CN110459755A - A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film, preparation method and applications - Google Patents
A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film, preparation method and applications Download PDFInfo
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- CN110459755A CN110459755A CN201910842232.4A CN201910842232A CN110459755A CN 110459755 A CN110459755 A CN 110459755A CN 201910842232 A CN201910842232 A CN 201910842232A CN 110459755 A CN110459755 A CN 110459755A
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Abstract
The present invention provides a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded films, preparation method and applications, belong to chemical energy storage battery technical field.Polypyrrole scion grafting is on redox graphene in the film；The graphene oxide and functionalized carbon nanotubes of reduction interweave with forming three-dimensional carbon skeleton；Elemental sulfur is carried in the three-dimensional carbon skeleton.The method causes self assembly using the redox reaction between pyrroles and graphene oxide, simultaneously, function multi-walled carbon nano-tube provides the quick transmission channel of ion/electronics as the second carbon skeleton, and a kind of laminated film of flexible self-supporting is constructed by step vacuum filtration and the load of rear sulphur.Utilize the synergistic effect for the interleaved three-dimensional conductive frame that strong adsorptivity and graphene and carbon nanotube of the polypyrrole to polysulfide are constructed, the problems such as can solve the inherently non-conductive property of elemental sulfur and polysulfide " shuttle effect ", further improves the chemical property of lithium-sulfur cell.
Description
Technical field
The present invention provides a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded films, preparation method and applications, belong to
In chemical energy storage battery technical field.
Background technique
In order to alleviate problem of environmental pollution and reduce the dependence to fossil fuel, reproducible alternative energy source is developed and utilized
Technology is extremely urgent.It is one of selection most viable in electrochemical storage device by the secondary cell of representative of lithium ion battery.
With the fast development of the related fieldss such as mobile electronic device, electric car and emerging wearable power technology, commercialization on the market
Battery is no longer satisfied demand, and higher requirements are also raised for the research and development of battery technology by people.Therefore, high volume energy
Density, high security, long circulation life and low cost environmentally friendly secondary cell have become research hotspot in recent years.As next
For competitor extremely promising in chargeable cell system, lithium-sulfur cell relies on sulphur anode unique advantage: the reason of superelevation
By energy density 2600W h/kg or 2800W h/L (being 3~5 times of traditional intercalation anode)；Comparatively safe low-work voltage
2.15V；Meanwhile elemental sulfur is as one of the most abundant element of content on the earth, theoretical specific capacity up to 1675mA h/g, at
This is cheap and environmental-friendly.
However, the commercial applications of lithium sulfur battery anode material and large-scale production nevertheless suffer from various obstructions, example
If (1) elemental sulfur and its electric discharge final product are electrons/ions insulator, cause active material utilization low；(2) intermediate product
The dissolution of more lithium sulfides and " shuttle effect " bring side reaction to recycle, and lead to the irreversible loss of active material, reduce battery
Coulombic efficiency, make battery capacity occur rapid decay；(3) volume expansion/contraction of sulphur can cause electricity in charge and discharge process
The crushing of pole material and structure are destroyed, and it is bad and make electricity that this further causes the interfacial contact between active material and collector
Pond cyclical stability is deteriorated.
To solve the above-mentioned problems, domestic and international researcher takes a series of measures to design and have complicated composition and rationally
The high-performance lithium-sulfur cell of structure.The most common strategy be by elemental sulfur in conjunction with the nanostructure composite material of high conductivity with
Reinforce kinetics, improve chemical property.Carbon-based material receives extensive pass because of its ideal physicochemical properties
Note, comprising: (1) enriching porosity can be realized high-sulfur load, alleviate the volume expansion in discharge process；(2) biggish to compare table
Area can physical barriers polysulfide, controllable surface chemical property can be anchored and adsorb polysulfide；(3) high conductivity
Guarantee that ion/electronics quickly transmits and improves utilization efficiency.Based on these advantages, Functional carbon sill is improving battery
Capacity and cycle performance etc. play an important role.In addition, conducting polymer is also because its pattern is abundant, electric conductivity is high, easy
In synthesis and environmental stability it is good the features such as and receive significant attention.In recent years, compound just about carbon-based material/conducting polymer
Application of the pole material in lithium-sulfur cell also has been reported that: patent application CN105070887A reports a kind of lithium-sulphur cell positive electrode material
Material, which is characterized in that the material includes sulphur/graphene oxide/CNTs compound, the sulphur/graphene oxide/CNTs compound
On be coated with electroconductive polymer layer, be coated with adhesive layer on the electroconductive polymer layer.Patent application CN106450245A report
A kind of flexibility in road can charge and discharge lithium sulfur battery anode material preparation method, use ammonium persulfate oxidation polymerization pyrroles, use
Hydrofluoric acid redox graphene obtains graphene-polypyrrole/sulphur-graphene sandwich-like by filtering preparation method layer by layer
Laminated film.
