrogen, the percentage by volume of fluorine gas is not more than 80%, preferably 15-30%.
6. a kind of method for preparing carbon fluoride nano-tube as Fluorine source using fluorine gas according to claim 1, which is characterized in that can
Pass through the degree of fluorination of the adjustment control carbon nanotube of fluorine gas percentage by volume, fluorination reaction temperature and time.
7. application of the carbon fluoride nano-tube of the method as described in claim 1 preparation as lithium primary cell positive electrode.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112394A (en) * | 2019-05-14 | 2019-08-09 | 中国民航大学 | A kind of preparation method of fluorocarbons/metal fluoride composite positive pole |
| CN110148747A (en) * | 2019-05-14 | 2019-08-20 | 中国民航大学 | A kind of preparation method of the fluorocarbons positive electrode with anti-expansion function |
| CN110165210A (en) * | 2019-05-14 | 2019-08-23 | 中国民航大学 | A kind of preparation method of the fluorocarbons positive electrode with height ratio capacity |
| CN112542584A (en) * | 2019-09-23 | 2021-03-23 | 天津大学 | Carbon fluoride nanohorn material for lithium primary battery positive electrode material and preparation method thereof |
| CN113233443A (en) * | 2021-04-22 | 2021-08-10 | 电子科技大学 | Preparation method of fluorinated spiral carbon nanotube and application of fluorinated spiral carbon nanotube in lithium primary battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0142113A2 (en) * | 1983-11-07 | 1985-05-22 | Daikin Kogyo Co., Ltd. | Active material for batteries |
| CN102730664A (en) * | 2012-07-04 | 2012-10-17 | 四川大学 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
| CN103276593A (en) * | 2013-05-28 | 2013-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for enhancing carbon nano tube fiber by utilizing fluorine-removing cross-linking reaction |
| CN103332669A (en) * | 2013-06-14 | 2013-10-02 | 谢子卓 | Method for preparing carbon monofluoride or fluorocarbon through inner circulation of fluorine |
| CN106008974A (en) * | 2016-06-02 | 2016-10-12 | 黑龙江科技大学 | Preparation method of highly hydrophobic carbon fluoride nanotube/polyimide composite material |
| CN106229506A (en) * | 2016-08-17 | 2016-12-14 | 天津大学 | A kind of method by graphene planes curvature regulation and control perfluorocarbon discharge voltage |
| CN106698410A (en) * | 2016-12-05 | 2017-05-24 | 四川大学 | Method for preparing nitrogen-atom doped carbon nanomaterial |
-
2017
- 2017-08-15 CN CN201710698631.9A patent/CN109411752A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0142113A2 (en) * | 1983-11-07 | 1985-05-22 | Daikin Kogyo Co., Ltd. | Active material for batteries |
| CN102730664A (en) * | 2012-07-04 | 2012-10-17 | 四川大学 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
| CN103276593A (en) * | 2013-05-28 | 2013-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for enhancing carbon nano tube fiber by utilizing fluorine-removing cross-linking reaction |
| CN103332669A (en) * | 2013-06-14 | 2013-10-02 | 谢子卓 | Method for preparing carbon monofluoride or fluorocarbon through inner circulation of fluorine |
| CN106008974A (en) * | 2016-06-02 | 2016-10-12 | 黑龙江科技大学 | Preparation method of highly hydrophobic carbon fluoride nanotube/polyimide composite material |
| CN106229506A (en) * | 2016-08-17 | 2016-12-14 | 天津大学 | A kind of method by graphene planes curvature regulation and control perfluorocarbon discharge voltage |
| CN106698410A (en) * | 2016-12-05 | 2017-05-24 | 四川大学 | Method for preparing nitrogen-atom doped carbon nanomaterial |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112394A (en) * | 2019-05-14 | 2019-08-09 | 中国民航大学 | A kind of preparation method of fluorocarbons/metal fluoride composite positive pole |
| CN110148747A (en) * | 2019-05-14 | 2019-08-20 | 中国民航大学 | A kind of preparation method of the fluorocarbons positive electrode with anti-expansion function |
| CN110165210A (en) * | 2019-05-14 | 2019-08-23 | 中国民航大学 | A kind of preparation method of the fluorocarbons positive electrode with height ratio capacity |
| CN110112394B (en) * | 2019-05-14 | 2021-12-10 | 中国民航大学 | Preparation method of carbon fluoride/metal fluoride composite positive electrode material |
| CN110165210B (en) * | 2019-05-14 | 2021-12-24 | 中国民航大学 | Preparation method of carbon fluoride anode material with high specific capacity |
| CN110148747B (en) * | 2019-05-14 | 2022-04-15 | 中国民航大学 | Preparation method of carbon fluoride anode material with anti-expansion function |
| CN112542584A (en) * | 2019-09-23 | 2021-03-23 | 天津大学 | Carbon fluoride nanohorn material for lithium primary battery positive electrode material and preparation method thereof |
| CN113233443A (en) * | 2021-04-22 | 2021-08-10 | 电子科技大学 | Preparation method of fluorinated spiral carbon nanotube and application of fluorinated spiral carbon nanotube in lithium primary battery |
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