CN102730664B - Carbon nano-tube with fluorine-containing surface and preparation method thereof - Google Patents
Carbon nano-tube with fluorine-containing surface and preparation method thereof Download PDFInfo
- Publication number
- CN102730664B CN102730664B CN201210229914.6A CN201210229914A CN102730664B CN 102730664 B CN102730664 B CN 102730664B CN 201210229914 A CN201210229914 A CN 201210229914A CN 102730664 B CN102730664 B CN 102730664B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- tube
- carbon nanotube
- gas
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y02P20/121—
Abstract
The invention discloses a carbon nano-tube with a fluorine-containing surface, wherein the surface of the carbon nano-tube is of a carbon-fluorine covalent bond structure, the content of fluorine in the surface is 4-14%, and the decrease rate of the content of the fluorine is smaller than 5% after a produced fluorocarbon nano-tube is treated for 1 hour under a vacuum condition at 350 DEG C. The preparation method of the carbon nano-tube comprises the following steps of: firstly treating the carbon nano-tube by utilizing strong acid, secondly placing the carbon nano-tube in a vacuum reactor, charging fluorine/inert gas mixture with fluorine partial pressure of 10-100KPa in nitrogen atmosphere under room temperature to react for 0.5-4 hours at 150-300 DEG C, and cooling down to be the room temperature to obtain the carbon nano-tube. The fluorocarbon nano-tube prepared by the preparation method disclosed by the invention has the advantages of high fluorine content, low reaction temperature, high safety, energy conservation, and simple process, a fluorine-containing group of the surface of the treated prepared fluorocarbon nano-tube has good heat resistance and lower cost, and the fluorocarbon nano-tube is suitable for large-batch production and has stronger application prospect.
Description
Technical field
The invention belongs to modified carbon nano-tube and preparing technical field thereof, be specifically related to a kind of fluorine-contained surface carbon nanotube and preparation method thereof.
Background technology
Carbon nanotube is because of its outstanding physical and mechanical properties, and peculiar electric property and good chemical stability, thermostability, have potential using value in all many-sides, particularly has broad application prospects in high molecule nano composite material field.But, due to carbon nano tube surface 'inertia' and strong van der Waals interaction, make himself very easily to reunite, cause carbon nanotube in machine solvent and resin matrix, to be difficult to dispersedly common are, limited its research in high molecule nano composite material field and application.Therefore, carbon nanotube is carried out to surface treatment just seem particularly important in order to obtain the high molecule nano composite material of excellent performance.
The main method of carbon nano tube surface processing at present has acid oxidation, surface grafting and direct surface fluorination method.Though acid oxidation is easy to operate, technique is simple and can improve the dispersiveness of carbon nanotube, but its shortcoming is also very obvious, because using strong acid as treatment media, and the oxygen-containing functional group poor heat stability of introducing on its surface.As the people's (Adv. Mater, 2005,17:17-29) such as S. Banerjee research shows, the general decomposition temperature of oxygen-containing functional group on carbon nanotube, 200 DEG C of left and right, has limited its application in thermally stable polymer matrix material.And there is on the one hand complex process in existing surface grafting method, production cost is higher, be unfavorable for the problem of large-scale continuous production, still there is on the other hand the not high problem of surface-functionalized group thermotolerance of its grafting, as Jianfeng Shen(Composites Science and Technology, 2007,67:3041-3050) and B.X. Yang(Nanotechnology, 2007,18:125606-125613) research shown in.Direct surface fluoridation technology is the effective surface modifying method of one that fast development is got up in recent years, and it is to utilize the fluorine gas of high reaction activity, as fluorination reagent, material surface is carried out to modification.It is low that direct fluorinated surface processing has cost, only forms nanometer layer at material surface, do not affect the advantages such as material body structure.Just because of the plurality of advantages of direct fluorinated surface treatment technology, such as the carbon nanotube after fluoridation has better dispersiveness in polar organic solvent; Carbon nanotube after fluoridation can be used for preparing novel high-performance lithium ion battery, can increase substantially its charge-discharge performance etc.Therefore, using this technology to carry out surface treatment to carbon nanotube attracts wide attention.But due to the relative unreactiveness of carbon nano tube surface, the functionalization group that obtain high surfaces fluorine content and fluoridize introducing has high thermostability just to be become and prepares important investigative technique difficult problem of high performance fluorine carbon nano tube.