Although the above-mentioned prior art improves the performance of lithium-sulfur cell to a certain extent, but still there are some apparent
Defect.If the tri compound anode in patent application CN105070887A is prepared by the method that traditional slurry is coated with,
The use of middle sulphur anode lower mass density, metal collector and adhesive inevitably hinders lithium-sulfur cell volume energy
The further promotion of metric density.The oxidation of pyrroles in the preparation process of patent application CN106450245A, graphene oxide also
Original is related to conventional reagent and method, however the use of conventional oxidation reduction agent often results in environmental pressure and introduces additional function
Group, therefore each experimental procedure is both needed to wash drying for several times to remove extra oxidant or reducing agent, complex process is time-consuming.
Summary of the invention
In view of this, improving the structure of C-base composte material it is an object of the invention to overcome the shortcomings of above-mentioned sulphur anode
Design and surface chemical property provide a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film, preparation method and its answer
With.This method mixes ageing by a kind of simple self assembly strategy, by pyrroles and graphene oxide, and oxidation between the two is also
Original reaction leads to the partial reduction of graphene oxide and the oligomerization of pyrroles, is not necessarily to other oxidations or reducing agent.In addition, addition official
On the one hand the electric conductivity and porosity of material, another party can be improved as the second carbon skeleton component in energy multi-walled carbon nano-tube
Graphene sheet layer can be isolated in face well, reduce and reunite.It filters to have obtained a kind of poly- pyrrole of lightweight self-supporting finally by a step
Cough up/carbon nano tube/graphene laminated film be used as sulfur-donor.The laminated film is used to press down significantly as the lithium-sulfur cell of anode
" the shuttle effect " for having made polysulfide, significantly reduces the self-discharge rate of battery, alleviates the volume in charge and discharge process
Variation, and then show good cyclical stability and high specific discharge capacity.
Above-mentioned purpose that the invention is realized by the following technical scheme:
A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film, the film is by elemental sulfur, polypyrrole, oxygen reduction
Graphite alkene and function multi-walled carbon nano-tube composition；Wherein, pyrroles mixes with graphene oxide, and pyrroles's in-situ polymerization is gathered
Pyrroles, simultaneous oxidation graphene are reduced to redox graphene；The polypyrrole is grafted on redox graphene；It is described
Redox graphene and function multi-walled carbon nano-tube interweave with forming three-dimensional carbon skeleton；The elemental sulfur is carried on the three-dimensional
The surface and inside of carbon skeleton；It is in terms of 100% by the total film mass, the mass fraction of elemental sulfur is 55%~60%, is gathered
The mass fraction of pyrroles is 1%~10%, and the mass fraction of function multi-walled carbon nano-tube is 20%~25%, remaining is reduction
Graphene oxide.
A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation method, the method comprises the following steps:
(1) preparation of polypyrrole/graphene compound aqueous solution:
Graphene oxide water solution is added into the aqueous solution of ethyl alcohol, pyrroles is added in 0.5~2h of ultrasonic disperse, and stirring is equal
After even, still aging 2~3 days at room temperature, kayexalate is added, be heated under stirring condition 80~90 DEG C of reactions 2~
4h is cooled to room temperature after reaction, is distributed in the water of deionized water purity or more after centrifuge washing, and polypyrrole/stone is obtained
Black alkene compound aqueous solution；Wherein, the mass ratio of graphene oxide, pyrroles and kayexalate is 1:10~100:5~10；
(2) polypyrrole/graphene/carbon nano-tube coextruded film preparation:
Into the polypyrrole/graphene compound aqueous solution be added function multi-walled carbon nano-tube in, after mixing evenly plus
Enter Triton X-100 (TritonX-100), 10~60min of ultrasonic disperse, obtains polypyrrole/graphene/carbon nanometer
Pipe compound aqueous solution；Above-mentioned compound aqueous solution is drawn, is filtered by vacuum with polypropylene screen, is removed after dry from polypropylene screen
To a kind of polypyrrole/graphene/carbon nano-tube coextruded film；Wherein, function multi-walled carbon nano-tube is to contain polar functional group
Multi-walled carbon nanotube, the quality of function multi-walled carbon nano-tube is 1~3 times of graphene oxide quality in step (1)；Poly- pyrrole
Cough up/graphene/carbon nanotube composite film with a thickness of 10~30 μm；
(3) sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation:
The toluene solution of sulphur is dropped evenly on the polypyrrole/graphene/carbon nano-tube coextruded film, inert gas is protected
It is first to heat to 150~160 DEG C under shield, keeps the temperature 8~12h, is then heated to 240~300 DEG C, keeps the temperature 0.5~1h, obtains one kind
Sulphur/polypyrrole/graphene/carbon nano-tube coextruded film；Wherein, it is added drop-wise to the polypyrrole/graphene/carbon nanotube THIN COMPOSITE
The quality of sulphur is 1~30mg on film.
Preferably, the volume ratio of second alcohol and water is 1:0.5~2 in the aqueous solution of ethyl alcohol described in step (1), and the water is
Water more than deionized water purity.
Preferably, concentration of the TritonX-100 in compound aqueous solution described in step (2) be 0.1wt%~
0.5wt%.
Preferably, function multi-walled carbon nano-tube described in step (2) is obtained after the acidified processing of multi-walled carbon nanotube
's.The specific method is as follows: the effective concentrated hydrochloric acid ultrasound 20~40min of immersion treatment of multi-wall carbon nano-tube prepared by CVD method, centrifugation are washed
After washing at 480~520 DEG C 0.5~1.5h of high-temperature process, obtain multi-walled carbon nanotube after purification；Again by multi wall after purification
Carbon nanotube is added in dust technology, and 6~12h of heated at constant temperature reflux, centrifuge washing obtain after vacuum drying at 100~120 DEG C
Functionalized carbon nanotubes.
