CN109056193A - The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film - Google Patents
The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film Download PDFInfo
- Publication number
- CN109056193A CN109056193A CN201810727262.6A CN201810727262A CN109056193A CN 109056193 A CN109056193 A CN 109056193A CN 201810727262 A CN201810727262 A CN 201810727262A CN 109056193 A CN109056193 A CN 109056193A
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile
- sulphur
- nano tube
- carbon nano
- composite fibre
- 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.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/413—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties containing granules other than absorbent substances
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/43—Acrylonitrile series
-
- 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
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 invention discloses the application of a kind of preparation method of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film and its flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film of preparation in metal sulphur cell positive electrode material.The preparation method is that: heating roasting is passed through using the polyacrylonitrile/carbon nano tube composite fibre film and elemental sulfur of electrostatic spinning preparation.Preparation process of the present invention is simple, and synthesis condition is relatively easy to control, and is suitble to industrialized production；Flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film obtained has preferable flexible, excellent high rate performance and cyclical stability, is a kind of very promising lithium-sulfur cell and positive electrode of sodium-sulfur cell material.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cell and positive electrode of sodium-sulfur cell material flexibility self-supporting sulphur/polyacrylonitrile/carbon nanometers
The preparation method for managing (S-PAN-CNT) composite cellulosic membrane, belongs to energy storage material technical field.
Background technique
With the sternness increasingly of energy problem, within half a century in past, rechargeable battery (also known as: secondary cell) conduct
A kind of high-efficiency energy-storage device has obtained swift and violent development.In numerous secondary cell systems, born by elemental sulfur anode, lithium metal
The lithium-sulfur cell of pole building has obviously advantage.Elemental sulfur theoretical specific capacity is up to 1675mAh/g, and sulphur price is low
Honest and clean, reserved resources are enriched, are small to environmental hazard, and therefore, lithium-sulfur cell has become next-generation high-energy density lithium secondary cell and grinds
The emphasis studied carefully and developed.However, traditional lithium-sulfur cell be readily dissolved in the polysulfide that charge and discharge process generates it is currently used
It in organic electrolyte, and passes through diaphragm and cathode of lithium and side reaction occurs, cause active material to lose, so as to cause battery capacity
It reduces, cycle performance deteriorates, therefore limits its commercialized development and application.Traditional lithium-sulfur cell there are aiming at the problem that, one
Kind relatively effective method be by sulphur simple substance with polyacrylonitrile is compound in a heated condition is used for lithium sulfur battery anode material.But
The sulphur reported at present/polyacrylonitrile composite material be used for electrode when need to be added binder, conductive black and metal collector with
Ensure the structural stability and electric conductivity of electrode, to generate a series of disadvantages, first is that preparation process is loaded down with trivial details, and is mostly used some high
Expensive raw material, increase preparation cost, are not suitable for industrialized production；Second is that the introducing of non-active material, will lead to battery
Energy density reduces.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of lithium-sulfur cell and positive electrode of sodium-sulfur cell material flexibility from propping up
Support sulphur/polyacrylonitrile/carbon nano tube composite fibre film and its preparation method and application, preparation process is simple, synthesis condition compared with
It is easy to control, it is suitble to industrialized production；Flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film obtained can have compared with
Good flexibility, excellent high rate performance and cyclical stability.
To solve the above-mentioned problems, the present invention provides a kind of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre films
Preparation method, which is characterized in that passed through using the polyacrylonitrile/carbon nano tube composite fibre film and elemental sulfur of electrostatic spinning preparation
Heating roasting.
Preferably, above-mentioned preparation method the following steps are included:
Step 1): carbon nanotube is placed in heated constant temperature in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid and is stirred, then will be mixed
Liquid is closed to dilute, be filtered, washed, drying to get the carbon nanotube of acidification is arrived；
Step 2): the carbon nanotube of acidification is added in n,N-Dimethylformamide solvent, then ultrasonic disperse is added
Polyacrylonitrile, it is lasting to stir, uniform sticky dispersion liquid is prepared；
Step 3): obtained dispersion liquid is subjected to electrostatic spinning, polyacrylonitrile/carbon nano tube composite fibre is prepared
Film；
Step 4): obtained polyacrylonitrile/carbon nano tube composite fibre film being mixed with elemental sulfur, is placed in tube furnace,
It roasts under an inert atmosphere, flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film is prepared.