Utilize at present direct fluorinated surface treatment technology to carry out fluoridation to carbon nanotube and mainly contain two kinds of high-temperature fluorination and low temperature fluorates.When high-temperature fluorination, temperature of reaction is higher, such as T. Nakajima(Eur J Solid Chem, 1996,33:831-840) and A. Hamwi(Carbon, 1997,35:723-728) research just can introduce in carbon nano tube surface carbon-fluorine bond (C-F) bond structure of good heat stability while showing that general temperature of reaction approaches 400 DEG C.But the sensitive temperature interval that this fluoridation temperature forms and decomposes in C-F key, thus fluoridation danger is larger, and the risk of explosion of especially mass-producing fluoridation carbon nanotube will be higher.Low temperature fluorate carbon nanotube refers to that being at room temperature aided with catalyzer carries out fluoridation to carbon nanotube.As A. Hamwi(Synthetic Metals, 26 (1988) 89-98) and Vinay Gupta(Journal of Fluorine Chemistry 120 (2003) 143-150) under catalyzer auxiliary, carbon nanotube is carried out to fluoridation though studied room temperature condition, the thermostability of the surface-functionalized group after it is fluoridized does not have clearly statement.The inventor is carrying out finding in correlative study process to low temperature fluorate carbon nanotube, in the time that low temperature (room temperature-100 DEG C) is fluoridized, although this fluorination process has been introduced higher fluorine content (7-9%) in carbon nano tube surface, but process 40 minutes-2 hours fluorine content at 250-300 DEG C and drop to 2% left and right, the thermostability of display surface functionalization group is poor, what this illustrated that it mainly forms is not the C-F key of good heat stability, but the fluoridation of carrying out with the existing oxygen-containing functional group of carbon nano tube surface, trace it to its cause, still at low temperatures, the carbon of carbon pipe relatively its surperficial oxygen-containing functional group itself has obvious unreactiveness, due to being not easy to react with fluorine gas.
Summary of the invention
Primary and foremost purpose of the present invention is for the deficiencies in the prior art, provides a kind of surface to have higher fluorine content and the good carbon nanotube of fluoro-containing group thermotolerance.
Another object of the present invention is to provide a kind of method of preparing above-mentioned fluorine-contained surface carbon nanotube.
The carbon nanotube of fluorine-contained surface provided by the invention, carbon-fluorine covalent bond structure is contained on the surface that it is characterized in that this carbon nanotube body, its surperficial fluorine content is 4 ~ 14%, gained carbon fluoride nano-tube is processed after 1 hour under 350 DEG C of vacuum conditions, its fluorine content rate of descent is less than 5%, is specially 3 ~ 4%.
The carbon nanotube of above-mentioned fluorine-contained surface, is characterized in that carbon nanotube body is any in multi-walled carbon nano-tubes, double-walled carbon nano-tube or Single Walled Carbon Nanotube.
The preparation method of above-mentioned fluorine-contained surface carbon nanotube provided by the invention, it is characterized in that the method is first carbon nanotube body to be carried out to oxide treatment to be placed in airtight vacuum reactor, then under atmosphere of inert gases, be filled with fluorine gas/rare gas element gas mixture, and be warming up to 150 ~ 300 DEG C reaction 0.5 ~ 4.0 hour, stop heating, question response device cool to room temperature also adopts after the remaining fluorinated gas of nitrogen replacement, can obtain carbon fluoride nano-tube, and wherein the dividing potential drop of fluorine gas remains on 10 ~ 100KPa.
In above method, atmosphere of inert gases used is at least one in nitrogen, argon gas, helium and carbon dioxide.