Preferably, the supersonic frequency that ultrasonic disperse described in step (2) uses is 80kW~100kW.
Preferably, the aperture of polypropylene screen is 0.22~0.45 μm in step (2).
Preferably, vacuum degree is -0.08MPa~-0.1MPa when vacuum filtration in step (2).
Preferably, the toluene solution concentration of sulphur is 10~30mg/mL in step (3).
A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film application, the film as lithium-sulfur cell just
Pole uses.
The utility model has the advantages that
(1) present invention, by controlling reaction condition, utilizes pyrroles and oxygen by directly mixing pyrroles and graphene oxide
Redox reaction between graphite alkene promotes the partial reduction of graphene oxide and the oligomerization of pyrroles, while not adding
Add other oxidations or reducing agent that product self assembly can be realized.
(2) stannic oxide/graphene nano piece and multi-walled carbon nanotube with high-specific surface area and pore structure provide for sulphur growth
Enough contact sites, can solve that active material load capacity in existing lithium sulfur battery anode material is few and active material utilization
The problems such as low；The passing through of oxygen-containing functional group of functionalized multi-walled carbon nanotube and the surface of graphene oxide of partial reduction remnants
Learning interaction has good anchoring to act on generated in-situ sulphur and soluble polysulfide intermediate, can significantly improve electricity
The cyclical stability and high rate performance in pond.
(3) polypyrrole rich in hetero atom nitrogen can form chemical bond with sulphur, strong affine between polypyrrole and polysulfide
Power can be effectively reduced polysulfide and be diffused into electrolyte, further suppress shuttle effect.
(4) polypyrrole/graphene/carbon nano tube three-dimensional network with high conductivity provides for ion/charge transmission
Express passway further improves kinetics, to increase the charge/discharge speed of battery, capacity and cyclical stability.This
Outside, the thin-film carrier of lightweight flexible is adapted to the volume change of active material in charge and discharge process, has effectively kept anode
Structural intergrity of the material in cyclic process, extends the service life of lithium-sulfur cell.
(5) present invention is prepared by a step suction method, and easy to operate, technique and technology are easy to accomplish, and product is environmentally protective,
Convenient for large-scale commercial production.Compound aqueous solution is filtered under the conditions of condition of high vacuum degree makes product have very thin thickness, is conducive to
Improve the volume and capacity ratio and volume energy density of battery.In addition, being taken out with the polypropylene screen that aperture is 0.22~0.45 μm
It filters and can avoid a large amount of losses of product during suction filtration, and make polypyrrole/graphene/carbon nano tube compound material after the drying
Removing obtains flexible self-supporting film carrier easily from filter membrane.
(6) sulphur is carried using rear sulphur load method in the present invention, the toluene solution of sulphur is first added dropwise on laminated film, received with load
Rice sulfur granules.Subsequent heat process carries out in two stages, and mixture is first to heat to 150 by the first stage under inert gas protection
~160 DEG C, 8~12h is kept the temperature, to ensure the infiltration of elemental sulfur energy substantially uniformity in laminated film；Second stage is warming up to 240~
300 DEG C, 0.5~2h is kept the temperature, at this moment ring-opening reaction occurs for the elemental sulfur in mixture, so that sulphur is fixed on laminated film.
Detailed description of the invention
In Fig. 1 (a) be comparative example 1, in comparative example 2 and embodiment 1 PG, CG and PCG TG figure, (b) be comparative example 1, it is right
The TG figure of PG-S, CG-S and PCG-S in ratio 2 and embodiment 1.
The SEM figure that (a) is PG in comparative example 1 in Fig. 2 is (b) the partial enlargement SEM figure of PG in comparative example 1, is (c) pair
The side view SEM figure of PG in ratio 1.
The SEM figure that (a) is CG in comparative example 2 in Fig. 3 is (b) the partial enlargement SEM figure of CG in comparative example 2, is (c) pair
The side view SEM figure of CG in ratio 2.
The SEM figure that (a) is PCG in embodiment 1 in Fig. 4 is (b) the partial enlargement SEM figure of PCG in embodiment 1, (c) is
The side view SEM figure of PCG in embodiment 1.
Electrochemical impedance of the battery that (a) is assembled by comparative example 1, comparative example 2 and embodiment 1 in Fig. 5 before circulation
(EIS) figure, (b) battery assembled by comparative example 1, comparative example 2 and embodiment 1 recycles 50 at 0.5C (1C=1675mA/g)
EIS figure after week.
Fig. 6 is that the circulation that the battery that comparative example 1, comparative example 2 and embodiment 1 are assembled carries out under different current densities is surveyed
Attempt.
Fig. 7 is the loop test figure that the battery that embodiment 1 is assembled carries out under 0.2C current density.
Fig. 8 is the loop test figure that the battery that embodiment 2 is assembled carries out under 0.2C current density.
Fig. 9 is the loop test figure that the battery that embodiment 3 is assembled carries out under 0.2C current density.