It is highly preferred that the volume ratio of the concentrated sulfuric acid and concentrated nitric acid in the step 1) is 1: 1~10: 1；Heating temperature is 60
~150 DEG C, heating time is 1~12h.
It is highly preferred that the mass ratio of the additional amount of the additional amount and polyacrylonitrile of carbon nanotube is 1: 25 in the step 2)
~10: 25, the additional amount of polyacrylonitrile and the mass ratio of n,N-Dimethylformamide are 1: 20~2: 5.
It is highly preferred that the time of ultrasonic disperse is 10~180min in the step 2)；The time persistently stirred be 2~
24h。
It is highly preferred that in the step 3) electrostatic spinning technological parameter are as follows: electrostatic 10~25kV of field voltage, spinning speed
0.02~0.2mm/min receives 10~25cm of distance.
It is highly preferred that the mass ratio of polyacrylonitrile/carbon nano tube composite fibre film and elemental sulfur is 1: 1 in the step 4)
~1: 12.
It is highly preferred that the maturing temperature in the step 4) is 200~800 DEG C, calcining time is 1~20h.
The present invention also provides above-mentioned flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film preparation methods
Application of the flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film of preparation in metal sulphur cell positive electrode material.
Preferably, the metal sulphur battery is lithium-sulfur cell or sodium-sulphur battery.
Compared with prior art, the beneficial effects of the present invention are:
(1) the primary raw material major part abundance used in the present invention, it is cheap；It is a kind of economical, clean, efficient
Green synthesis method；
(2) present invention process is simple, and technological parameter is relatively easy to control, reproducible, has a good application prospect；
(3) carbon nanotube of one of raw material improves the electric conductivity of positive electrode, solves sulfurized polyacrylonitrile electric conductivity
The disadvantage of difference；
(4) present invention solves traditional lithium-sulfur cell the discharge capacity caused by the dissolution of polysulfide and diffusion
Disadvantage low, coulombic efficiency is low, poor circulation and self-discharge rate are high；
(5) flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film prepared by the present invention can be directly as lithium
Sulphur battery and positive electrode of sodium-sulfur cell material improve the energy of battery without the addition of additional conductive black and adhesive
Metric density.
(6) flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film prepared by the present invention as lithium-sulfur cell and
On the one hand positive electrode of sodium-sulfur cell material has excellent chemical property, on the other hand have preferable flexibility, can be further
Applied to flexible lithium sulphur battery and sodium-sulphur battery, to meet the needs of flexible electronic device.
Detailed description of the invention
Fig. 1 is the SEM figure of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film prepared by embodiment 1；
Fig. 2 is the FTIR spectrum of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film prepared by embodiment 1；
Fig. 3 is flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film of the preparation of embodiment 1 as lithium-sulphur cell positive electrode
The 1st circle, the 10th circle, the 50th constant current charge-discharge capacity voltage curve enclosed of material；
Fig. 4 is flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film of the preparation of embodiment 1 as lithium-sulphur cell positive electrode
The corresponding cycle performance of material and coulombic efficiency figure；Wherein, current density: 200mA/g, voltage window: 1.0~3.0V；
Fig. 5 is flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film of the preparation of embodiment 1 as lithium-sulphur cell positive electrode
The high rate performance figure under different current densities as lithium sulfur battery anode material of material.
Fig. 6 is flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film of the preparation of embodiment 1 as positive electrode of sodium-sulfur cell
The corresponding cycle performance of material and coulombic efficiency figure；Wherein, current density: 167mA/g, voltage window: 1.0~3.0V.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment 1
A kind of preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film:
(1) carbon nanotube is added in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, at 70 DEG C heated at constant temperature and continue
Magnetic agitation 1h, obtains black suspension.