Oxide treatment described in above method be by carbon nanotube body with strong acid after ultrasonic mixing, stirring and refluxing 15 ~ 48 hours at 25 ~ 100 DEG C of reflux temperatures, takes out and is washed till neutrality with deionized water, vacuum-drying obtain the carbon nanotube of oxide treatment.Wherein strong acid used is at least one in sulfuric acid, nitric acid and hydrochloric acid.The oxide treatment carbon nanotube obtaining shows that body construction is not destroyed by strong acid after Raman spectrum test, as shown in Figure 1.
In above method, carbon nanotube body used is any in multi-walled carbon nano-tubes, double-walled carbon nano-tube or Single Walled Carbon Nanotube.
In above method, the dividing potential drop of fluorine gas in reactor preferably remains on 30 ~ 80KPa, maintains preferably 170 ~ 250 DEG C of fluorination reaction temperature, maintains preferably 1.0 ~ 2.5 hours time of fluoridizing of this fluorination reaction temperature.
In above method, fluorine gas/rare gas element gas mixture used is made up of at least one in fluorine gas and nitrogen, argon gas, helium and carbon dioxide.
Compared with prior art, it has following beneficial effect in the present invention:
1. because the present invention first processes carbon nanotube strong acid appropriateness, remove on the one hand impurity remaining in carbon nanotube, the more important thing is and under the prerequisite of destroying carbon nanometer tube body construction not, in carbon nano tube surface, introduce more oxygen-containing functional groups, and utilize the thermolability of oxygen-containing functional group, progressively heating up in fluorination process, oxygen-containing functional group thermolysis when removing from carbon nano tube surface, these scission of link points of fluorine gas attack immediately are around reacted, thereby more easily produce more carbon-fluorine covalent bond structure in carbon nano tube surface, realize the object of carbon nanotube being carried out greater efficiency surface fluorination at lower temperature, give carbon nanotube good thermotolerance.
2. owing to present invention can be implemented under lesser temps, carbon nanotube is fluoridized, thereby both can the in the situation that of destroying carbon nanometer tube body construction not, realize the fluoridizing of carbon nanotube, process safety is higher, is applicable to scale operation, can reduce again energy consumption, reduce production costs.
3. because technique of the present invention is simply controlled, thereby can prepare neatly by adjusting flaorination process the serial carbon nanotube of surperficial different fluorine contents, there is stronger application prospect.
4. because carbon fluoride nano-tube fluoro-containing group provided by the present invention has good thermotolerance, thereby can have a good application prospect in fields such as thermally stable polymer field of nanocomposite materials and lithium ion batteries.
5. the mentality of designing of the fluorine-contained surface carbon nanotube of preparing due to the inventive method is ingenious, thereby not only provides a kind of surperficial fluorine content high, and the carbon fluoride nano-tube of good heat resistance, also provides a kind of new approach and new thought for preparing carbon fluoride nano-tube.
Brief description of the drawings
Fig. 1 is the Raman spectrogram of the multi-walled carbon nano-tubes after acidification and untreated multi-walled carbon nano-tubes in the embodiment of the present invention 5.As can be seen from the figure the peak type of the Raman spectrogram of two kinds of multi-wall carbon nano-tubes does not have considerable change, this explanation multi-walled carbon nano-tubes show that body construction is not destroyed after strong acid acidifying.
Fig. 2 is the x-ray photoelectron energy spectrogram of the embodiment of the present invention 5, embodiment 2 and comparative example 1.The carbon fluoride nano-tube of the embodiment of the present invention 5 and 2 is at the 698eV of spectrogram in conjunction with the power spectrum peak that can locate all to have fluorine element as we can see from the figure, and comparative example 1 does not have, and this explanation the inventive method is for the validity of carbon fluoride nano-tube.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the person skilled in the art in this field makes according to the content of the invention described above, still belong to protection scope of the present invention
What deserves to be explained is, the fluorine content of products therefrom is to obtain by x-ray photoelectron power spectrum measuring and calculation.