Figure 10 be function multi-walled carbon nano-tube (MWCNT) in embodiment 1, graphene oxide (GO), polypyrrole (PPy) and
X-ray diffraction (XRD) figure of PCG.
Figure 11 is the flexible structure figure of PCG-S in embodiment 1.
Specific embodiment
The objectives, technical solutions, and advantages of the present invention are described in order to be more clearly understood, below in conjunction with specific implementation
The present invention will be described in further detail for example.It should be understood that following described embodiment is for explaining only the invention,
And it is not construed as limiting the scope of the invention.Reagents or instruments used without specified manufacturer, being can be by commercially available purchase
Buy the conventional products of acquisition.In addition, the endpoint of disclosed range and any value are not limited to the accurate range herein
Or value, these ranges or value should be understood as comprising the value close to these ranges or value.
In following embodiment:
Thermogravimetric analysis (TG) test: STA449F3 type synchronous solving, resistance to speed (NETZSCH) of Germany.
Scanning electron microscope (SEM) test: HITACHI S-4800 type field emission scanning electron microscope, Japan.
X-ray diffraction (XRD) test: Rigaku UltimaIV-185 type X-ray diffractometer, Japan.
Kayexalate is purchased from aladdin, Mw=70000.
Pyrroles is purchased from Sinopharm Chemical Reagent Co., Ltd., needs the pyrroles that will be bought under 60 DEG C of water bath conditions before use
Vacuum distillation is to be further purified removing polymerization inhibitor.
The assembling and test of CR2025 button cell: the manual pole of the laminated film that comparative example or embodiment are prepared
Piece guillotine is cut into the sequin that diameter is 1cm and is used as anode, and metal lithium sheet is used as cathode, Celgard2300 perforated membrane conduct
Diaphragm, electrolyte used are 1,3- dioxolanes and glycol dimethyl ether (DOL:DME=1:1v/v) and the bis- fluoroforms of 1.0M
Base sulfimide lithium (LiTFSI) and 0.2M LiNO3As the mixture of additive, finally in the glove box end group for being full of argon gas
Dress up 2025 formula button cells.
Constant current charge-discharge test: CT2001A LAND battery test system, Wuhan；Charging/discharging voltage section is 1.7-2.8V
(vs.Li/Li+)；Test temperature is 33 DEG C.
Ac impedance measurement: CHI660E electrochemical workstation, Shanghai；Test voltage is 2.4V, and test frequency range is
0.01Hz~100kHz, amplitude 5mV, using to electrode as reference electrode.
Comparative example 1
A kind of lithium sulfur battery anode material, the material include sulphur/polypyrrole/graphene compound, what this comparative example used
Technical scheme steps are as follows:
1) preparation of graphene oxide:
Graphene oxide is prepared using Hummers method is improved: being 150 μm by 1.5g granularity under ice bath and stirring condition
Expanded graphite powder and 180mL mass fraction be 98% the concentrated sulfuric acid, 20mL phosphoric acid mix and infiltrates 0.5h；Then, slowly add
Enter 9g potassium permanganate, controls temperature at 5 DEG C or less；After sufficiently reaction 0.5h, reaction system is continued under 50 DEG C of water bath conditions
Stirring is for 24 hours；After completion of the reaction, above-mentioned reaction solution is poured into 220g ice cube, and 5mL mass fraction is slowly added thereto and is
30% hydrogen peroxide, until solution colour becomes ecru；Then it filters to discard strong acid, is respectively 5% with mass fraction
Hydrochloric acid and deionized water washing three times；Graphene oxide mother liquor is obtained after spin dialysis processing.The mother liquor is ultrasonically treated
2h and the graphene oxide water solution for being configured to 10mg/mL.
2) preparation of polypyrrole/graphene laminated film (PG):
It is added into 200mL ethyl alcohol and the mixed solution (volume ratio of ethyl alcohol and deionized water is 1:1) of deionized water
The graphene oxide water solution of 5.6mL step 1) preparation, ultrasonic disperse 1h under frequency 100kW；2.8mL pyrroles is added, stirring is equal
After even, it is aged three days at room temperature, solution colour becomes brownish black from brown color, obtains polypyrrole/graphene mixing suspension；
0.28g kayexalate is added into above-mentioned suspension as dispersing agent；Then by mixed solution in magnetic agitation condition
With further redox graphene, solution colour was by the further blackening of brownish black in 4 hours for lower 80 DEG C of heating water baths；To naturally cold
But to after room temperature, three times by obtained suspension centrifuge washing, be subsequently dispersed in the deionized water of 240mL obtain polypyrrole/
Graphene composite solution；30mL composite solution is drawn, the polypropylene screen for being 0.22 μm with aperture is in the item that vacuum degree is -0.1MPa
It is filtered under part, removing from filter paper after dry can be obtained polypyrrole/graphene laminated film.
3) sulphur/polypyrrole/graphene laminated film (PG-S) preparation:
It prepares the toluene solution of 20mg/mL sulphur: taking out the distillation sulphur powder 300mg being stored in 60 DEG C of vacuum ovens, add
Enter 15mL toluene, seal, be placed on heat collecting type constant-temperature heating magnetic stirring apparatus, with 60 DEG C of temperature heating stirring, until sulphur
Powder is dissolved completely in toluene solution.