(2) deionized water dilution will be added in suspension obtained above, is then filtered by vacuum and is washed with deionized, most
80 DEG C of dry 12h, the carbon nanotube being acidified in vacuum drying oven afterwards.
(3) carbon nanotube for weighing 120mg acidification is placed in 9gN, in dinethylformamide solvent, ultrasonic disperse 45min,
Then 1g polyacrylonitrile is added and continuing magnetic force stirs 12h, obtains uniform sticky dispersion liquid.
(4) obtained dispersion liquid is subjected to electrostatic spinning, adjusts technological parameter are as follows: electrostatic field voltage 16kV, spinning speed
0.1mm/min is spent, distance 20cm is received, polyacrylonitrile/carbon nano tube composite fibre film is prepared.
(5) polyacrylonitrile/carbon nano tube composite fibre film is uniformly mixed with elemental sulfur (mass ratio 1: 10), is then existed
Roasting obtains flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film under inert atmosphere；Wherein, maturing temperature 350
DEG C, calcining time 3h, heating rate is 5 DEG C per minute, and inert atmosphere is nitrogen.
Implementation is characterized using scanning electron microscope (SEM), Fourier infrared spectrograph (FTIR), battery test system
The preparation-obtained flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film pattern of example 1 and structure and be used as lithium sulphur
The chemical property of battery and positive electrode of sodium-sulfur cell material, result are as follows:
(1) SEM test result shows: prepared flexible self-supporting sulphur/polyacrylonitrile/carbon nanotube is compound in the present invention
Fiber membrane is made of the nanofiber of three-dimensional interpenetrating, and fiber thickness is uniform, and diameter is about 400nm.
(2) FTIR test result shows: prepared flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film
In there are carbon-carbon double bond, carbon-carbon single bond, carbon-to-nitrogen double bons, corresponding to the cyclized structure that polyacrylonitrile generates in sulfidation, carbon
The presence of sulfide linkage shows that sulphur is combined in the form of chemical bond with polyacrylonitrile.
(3) Electrochemical results show: prepared flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre
Film is as lithium sulfur battery anode material, and charge/discharge capacity voltage curve (Fig. 3) in the case where current density is 200mA/g occurs
One discharge platform, this platform correspond to the electrochemical lithium metaplasia of sulphur into the lithiumation process of lithium sulfide；It is in current density
When 200mA/g, charge and discharge cycles test show its with stable cycle performance, discharge capacity can stablize 1370mAh/g with
Upper (Fig. 4)；When current density increases to 1.6A/g from 0.2A/g, the charge-discharge test of the 100th circle shows it with excellent
High rate performance, discharge capacity are respectively 1368,1257,1138,890,670mAh/g (Fig. 5).Prepared flexible self-supporting sulphur/
Polyacrylonitrile/carbon nano tube composite fibre film is as positive electrode of sodium-sulfur cell material, when current density is 167mA/g, charge and discharge
Loop test shows it with stable cycle performance (Fig. 6).
Embodiment 2
A kind of preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film:
(1) carbon nanotube is added in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, at 70 DEG C heated at constant temperature and continue
Magnetic agitation 1h, obtains black suspension.
(2) deionized water dilution will be added in suspension obtained above, is then filtered by vacuum and is washed with deionized, most
80 DEG C of dry 12h, the carbon nanotube being acidified in vacuum drying oven afterwards.
(3) carbon nanotube for weighing 80mg acidification is placed in 9gN, in dinethylformamide solvent, ultrasonic disperse 45min,
Then 1g polyacrylonitrile is added and continuing magnetic force stirs 12h, obtains uniform sticky dispersion liquid.
(4) obtained dispersion liquid is subjected to electrostatic spinning, adjusts technological parameter are as follows: electrostatic field voltage 16kV, spinning speed
0.1mm/min is spent, distance 20cm is received, polyacrylonitrile/carbon nano tube composite fibre film is prepared.
(5) polyacrylonitrile/carbon nano tube composite fibre film is uniformly mixed with elemental sulfur (mass ratio 1: 6), is then existed
Roasting obtains flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film under inert atmosphere；Wherein, maturing temperature 400
DEG C, calcining time 4h, heating rate is 5 DEG C per minute, and inert atmosphere is nitrogen.