Embodiment 1
By multi-wall carbon nano-tube tube body with hydrochloric acid after ultrasonic mixing, stirring and refluxing 15 hours at 25 DEG C of reflux temperatures, takes out and is washed till neutrality, vacuum-drying with deionized water; To be placed in airtight vacuum reactor with acid treatment vacuum drying multi-walled carbon nano-tubes, then vacuumize, and with after the air in nitrogen replacement reactor three times, in vacuum reactor, be filled with delivery of fluorine/nitrogen gas mixture, controlling fluorine gas dividing potential drop in reactor is 10KPa, and being warming up to 300 DEG C, fluoridation 0.5 hour, takes out sample after question response device naturally cooling and obtains carbon fluoride nano-tube.The fluorine content of XPS test carbon fluoride nano-tube is 4%.Gained carbon fluoride nano-tube is processed after 1 hour under 350 DEG C of vacuum conditions, and its fluorine content drops to 3.88 %, and rate of descent is 3.0 %.
Embodiment 2
By multi-wall carbon nano-tube tube body with nitric acid after ultrasonic mixing, stirring and refluxing 48 hours at 100 DEG C of reflux temperatures, takes out and is washed till neutrality, vacuum-drying with deionized water; To be placed in airtight vacuum reactor with acid treatment vacuum drying multi-walled carbon nano-tubes, then vacuumize, and with after the air in nitrogen replacement reactor three times, in vacuum reactor, be filled with delivery of fluorine/nitrogen gas mixture, controlling fluorine gas dividing potential drop in reactor is 30KPa, and being warming up to 250 DEG C, fluoridation 1 hour, takes out sample after question response device naturally cooling and obtains carbon fluoride nano-tube.The fluorine content of XPS test carbon fluoride nano-tube is 8%.Gained carbon fluoride nano-tube is processed after 1 hour under 350 DEG C of vacuum conditions, and its fluorine content drops to 7.67 %, and rate of descent is 4.1 %.
Embodiment 3
By double-walled carbon nano-tube body with sulfuric acid after ultrasonic mixing, stirring and refluxing 30 hours at 30 DEG C of reflux temperatures, takes out and is washed till neutrality, vacuum-drying with deionized water; To be placed in airtight vacuum reactor with acid treatment vacuum drying double-walled carbon nano-tube, then vacuumize, and with after the air in nitrogen replacement reactor three times, in vacuum reactor, be filled with delivery of fluorine/nitrogen/argon gas gas mixture, controlling fluorine gas dividing potential drop in reactor is 50KPa, and being warming up to 200 DEG C, fluoridation 2 hours, takes out sample after question response device naturally cooling and obtains carbon fluoride nano-tube.The fluorine content of XPS test carbon fluoride nano-tube is 7.45%.Gained carbon fluoride nano-tube is processed after 1 hour under 350 DEG C of vacuum conditions, and its fluorine content drops to 7.15 %, and rate of descent is 4.0 %.
Embodiment 4
By Single Walled Carbon Nanotube body with hydrochloric acid after ultrasonic mixing, stirring and refluxing 17 hours at 30 DEG C of reflux temperatures, takes out and is washed till neutrality, vacuum-drying with deionized water; To be placed in airtight vacuum reactor by acid treatment vacuum drying Single Walled Carbon Nanotube, then vacuumize, and with after the air in nitrogen/argon oxygen mixture metathesis reactor three times, in vacuum reactor, be filled with delivery of fluorine/nitrogen gas mixture, controlling fluorine gas dividing potential drop in reactor is 100KPa, and being warming up to 150 DEG C, fluoridation 4 hours, takes out sample after question response device naturally cooling and obtains carbon fluoride nano-tube.The fluorine content of XPS test carbon fluoride nano-tube is 4.25%.Gained carbon fluoride nano-tube is processed after 1 hour under 350 DEG C of vacuum conditions, and its fluorine content drops to 4.11 %, and rate of descent is 3.2 %.