It takes the toluene solution 0.5mL of above-mentioned sulphur to drop evenly on the polypyrrole/graphene laminated film, is then filling
155 DEG C are heated in the closed container of full argon gas and keeps the temperature 10 hours, then, are continuously heating to 240 DEG C of heat preservation 0.5h, are obtained one kind
Sulphur/polypyrrole/graphene laminated film.
Test results are shown in figure 1 by the TG of PG and PG-S, and calculating polypyrrole content is 6.8wt%, corresponding sulphur load
Amount is 41.8wt%, and activity substance content is lower.
Test results are shown in figure 2 by the SEM of PG, and as can be seen from the figure PG has relatively gentle cotton-shaped surface, surface
Roughness is lower, and porosity is lower；Side view shows that PG thickness is about 5.8 μm, and fine and close layer structure is due to aoxidizing stone
Irreversible reunion and stacking has occurred in black alkene during reduction and suction filtration.
As shown in figure 5, since conductivity is poor, PG-S circulation front and back is all shown greatly PG-S electrochemical impedance result
Charge-transfer resistance.
The battery performance that PG-S is assembled is as shown in fig. 6, since conductivity is poor, and kinetics is slower, PG-
The specific discharge capacity of S is lower；Concrete outcome is shown in Table 1.
Comparative example 2
A kind of lithium sulfur battery anode material, the material include sulphur/graphene/carbon nano-tube compound, this comparative example uses
Technical scheme steps it is as follows:
1) preparation of graphene oxide is the same as step 1) in comparative example 1；
2) purifying and acidification of carbon nanotube:
The concentrated hydrochloric acid ultrasound immersion treatment 30min of the effective 12mol/L of multi-wall carbon nano-tube prepared by commercially available CVD method, centrifugation
High-temperature heating treatment 1h at 480 DEG C after washing three times；Multi-walled carbon nanotube after taking 1g purification process again is added to 100mL concentration
For in the dust technology of 2.6mol/L, centrifuge washing to neutrality, last 60 DEG C is dried in vacuo after constant temperature is stirred at reflux 12h at 100 DEG C
Functionalized carbon nanotubes can be obtained for 24 hours.
3) preparation of graphene/carbon nanotube composite film (CG):
Graphene oxide water solution made from 5.6mL step 1) is dispersed in the deionized water of 240mL, frequency 100kW
Lower ultrasonic disperse 1h；The functionalized carbon nanotubes of 112mg after purification are added, obtain graphene oxide/carbon nanometer after mixing evenly
Pipe mixing suspension.0.56g kayexalate and 560 μ L Triton-X are added into above-mentioned suspension as dispersing agent,
Ultrasonic disperse 30min under frequency 100kW adds 1400 μ L sodium ascorbate solutions (1M) and heats 3 under 80 DEG C of magnetic agitations
Hour is with redox graphene.After being cooled to room temperature, 30mL composite solution is drawn, is existed with the polypropylene screen that aperture is 0.45 μm
Vacuum degree is filtered under conditions of being -0.08MPa, it is dry after to can be obtained graphene/carbon nano-tube multiple for removing from filter paper
Close film.
4) preparation of sulphur/graphene/carbon nanotube composite film (CG-S):
It prepares the toluene solution of 20mg/mL sulphur: taking out the distillation sulphur powder 300mg being stored in 60 DEG C of vacuum ovens, add
Enter 15mL toluene, seal, be placed on heat collecting type constant-temperature heating magnetic stirring apparatus, with 60 DEG C of temperature heating stirring, until sulphur
Powder is dissolved completely in toluene solution.
It takes the toluene solution 0.5mL of above-mentioned sulphur to drop evenly on the graphene/carbon nanotube composite film, then exists
It is heated to 155 DEG C in closed container full of argon gas and keeps the temperature 10 hours, then, is continuously heating to 240 DEG C of heat preservation 0.5h, obtains one
Kind sulphur/graphene/carbon nanotube composite film.
Test results are shown in figure 1 by the TG of CG and CG-S, and calculating corresponding sulphur load capacity is 53.8wt%, active material
Content is promoted compared with PG-S.
Test results are shown in figure 3 by the SEM of CG, and as can be seen from the figure the surface CG has apparent protrusion, rough surface
Degree and porosity are higher；Side view shows that CG thickness is about 16.2 μm, observes that structure has apparent layering.
CG-S electrochemical impedance result is as shown in figure 5, carbon nanotube greatly changes as the second constituent of carbon skeleton
The conductivity of electrode has been apt to it, the Charge-transfer resistance of CG-S circulation front and back is below PG-S.
The battery performance that CG-S is assembled is as shown in fig. 6, the improvement of conductivity obtains specific discharge capacity centainly
The promotion of degree, but due to lacking polypyrrole to the chemisorption of polysulfide, CG-S is compared with cycle performance under high magnification
It is poor；Concrete outcome is shown in Table 1.