Embodiment 3
A kind of preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film:
(1) carbon nanotube is added in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, at 70 DEG C heated at constant temperature and continue
Magnetic agitation 1h, obtains black suspension.
(2) deionized water dilution will be added in suspension obtained above, is then filtered by vacuum and is washed with deionized, most
80 DEG C of dry 12h, the carbon nanotube being acidified in vacuum drying oven afterwards.
(3) carbon nanotube for weighing 40mg acidification is placed in 9gN, in dinethylformamide solvent, ultrasonic disperse 45min,
Then 1g polyacrylonitrile is added and continuing magnetic force stirs 12h, obtains uniform sticky dispersion liquid.
(4) obtained dispersion liquid is subjected to electrostatic spinning, adjusts technological parameter are as follows: electrostatic field voltage 16kV, spinning speed
0.1mm/min is spent, distance 20cm is received, polyacrylonitrile/carbon nano tube composite fibre film is prepared.
(5) polyacrylonitrile/carbon nano tube composite fibre film is uniformly mixed with elemental sulfur (mass ratio 1: 12), is then existed
Roasting obtains flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film under inert atmosphere；Wherein, maturing temperature 450
DEG C, calcining time 6h, heating rate is 5 DEG C per minute, and inert atmosphere is nitrogen.
Claims (10)
1. a kind of preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film, which is characterized in that use Static Spinning
Polyacrylonitrile/carbon nano tube composite fibre the film and elemental sulfur of silk preparation pass through heating roasting.
2. the preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film as described in claim 1, feature exist
In, comprising the following steps:
Step 1): carbon nanotube is placed in heated constant temperature in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid and is stirred, then by mixed liquor
It dilutes, be filtered, washed, drying to get the carbon nanotube of acidification is arrived；
Step 2): the carbon nanotube of acidification is added in n,N-Dimethylformamide solvent, ultrasonic disperse, is then added poly- third
Alkene nitrile, it is lasting to stir, uniform sticky dispersion liquid is prepared；
Step 3): obtained dispersion liquid is subjected to electrostatic spinning, polyacrylonitrile/carbon nano tube composite fibre film is prepared；
Step 4): obtained polyacrylonitrile/carbon nano tube composite fibre film is mixed with elemental sulfur, is placed in tube furnace, lazy
It is roasted under property atmosphere, flexible self-supporting sulphur/polyacrylonitrile/carbon nano tube composite fibre film is prepared.
3. the preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film as claimed in claim 2, feature exist
In the volume ratio of the concentrated sulfuric acid and concentrated nitric acid in the step 1) is 1: 1~10: 1；Heating temperature is 60~150 DEG C, when heating
Between be 1~12h.
4. the preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film as claimed in claim 2, feature exist
In the mass ratio of the additional amount of the additional amount and polyacrylonitrile of carbon nanotube is 1: 25~6: 25 in the step 2), polypropylene
The additional amount of nitrile and the mass ratio of n,N-Dimethylformamide are 1: 20~2: 5.
5. the preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film as claimed in claim 2, feature exist
In the time of ultrasonic disperse is 10~180min in the step 2)；The time persistently stirred be 2~for 24 hours.
6. the preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film as claimed in claim 2, feature exist
In the technological parameter of electrostatic spinning in the step 3) are as follows: electrostatic 10~25kV of field voltage, 0.02~0.2mm/ of spinning speed
Min receives 10~25cm of distance.
7. the preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film as claimed in claim 2, feature exist
In the mass ratio of polyacrylonitrile/carbon nano tube composite fibre film and elemental sulfur is 1: 1~1: 12 in the step 4).
8. the preparation method of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film as claimed in claim 2, feature exist
In the maturing temperature in the step 4) is 200~800 DEG C, and calcining time is 1~20h.
9. the preparation side of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film described in a kind of claim 1-8 any one
Application of the flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film of method preparation in metal sulphur cell positive electrode material.