Embodiment 5
By Single Walled Carbon Nanotube body with nitric acid after ultrasonic mixing, stirring and refluxing 40 hours at 75 DEG C of reflux temperatures, takes out and is washed till neutrality, vacuum-drying with deionized water; To be placed in airtight vacuum reactor by acid treatment vacuum drying Single Walled Carbon Nanotube, then vacuumize, and with after the air in argon replaces reactor three times, in vacuum reactor, be filled with delivery of fluorine/nitrogen gas mixture, controlling fluorine gas dividing potential drop in reactor is 100KPa, and being warming up to 250 DEG C, fluoridation 1 hour, takes out sample after question response device naturally cooling and obtains carbon fluoride nano-tube.The fluorine content of XPS test carbon fluoride nano-tube is 14%.Gained carbon fluoride nano-tube is processed after 1 hour under 350 DEG C of vacuum conditions, and its fluorine content drops to 13.44 %, and rate of descent is 4 %.
Embodiment 6
By Single Walled Carbon Nanotube body with sulfuric acid after ultrasonic mixing, stirring and refluxing 35 hours at 55 DEG C of reflux temperatures, takes out and is washed till neutrality, vacuum-drying with deionized water; To be placed in airtight vacuum reactor with acid treatment vacuum drying multi-walled carbon nano-tubes, then vacuumize, and with after the air in argon replaces reactor three times, in vacuum reactor, be filled with delivery of fluorine/nitrogen/carbon dioxide mix gas, controlling fluorine gas dividing potential drop in reactor is 80KPa, and being warming up to 170 DEG C, fluoridation 2.5 hours, takes out sample after question response device naturally cooling and obtains carbon fluoride nano-tube.The fluorine content of XPS test carbon fluoride nano-tube is 5.87%.Gained carbon fluoride nano-tube is processed after 1 hour under 350 DEG C of vacuum conditions, and its fluorine content drops to 5.68 %, and rate of descent is 3.3 %.
Comparative example 1
Multi-walled carbon nano-tubes is placed in to airtight vacuum reactor, then vacuumizes, and with after the air in nitrogen replacement reactor three times, again vacuumize and be warming up to 250 DEG C, and maintain this temperature and within 1 hour, allow carbon nanotube fully remove oxy radical.Now, in reactor, be filled with delivery of fluorine/nitrogen gas mixture, controlling fluorine gas dividing potential drop in reactor is 80KPa, under 250 DEG C of conditions, reacts 2 hours, after question response device naturally cooling, take out sample and obtain carbon fluoride nano-tube, the fluorine content of XPS test carbon fluoride nano-tube is 0.41%.
Comparative example 2
By Single Walled Carbon Nanotube body with nitric acid after ultrasonic mixing, stirring and refluxing 40 hours at 75 DEG C of reflux temperatures, takes out and is washed till neutrality, vacuum-drying with deionized water; To be placed in airtight vacuum reactor by acid treatment vacuum drying Single Walled Carbon Nanotube, then vacuumize, and with after the air in nitrogen replacement reactor three times, in vacuum reactor, be filled with delivery of fluorine/nitrogen gas mixture, controlling fluorine gas dividing potential drop in reactor is 100KPa, and being warming up to 25 DEG C, fluoridation 3 hours, takes out sample after question response device naturally cooling and obtains carbon fluoride nano-tube.The fluorine content of XPS test carbon fluoride nano-tube is 10%.After this carbon fluoride nano-tube is processed to 1 hour under 350 DEG C of vacuum conditions, test its fluorine content and drop to 1.15%, rate of descent is 88.5 %.
Claims (10)
1. the carbon nanotube of a fluorine-contained surface, it is characterized in that this carbon nanotube be first with strong acid after ultrasonic mixing, stirring and refluxing 15～48 hours at 25～100 DEG C of reflux temperatures, taking-up is washed till neutrality with deionized water, vacuum-drying is placed in airtight vacuum reactor, then under atmosphere of inert gases, be filled with fluorine gas/rare gas element gas mixture, wherein the dividing potential drop of fluorine gas remains on 10～100KPa, and be warming up to 150～300 DEG C reaction 0.5～4.0 hour, stop heating, question response device cool to room temperature and adopt the remaining fluorinated gas of nitrogen replacement after obtain, carbon-fluorine covalent bond structure is contained on the surface of its body, its surperficial fluorine content is 4～14%, gained carbon fluoride nano-tube is processed after 1 hour under 350 DEG C of vacuum conditions, its fluorine content rate of descent is less than 5%.