Embodiment 1
A kind of positive pole material for high-performance lithium-sulfur battery, the material include sulphur/polypyrrole/graphene/carbon mano-tube composite,
The technical scheme steps that the present embodiment uses are as follows:
1) preparation of graphene oxide is the same as step 1) in comparative example 1；
2) purifying and acidification of carbon nanotube are the same as step 2) in comparative example 2；
3) preparation of polypyrrole/graphene/carbon nano-tube coextruded film (PCG):
It is added into 200mL ethyl alcohol and the mixed solution (volume ratio of ethyl alcohol and deionized water is 1:1) of deionized water
The graphene oxide water solution of 5.6mL step 1) preparation, ultrasonic disperse 1h under frequency 100kW；2.8mL pyrroles is added, stirring is equal
After even, it is aged three days at room temperature, solution colour becomes brownish black from brown color, obtains polypyrrole/graphene mixing suspension；
0.28g kayexalate is added into above-mentioned suspension as dispersing agent；Then by above-mentioned mixed solution in magnetic agitation
Under the conditions of 80 DEG C heating water bath 4 hours with further redox graphene, solution colour is by the further blackening of brownish black；To certainly
After being so cooled to room temperature, three times by precursor suspension centrifuge washing, it is subsequently dispersed in the deionized water of 240mL and obtains poly- pyrrole
Cough up/graphene composite solution；The carboxyl carbon nanotube of 112mg after purification, mixing are added into polypyrrole/graphene composite solution
Add the TritonX-100 of 560 μ L, ultrasonic disperse 30min under frequency 80kW after mixing evenly, obtain polypyrrole/graphene/
Carbon nanotube compound aqueous solution.Draw 30mL compound aqueous solution, with aperture be 0.45 μm polypropylene screen vacuum degree be-
It is filtered under conditions of 0.08MPa, removing from polypropylene screen after dry can be obtained fine and close polypyrrole/graphene/carbon
Nanotube composite film, as active ingredient carriers.
4) sulphur/polypyrrole/graphene/carbon nano-tube coextruded film (PCG-S) preparation:
It prepares the toluene solution of 20mg/mL sulphur: taking out the distillation sulphur powder 300mg being stored in 60 DEG C of vacuum ovens, add
Enter 15mL toluene, seal, be placed on heat collecting type constant-temperature heating magnetic stirring apparatus, with 60 DEG C of temperature heating stirring, until sulphur
Powder is dissolved completely in toluene solution.
The toluene solution 0.5mL of above-mentioned sulphur is taken to drop evenly in the polypyrrole/graphene/carbon nano-tube coextruded film
On, it is then heated to 155 DEG C in the closed container full of argon gas and keeps the temperature 10 hours, then, is continuously heating to 240 DEG C of heat preservations
0.5h obtains a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film.
Test results are shown in figure 1 by the TG of PCG-S, and calculating polypyrrole content is 3.5wt%, and corresponding sulphur load capacity is
57wt%, activity substance content are higher.
Test results are shown in figure 4 by the SEM of PCG, and as can be seen from the figure PCG surface texture is similar to CG, rough surface
Degree is higher, and a large amount of fold, braided protrusion improve the specific surface area and porosity of material；Side view shows PCG thickness
About 14.6 μm, observe that PCG is three-dimensional hierarchical structure.
PCG-S electrochemical impedance result is as shown in figure 5, it can be seen from the figure that the electric charge transfer resistance of PCG-S circulation front and back
It is anti-smaller, this is because polypyrrole/graphene/carbon nano tube three-dimensional network promotes the quick transmission of ion/charge, limit
" the shuttle effect " of polysulfide, improves the wetability of electrode, to further improve kinetics.
The battery performance that PCG-S is assembled as shown in fig. 6-7, due to sulphur, polypyrrole, graphene and carbon nanotube
The synergistic effect of each component, specific discharge capacity is up to 1201.9mAh/g at 0.2C by PCG-S, still there is capacity after 300 weeks circulations
790.2mAh/g；Coulombic efficiency is more than 98% under 1C, and capacity retention ratio is up to 88% or more after 200 circulations, compared under high magnification
Electrochemically stable performance improve it is obvious.Concrete outcome is shown in Table 1.
Test results are shown in figure 10 by the XRD of PCG, and the peak in PCG spectrum near 12.7 ° disappears, but occurs at 23.5 °
One big Bao Feng.Thus demonstrate and redox reaction occurs between pyrroles and graphene oxide: pyrroles is embedding by in-situ polymerization
Enter into graphene oxide layer, further results in the reduction of graphene oxide and the expansion of interlamellar spacing.
The flexible of PCG-S show as shown in figure 11, it can be seen from the figure that even if in the case where bending doubling, material
Structural intergrity still keeps good.