10. the application of flexibility sulphur/polyacrylonitrile/carbon nano tube composite fibre film as claimed in claim 9, which is characterized in that
The metal sulphur battery is lithium-sulfur cell or sodium-sulphur battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810727262.6A CN109056193A (en) | 2018-07-04 | 2018-07-04 | The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810727262.6A CN109056193A (en) | 2018-07-04 | 2018-07-04 | The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109056193A true CN109056193A (en) | 2018-12-21 |
Family
ID=64819165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810727262.6A Pending CN109056193A (en) | 2018-07-04 | 2018-07-04 | The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109056193A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888219A (en) * | 2019-02-22 | 2019-06-14 | 东华大学 | A kind of Cu oxide/carbon nano-fiber/sulfur electrode material and its preparation and application |
| CN110197899A (en) * | 2019-06-20 | 2019-09-03 | 荆门市亿美工业设计有限公司 | A kind of preparation method of lithium foil |
| CN110729478A (en) * | 2019-09-20 | 2020-01-24 | 中南大学 | Antimony trisulfide nano-dot/sulfur-doped carbon composite material, preparation method thereof and application thereof in sodium/potassium ion battery |
| CN111082063A (en) * | 2019-12-26 | 2020-04-28 | 内蒙古民族大学 | Flexible conductive carbon/metal composite nanofiber membrane, preparation method and application thereof, and lithium-sulfur battery |
| CN111430776A (en) * | 2020-04-01 | 2020-07-17 | 中国科学院电工研究所 | Flexible lithium-sulfur battery and preparation method thereof |
| CN111900326A (en) * | 2020-08-04 | 2020-11-06 | 大连理工大学 | Preparation method and application of positive electrode-interlayer integrated membrane material for lithium-sulfur battery |
| CN112382755A (en) * | 2020-11-11 | 2021-02-19 | 苏州大学 | Transition metal doped polyacrylonitrile sulfide flexible positive electrode material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433614A (en) * | 2011-08-23 | 2012-05-02 | 东华大学 | Preparation method of low-shrinkage high-strength carbon nanofiber |
| EP2711338A1 (en) * | 2012-09-24 | 2014-03-26 | Samsung Electronics Co., Ltd | Composite anode active material, anode and lithium battery each including the composite anode active material, method of preparing the composite anode active material |
| CN104372434A (en) * | 2014-11-15 | 2015-02-25 | 辽宁石油化工大学 | Preparation method of PAN/CoCl2/CNTs composite nano fibers and application of PAN/CoCl2/CNTs composite nano fibers to NaBH4 hydrogen production |
| CN106076377A (en) * | 2016-06-06 | 2016-11-09 | 复旦大学 | A kind of cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping and preparation method thereof |
| CN107460725A (en) * | 2017-07-13 | 2017-12-12 | 东华大学 | A kind of phosphatization cobalt carbon nano-fiber composite material of sulfur doping and preparation method thereof |
| CN108091828A (en) * | 2017-12-15 | 2018-05-29 | 苏州大学 | Sulfurized polyacrylonitrile flexibility anode based on electrostatic spinning technique and preparation method thereof |
-
2018
- 2018-07-04 CN CN201810727262.6A patent/CN109056193A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433614A (en) * | 2011-08-23 | 2012-05-02 | 东华大学 | Preparation method of low-shrinkage high-strength carbon nanofiber |
| EP2711338A1 (en) * | 2012-09-24 | 2014-03-26 | Samsung Electronics Co., Ltd | Composite anode active material, anode and lithium battery each including the composite anode active material, method of preparing the composite anode active material |
| CN104372434A (en) * | 2014-11-15 | 2015-02-25 | 辽宁石油化工大学 | Preparation method of PAN/CoCl2/CNTs composite nano fibers and application of PAN/CoCl2/CNTs composite nano fibers to NaBH4 hydrogen production |
| CN106076377A (en) * | 2016-06-06 | 2016-11-09 | 复旦大学 | A kind of cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping and preparation method thereof |
| CN107460725A (en) * | 2017-07-13 | 2017-12-12 | 东华大学 | A kind of phosphatization cobalt carbon nano-fiber composite material of sulfur doping and preparation method thereof |
| CN108091828A (en) * | 2017-12-15 | 2018-05-29 | 苏州大学 | Sulfurized polyacrylonitrile flexibility anode based on electrostatic spinning technique and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888219A (en) * | 2019-02-22 | 2019-06-14 | 东华大学 | A kind of Cu oxide/carbon nano-fiber/sulfur electrode material and its preparation and application |