2. the carbon nanotube of fluorine-contained surface according to claim 1, is characterized in that carbon nanotube body is any in multi-walled carbon nano-tubes, double-walled carbon nano-tube or Single Walled Carbon Nanotube.
3. the preparation method of a fluorine-contained surface carbon nanotube claimed in claim 1, it is characterized in that the method be first by carbon nanotube with strong acid after ultrasonic mixing, stirring and refluxing 15～48 hours at 25～100 DEG C of reflux temperatures, taking-up is washed till neutrality with deionized water, vacuum-drying is placed in airtight vacuum reactor, then under atmosphere of inert gases, be filled with fluorine gas/rare gas element gas mixture, and be warming up to 150～300 DEG C reaction 0.5～4.0 hour, stop heating, question response device cool to room temperature also adopts after the remaining fluorinated gas of nitrogen replacement, can obtain carbon fluoride nano-tube, wherein the dividing potential drop of fluorine gas remains on 10～100KPa.
4. the preparation method of fluorine-contained surface carbon nanotube according to claim 3, is characterized in that the method strong acid used is at least one in sulfuric acid, nitric acid or hydrochloric acid.
5. according to the preparation method of the fluorine-contained surface carbon nanotube described in claim 3 or 4, it is characterized in that the method carbon nanotube body used is any in multi-walled carbon nano-tubes, double-walled carbon nano-tube or Single Walled Carbon Nanotube.
6. according to the method for preparing fluorine-contained surface carbon nanotube described in claim 3 or 4, it is characterized in that in the method, the dividing potential drop of fluorine gas in reactor remains on 30～80KPa, maintaining fluorination reaction temperature is 170～250 DEG C, and the time of fluoridizing that maintains this fluorination reaction temperature is 1.0～2.5 hours.
7. the method for preparing fluorine-contained surface carbon nanotube according to claim 5, it is characterized in that in the method, the dividing potential drop of fluorine gas in reactor remains on 30～80KPa, maintaining fluorination reaction temperature is 170～250 DEG C, and the time of fluoridizing that maintains this fluorination reaction temperature is 1.0～2.5 hours.
8. according to the preparation method of the fluorine-contained surface carbon nanotube described in claim 3 or 4, it is characterized in that the method fluorine gas/rare gas element gas mixture used is made up of at least one in fluorine gas and nitrogen, argon gas, helium and carbon dioxide.
9. the preparation method of fluorine-contained surface carbon nanotube according to claim 5, is characterized in that the method fluorine gas/rare gas element gas mixture used is made up of at least one in fluorine gas and nitrogen, argon gas, helium and carbon dioxide.