Embodiment 2
A kind of positive pole material for high-performance lithium-sulfur battery, the material include sulphur/polypyrrole/graphene/carbon mano-tube composite,
The technical scheme steps that the present embodiment uses are as follows:
1) preparation of graphene oxide is the same as step 1) in comparative example 1；
2) purifying and acidification of carbon nanotube are the same as step 2) in comparative example 2；
3) preparation of polypyrrole/graphene/carbon nano-tube coextruded film (PCG):
It is added into 300mL ethyl alcohol and the mixed solution (volume ratio of ethyl alcohol and deionized water is 1:2) of deionized water
The graphene oxide water solution of 5.6mL step 1) preparation, frequency 100kW ultrasound 2h；5.6mL pyrroles, after mixing evenly, In is added
It is aged 48h at room temperature, solution colour becomes brownish black from brown color, obtains polypyrrole/graphene mixing suspension；It is hanged to above-mentioned
0.56g kayexalate is added in supernatant liquid as dispersing agent；Then by mixed solution 90 DEG C of water under the conditions of magnetic agitation
With further redox graphene, solution colour is by the further blackening of brownish black within 2 hours for bath heating；After naturally cool to room temperature
Afterwards, three times by precursor suspension centrifuge washing, it is subsequently dispersed in the deionized water of 240mL that obtain polypyrrole/graphene compound
Solution；The carboxyl carbon nanotube of 168mg after purification is added into polypyrrole/graphene composite solution, after being mixed evenly again
The TritonX-100 of 1.2mL is added, it is multiple to obtain polypyrrole/graphene/carbon nanotube by ultrasonic disperse 60min under frequency 100kW
Heshui solution.60mL compound aqueous solution is drawn, the polypropylene screen for being 0.45 μm with aperture is in the condition that vacuum degree is -0.08MPa
Under filtered, it is dry after from polypropylene screen removing fine and close polypyrrole/graphene/carbon nanotube THIN COMPOSITE can be obtained
Film, as active ingredient carriers.
4) sulphur/polypyrrole/graphene/carbon nano-tube coextruded film (PCG-S) preparation:
It prepares the toluene solution of 30mg/mL sulphur: taking out the distillation sulphur powder 450mg being stored in 60 DEG C of vacuum ovens, add
Enter 15mL toluene, seal, be placed on heat collecting type constant-temperature heating magnetic stirring apparatus, with 60 DEG C of temperature heating stirring, until sulphur
Powder is dissolved completely in toluene solution.
The toluene solution 1mL of above-mentioned sulphur is taken to drop evenly on the polypyrrole/graphene/carbon nano-tube coextruded film,
Then 155 DEG C of heat preservation 12h are heated in the closed container full of argon gas, then, are continuously heating to 300 DEG C of heat preservation 1h, obtain
A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film.
The battery performance that PCG-S is assembled is as shown in figure 8, the specific discharge capacity under 0.2C current density is specifically tied
Fruit is shown in Table 1.
Embodiment 3
A kind of positive pole material for high-performance lithium-sulfur battery, the material include sulphur/polypyrrole/graphene/carbon mano-tube composite,
The technical scheme steps that the present embodiment uses are as follows:
1) preparation of graphene oxide is the same as step 1) in comparative example 1；
2) purifying and acidification of carbon nanotube are the same as step 2) in comparative example 2；
3) preparation of polypyrrole/graphene/carbon nano-tube coextruded film (PCG):
It is added into 300mL ethyl alcohol and the mixed solution (volume ratio of ethyl alcohol and deionized water is 2:1) of deionized water
The graphene oxide water solution of 5.6mL step 1) preparation, ultrasonic disperse 0.5h under frequency 100kW；0.56mL pyrroles, stirring is added
After uniformly, it is aged three days at room temperature, solution colour becomes brownish black from brown color, obtains polypyrrole/graphene mix suspending
Liquid；0.28g kayexalate is added into above-mentioned suspension as dispersing agent；Then by mixed solution in magnetic agitation item
With further redox graphene, solution colour was by the further blackening of brownish black in 3 hours for the lower 90 DEG C of heating water baths of part；To nature
After being cooled to room temperature, three times by precursor suspension centrifuge washing, be subsequently dispersed in the deionized water of 240mL obtain polypyrrole/
Graphene composite solution；The carboxyl carbon nanotube of 56mg after purification is added into polypyrrole/graphene composite solution, is mixed
The TritonX-100 of 280 μ L is added after uniformly, ultrasonic disperse 30min under frequency 80kW obtains polypyrrole/graphene/carbon and receives
Mitron compound aqueous solution.30mL compound aqueous solution is drawn, the polypropylene screen for being 0.22 μm with aperture is -0.1MPa in vacuum degree
Under the conditions of filtered, it is dry after that fine and close polypyrrole/graphene/carbon nanotube can be obtained is compound for removing from polypropylene screen
Film, as active ingredient carriers.
4) sulphur/polypyrrole/graphene/carbon nano-tube coextruded film (PCG-S) preparation:
It prepares the toluene solution of 10mg/mL sulphur: taking out the distillation sulphur powder 150mg being stored in 60 DEG C of vacuum ovens, add
Enter 15mL toluene, seal, be placed on heat collecting type constant-temperature heating magnetic stirring apparatus, with 60 DEG C of temperature heating stirring, until sulphur
Powder is dissolved completely in toluene solution.
The toluene solution 0.1mL of above-mentioned sulphur is taken to drop evenly in the polypyrrole/graphene/carbon nano-tube coextruded film
On, 155 DEG C of heat preservation 8h then are heated in the closed container full of argon gas, then, are continuously heating to 240 DEG C of heat preservation 0.5h,
Obtain a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film.
The battery performance that PCG-S is assembled is as shown in figure 9, the specific discharge capacity under 0.2C current density is specifically tied
Fruit is shown in Table 1.
Specific discharge capacity (mA h/g) result under the different current densities of table 1
By above-mentioned test result it is found that laminated film of the present invention can be obviously improved lithium as lithium-sulphur cell positive electrode
The activity substance content and utilization rate of sulphur cell positive electrode material, and then discharge capacity and cycle performance are significantly improved, especially
It is to be become apparent compared with the chemical property improvement under high magnification.It is raw materials used environmental-friendly in method shown in the present invention, technique
Process is simple, efficient, and experiment condition is wide in range, provides an alternative approach for exploitation high-performance flexible lithium-sulfur cell.
The present invention includes but is not limited to above embodiments, it is all carried out under the principle of spirit of that invention it is any equivalent
Replacement or local improvement, all will be regarded as within the scope of the present invention.
Claims (10)
1. a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film, it is characterised in that: the film is by elemental sulfur, poly- pyrrole
It coughs up, redox graphene and function multi-walled carbon nano-tube composition；Wherein, pyrroles mixes with graphene oxide, and pyrroles is in situ
Polymerization obtains polypyrrole, and simultaneous oxidation graphene is reduced to redox graphene；The polypyrrole is grafted on oxygen reduction fossil
On black alkene；The redox graphene and function multi-walled carbon nano-tube interweave with forming three-dimensional carbon skeleton；The elemental sulfur is negative
It is loaded in the surface and inside of the three-dimensional carbon skeleton；It is in terms of 100% by the total film mass, the mass fraction of elemental sulfur is
55%~60%, the mass fraction of polypyrrole is 1%~10%, the mass fraction of function multi-walled carbon nano-tube is 20%~
25%, remaining is redox graphene.
2. a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film as described in claim 1, it is characterised in that: described
Function multi-walled carbon nano-tube is obtained after the acidified processing of multi-walled carbon nanotube.
3. a kind of sulphur as described in claim 1/polypyrrole/graphene/carbon nano-tube coextruded film preparation method, feature
It is: the method comprises the following steps:
(1) preparation of polypyrrole/graphene compound aqueous solution:
Graphene oxide water solution is added into the aqueous solution of ethyl alcohol, pyrroles is added in 0.5~2h of ultrasonic disperse, after mixing evenly,
Still aging 2~3 days at room temperature, kayexalate is added, is heated to 80~90 DEG C of 2~4h of reaction under stirring condition, instead
It is cooled to room temperature, is distributed to after centrifuge washing in the water of deionized water purity or more after answering, it is multiple to obtain polypyrrole/graphene
Heshui solution；Wherein, the mass ratio of graphene oxide, pyrroles and kayexalate is 1:10~100:5~10；
(2) polypyrrole/graphene/carbon nano-tube coextruded film preparation:
It is added in function multi-walled carbon nano-tube, is stirring evenly and then adding into the polypyrrole/graphene compound aqueous solution
TritonX-100,10~60min of ultrasonic disperse obtain polypyrrole/graphene/carbon nanotube compound aqueous solution；It draws above-mentioned multiple
Heshui solution, is filtered by vacuum with polypropylene screen, removes to obtain a kind of polypyrrole/graphene/carbon from polypropylene screen after dry
Nanotube composite film；Wherein, function multi-walled carbon nano-tube is the multi-walled carbon nanotube containing polar functional group, is functionalized more
The quality of wall carbon nano tube is 1~3 times of graphene oxide quality in step (1)；Polypyrrole/graphene/carbon nanotube is compound
Film with a thickness of 10~30 μm；
(3) sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation:
The toluene solution that sulphur is dropped evenly on the polypyrrole/graphene/carbon nano-tube coextruded film, under inert gas shielding
Be first to heat to 150~160 DEG C, keep the temperature 8~12h, be then heated to 240~300 DEG C, keep the temperature 0.5~1h, obtain a kind of sulphur/
Polypyrrole/graphene/carbon nano-tube coextruded film；Wherein, it is added drop-wise to polypyrrole/graphene/the carbon nano-tube coextruded film
The quality of upper sulphur is 1~30mg.
4. a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation method as claimed in claim 3, feature
Be: the volume ratio of second alcohol and water is 1:0.5~2 in the aqueous solution of ethyl alcohol described in step (1), and the water is that deionized water is pure
Degree or more water.
5. a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation method as claimed in claim 3, feature
Be: concentration of the TritonX-100 in compound aqueous solution described in step (2) is 0.1wt%~0.5wt%.
6. a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation method as claimed in claim 3, feature
Be: the supersonic frequency that ultrasonic disperse described in step (2) uses is 80kW~100kW.
7. a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation method as claimed in claim 3, feature
Be: the aperture of polypropylene screen is 0.22~0.45 μm in step (2).
8. a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation method as claimed in claim 3, feature
Be: vacuum degree is -0.08MPa~-0.1MPa when vacuum filtration in step (2).
9. a kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film preparation method as claimed in claim 3, feature
Be: the toluene solution concentration of sulphur is 10~30mg/mL in step (3).
10. a kind of sulphur as claimed in claim 1 or 2/polypyrrole/graphene/carbon nano-tube coextruded film application, feature
Be: the laminated film is used as the anode of lithium-sulfur cell.
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