| CN110197899A (en) * | 2019-06-20 | 2019-09-03 | 荆门市亿美工业设计有限公司 | A kind of preparation method of lithium foil |
| CN110197899B (en) * | 2019-06-20 | 2021-11-09 | 荆门市亿美工业设计有限公司 | Preparation method of lithium foil |
| CN110729478A (en) * | 2019-09-20 | 2020-01-24 | 中南大学 | Antimony trisulfide nano-dot/sulfur-doped carbon composite material, preparation method thereof and application thereof in sodium/potassium ion battery |
| CN111082063A (en) * | 2019-12-26 | 2020-04-28 | 内蒙古民族大学 | Flexible conductive carbon/metal composite nanofiber membrane, preparation method and application thereof, and lithium-sulfur battery |
| CN111430776A (en) * | 2020-04-01 | 2020-07-17 | 中国科学院电工研究所 | Flexible lithium-sulfur battery and preparation method thereof |
| CN111430776B (en) * | 2020-04-01 | 2021-06-22 | 中国科学院电工研究所 | Flexible lithium-sulfur battery and preparation method thereof |
| CN111900326A (en) * | 2020-08-04 | 2020-11-06 | 大连理工大学 | Preparation method and application of positive electrode-interlayer integrated membrane material for lithium-sulfur battery |
| CN112382755A (en) * | 2020-11-11 | 2021-02-19 | 苏州大学 | Transition metal doped polyacrylonitrile sulfide flexible positive electrode material and preparation method thereof |
| CN112382755B (en) * | 2020-11-11 | 2022-04-12 | 苏州大学 | Transition metal doped polyacrylonitrile sulfide flexible positive electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109056193A (en) | The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film | |
| Ye et al. | Coordination derived stable Ni–Co MOFs for foldable all-solid-state supercapacitors with high specific energy | |
| CN107316979B (en) | Molybdenum disulfide/carbon fiber network flexible electrode and preparation method and application thereof | |
| CN108666553B (en) | Cobalt sulfide/carbon fiber compound and preparation method and application thereof | |
| CN112563586B (en) | Method for improving performance of zinc-iodine battery based on halogen bond effect | |
| CN107768652A (en) | A kind of lithium sulfur battery anode material based on middle micro-diplopore metal oxide or spinelle and preparation method thereof | |
| CN108630921A (en) | The preparation method of ferriferous oxide/carbon fiber composite lithium ion battery cathode material | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN106654236B (en) | A kind of three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping and its preparation method and application | |
| CN105977484B (en) | A kind of di-iron trioxide nano-tube material and the preparation method and application thereof | |
| CN109360939A (en) | A kind of flexibility of lithium ion battery is without collector thin film pole piece preparation method | |
| CN110459755A (en) | A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film, preparation method and applications | |
| CN112038626A (en) | Tin-carbon composite material for lithium ion battery cathode and preparation method thereof | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN104993116B (en) | A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method | |
| CN110828802A (en) | Preparation method of high-power aqueous zinc ion battery positive electrode material | |
| CN106058263B (en) | A kind of Preparation method and use of cobaltosic oxide porous fibrous material | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN110078053A (en) | A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating | |
| CN110676432A (en) | Preparation method and application of flexible antimony nanoparticle @ carbon nanowire negative electrode material | |
| CN106654182A (en) | Manganese dioxide sulfur-carbon positive electrode and preparation method | |
| CN110400918A (en) | A kind of preparation method of cobalt sulphur compound/sulfur doping carbon composite | |
| CN107742710B (en) | Preparation method of chromium-based lithium ion battery composite negative electrode material | |
| CN109616644A (en) | Silk gum carbon film coated Co3O4Porous microsphere composite material and preparation method | |
| CN111244435A (en) | Preparation method and application of nano linear vanadium pentoxide electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181221 |