10. the preparation method of fluorine-contained surface carbon nanotube according to claim 7, is characterized in that the method fluorine gas/rare gas element gas mixture used is made up of at least one in fluorine gas and nitrogen, argon gas, helium and carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210229914.6A CN102730664B (en) | 2012-07-04 | 2012-07-04 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210229914.6A CN102730664B (en) | 2012-07-04 | 2012-07-04 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102730664A CN102730664A (en) | 2012-10-17 |
| CN102730664B true CN102730664B (en) | 2014-11-05 |
Family
ID=46987070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210229914.6A Active CN102730664B (en) | 2012-07-04 | 2012-07-04 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102730664B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241724B (en) * | 2013-05-09 | 2015-06-10 | 上海应用技术学院 | Fluorine-containing polymer functionalized carbon nanotube and preparation method thereof |
| CN106592215B (en) * | 2016-12-19 | 2018-11-02 | 曲阜师范大学 | A method of preparing fluorine content and size adjustable fluorinated carbon fiber |
| CN107163912B (en) * | 2017-06-13 | 2019-08-20 | 四川大学 | A kind of MWCNTSWave absorbing agent, preparation method and absorbing material |
| 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 |
| CN109179374A (en) * | 2018-08-17 | 2019-01-11 | 山东重山光电材料股份有限公司 | A kind of method of low temperature preparation fluorinated carbon material |
| CN110875475A (en) * | 2018-09-04 | 2020-03-10 | 天津大学 | Method for preparing high-specific-energy carbon fluoride anode material by gas-phase fluoridation of fruit shell carbon |
| CN109449330A (en) * | 2018-09-21 | 2019-03-08 | 江苏微能电子科技有限公司 | Vehicle-mounted new energy battery pack |
| CN110862700A (en) * | 2019-12-03 | 2020-03-06 | 祁娟 | Preparation method of oil-water amphiphilic powder and powder prepared by same |
| CN111005211B (en) * | 2019-12-30 | 2021-08-13 | 四川大学 | Aromatic polymer fiber with excellent interface performance and preparation method thereof |
| CN112591732B (en) * | 2020-12-15 | 2022-06-24 | 西北大学 | Preparation method of fluorinated graphene and fluorinated carbon nanotube with controllable fluorine content |
| CN115939417A (en) * | 2023-01-06 | 2023-04-07 | 中国科学院长春应用化学研究所 | Membrane electrode for proton exchange membrane fuel cell and preparation method thereof |
-
2012
- 2012-07-04 CN CN201210229914.6A patent/CN102730664B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 直接氟化制备氟化多壁碳纳米管新途径研究;陈一等;《2011年全国高分子学术论文报告会论文摘要集》;20110924;884 * |
| 陈一等.直接氟化制备氟化多壁碳纳米管新途径研究.《2011年全国高分子学术论文报告会论文摘要集》.2011, * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102730664A (en) | 2012-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102730664B (en) | Carbon nano-tube with fluorine-containing surface and preparation method thereof | |
| CN102070142B (en) | Method for preparing graphene by chemical oxidation reduction | |
| CN103332681B (en) | Method for preparing porous carbon based nanomaterial through carbon dioxide conversion | |
| CN102698774B (en) | Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material | |
| CN102683710A (en) | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof | |
| CN108264037B (en) | Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene | |
| CN103466607A (en) | Graphene-metallic oxide nano-particle three-dimensional porous composite material | |
| CN106744894B (en) | A kind of preparation method of graphene powder | |
| CN103359709A (en) | Preparation method of nitrogen-doped graphene | |
| CN104944392A (en) | Mass preparation method of graphite-phase carbon nitride nanosheets | |
| CN102718209B (en) | Method for preparing graphene based on reduction of divalent iron ion | |
| CN105197910B (en) | A kind of method that porous nano carbon material is prepared using biomass as carbon source | |
| CN109755485A (en) | A kind of SnO2/ graphene lithium ion battery cathode material preparation method | |
| CN103387223A (en) | Preparation method of graphite | |
| CN108190878A (en) | A kind of method that one-step method under cryogenic prepares graphene oxide | |
| CN105752970B (en) | A kind of preparation method of carbon nano tube/graphene compound | |
| CN109671916A (en) | The Preparation method and use of mesoporous iron oxide composite carbon nanometer tube | |
| CN106976854B (en) | A method of preparing carbon material | |
| CN104030265B (en) | Nitrogen-doped carbon nanometer pipe and preparation method thereof | |
| CN105562005A (en) | Nano composite material with carbon-coated Ni nano crystal particles loaded on graphene and preparation method of nano composite material | |
| CN103641101A (en) | Two-dimensional structural carbon nanomaterial and preparation method thereof | |
| CN104466133B (en) | A kind of graphene carbon composite of N doping and preparation method thereof | |
| Liu et al. | CuS nanotubes prepared using Cu (OH) 2 nanowires as self-sacrificial template | |
| Azodpour et al. | Microwave assisted purification of multi-walled carbon nanotubes by potassium permanganate; effect of acid to oxidant molar ratio and treatment time | |
| Liu et al. | Hydrothermal synthesis and characterization of graphene/self-assembled SnO2 hybrid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |