CN105970605A - Graphene oxide composite non-woven fabric and preparation method and application thereof - Google Patents
Graphene oxide composite non-woven fabric and preparation method and application thereof Download PDFInfo
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- CN105970605A CN105970605A CN201610362356.9A CN201610362356A CN105970605A CN 105970605 A CN105970605 A CN 105970605A CN 201610362356 A CN201610362356 A CN 201610362356A CN 105970605 A CN105970605 A CN 105970605A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/22—Polymers or copolymers of halogenated mono-olefins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to non-woven fabric, in particular to graphene oxide composite non-woven fabric and a preparation method and application thereof. The graphene oxide composite non-woven fabric is provided with a non-woven fabric base material, pulp is poured into the non-woven fabric base material, or the surface of the non-woven fabric base material is coated with a pulp layer; the pulp is prepared from graphene oxide or graphene oxide blend, an adhesive and a solvent, and the graphene oxide blend is prepared from graphene oxide, a polymer and an inorganic substance. The preparation method comprises the steps that 1, graphene oxide or the graphene oxide blend, the adhesive and the solvent are mixed and then subjected to ball milling, and the pulp is obtained; 2, the pulp is poured into the non-woven fabric base material or smeared to the surface of the non-woven fabric base material, and after drying, the graphene oxide composite non-woven fabric is obtained. The graphene oxide composite non-woven fabric can be applied to preparation of a lithium sulphur battery, and according to the application, the graphene oxide composite non-woven fabric serves as a diaphragm in the lithium sulphur battery.
Description
Technical field
The present invention relates to non-woven fabrics, be specifically related to a kind of graphene oxide compound nonwoven cloth and preparation method and application.
Background technology
At present, the electrochmical power source system such as lithium ion battery etc. of liquid electrolyte is used to need to use diaphragm material to intercept
Positive and negative electrode, it is to avoid short circuit.Diaphragm material mainly with polyethylene (Polyethylene, PE), polypropylene (Polypropylene,
PP), the polymerization containing microcellular structure that politef (Polytetrafluoroethylene, PTFE) etc. are main component
Thing film, non-woven fabrics and electrostatic spinning barrier film.(carbonates usually containing electrolytic salt is organic molten for liquid electrolyte
Agent) it is present in microcellular structure, it is achieved ion conduction between positive and negative electrode.Barrier film constitutes with liquid electrolyte
Electrolyte system.
Along with the development in the fields such as electric automobile, capacity and power for electrochmical power source systems such as lithium ion batteries propose
Higher requirement, therefore the safety of battery is the most more and more paid attention to.Lithium-sulfur cell is the one of lithium battery,
Lithium-sulfur cell is that lithium metal is as a kind of lithium battery of negative pole using element sulphur as anode.Specific capacity is up to
1675mAh/g, the capacity of the most commercial wide variety of cobalt acid lithium battery (< 150mAh/g).And sulfur is
A kind of environment amenable element, does not the most pollute environment, is the most promising lithium battery of one.
The problem that lithium-sulfur cell exists at present mainly has:
The first, electron conduction and the ionic conductivity of elemental sulfur is poor, sulfur materials electrical conductivity at room temperature extremely low (5.0
×10-30S·cm-1), the end product Li of reaction2S2And Li2S is also electronic body, is unfavorable for the high magnification of battery
Performance.
The second, the middle discharging product of lithium-sulfur cell can be dissolved in organic electrolyte, increases the viscosity of electrolyte, fall
Low ionic conductivity.Many sulphions can migrate (Shuttle effect) between both positive and negative polarity, cause active substance loss and
The waste of electric energy.The polysulfide dissolved can be crossed over barrier film and be diffused into negative pole, with negative reaction, destroys consolidating of negative pole
Body electrolyte interface film (SEI film).
3rd, final discharging product Li of lithium-sulfur cell2Sn(n=1～2) electronic isolation and insoluble in electrolyte, is deposited on
The surface of conducting matrix grain；Partial vulcanization lithium departs from conducting matrix grain, it is impossible to by reversible charging process reaction become sulfur or
The polysulfide of person's higher order, causes the significant attenuation of capacity.
The density of the 4th, sulfur and lithium sulfide is respectively 2.07 and 1.66g cm-3, charge and discharge process has up to 79%
Volumetric expansion/contraction, this expansion can cause the change of positive pole pattern and structure, causes the disengaging of sulfur and conducting matrix grain,
Thus cause the decay of capacity；This bulk effect is not notable under button cell, but bulk effect in large-sized battery
Can amplify, significant capacity attenuation can be produced, it is possible to cause the damage of battery, huge change in volume can destroy electricity
Electrode structure.
5th, lithium-sulfur cell uses lithium metal as negative pole, and except the high activity of lithium metal self, lithium anode exists
Charge and discharge process can occur change in volume, and easily forms dendrite.
6th, the laboratory scale research of lithium-sulfur cell is carried out more, and in unit are, sulfur carrying capacity typically all exists
3.0mg·cm-2Hereinafter, the research carrying out high capacity amount pole piece has important value for obtaining high-performance lithium-sulfur cell.
Solution for problem above generally designs and electrolysis additive from the modification of electrode material and structure
Two aspects are started with.The micron order sulfur granules being coated with such as the modified graphene oxide of patent CN104852025A announcement,
Nano-sulfur particles and hollow sulfur granules, prepared combination electrode electrode material has good cycle, and high rate performance is high,
Have broad application prospects in energy storage field.With the polymer of unsaturated carbon-carbon double bond in patent CN104485449A
With the sulfur materials that elemental sulfur forms carbon cladding, the sulfur content of composite prepared by the method is higher, and technique is simple,
With low cost.By one or more of silane ethers as electrolysis additive in patent CN103855425A, this
Electrolyte has the characteristics such as viscosity is low, electrical conductivity is high, inhibition sulphion animal migration is good.Therefore hinder polysulfide ion just
Migration between negative pole is the effective way improving lithium-sulfur cell capacity.
Summary of the invention
It is an object of the invention to provide a kind of graphene oxide compound nonwoven cloth.
Another object of the present invention is to provide the preparation method of graphene oxide compound nonwoven cloth.
It is still another object of the present invention to provide the application of graphene oxide compound nonwoven cloth.
Described a kind of graphene oxide composite non woven is laid with non-woven fabrics base material, cast serosity inside non-woven fabrics base material, or
Non-woven fabrics base material surface-coated slurry layer；Described serosity is by graphene oxide or graphene oxide blend, binding agent and solvent
Composition, described graphene oxide blend is made up of graphene oxide, polymer and inorganic matter, and described polymer is selected from perfluor
Sulfonate resin, polyimides, polyetheramides, polyethylene glycol oxide, poly(ethylene oxide), polrvinyl chloride, poly-isophthalic diformazan
At least one in acyl m-diaminobenzene. resin, polyethylene terephthalate etc.；Described inorganic matter selected from silicon oxide or
Aluminium oxide；The mass ratio of described graphene oxide or graphene oxide blend and non-woven fabrics base material is 1: (0.1～10), institute
The mass ratio stating graphene oxide or graphene oxide blend and binding agent is (19～4): 1；Described solvent and binding agent and
The mass ratio of the gross mass of graphene oxide or graphene oxide blend is (199～4): 1.
The thickness of described slurry layer can be 1～20 μm, preferably 1～5 μm.
Described non-woven fabrics base material is selected from politef (Polytetrafluoroethylene, PTFE), Kynoar
(Polyvinylidene fluoride, PVDF), polrvinyl chloride (Polyvinyl chloride, PVC), poly-isophthalic diformazan
Acyl m-diaminobenzene. resin (Polym-phenylene isophthalamide, PMIA), polyethylene terephthalate
One in (polyethylene glycol terephthalate, PET) etc..
Described binding agent is selected from Kynoar (Polyvinylidene fluoride, PVDF), Kynoar-six
Fluoropropene copolymer (Polyvinylidene fluoride-hexafluoropropylene, PVDF-HFP), poly-methyl-prop
E pioic acid methyl ester (polymethyl methacrylate, PMMA), polyacrylonitrile (Polyacrylonitrile, PAN),
Polyimides (Polyimide, PI), polyvinylpyrrolidone (Polyvinylpyrrolidone, PVP), polycyclic oxygen
Ethane (Polyethylene oxide, PEO), polyvinyl alcohol (Polyving akohol, PVA), carboxymethyl cellulose
Sodium (Polymethyl methacrylate, CMC), butadiene-styrene rubber (Styrene-butadiene rubber, SBR), bright
At least one in glue etc..
Described binding agent accounts for described graphene oxide and graphene oxide blend, binding agent and solvent gross mass are preferred
0.5%～20%.
The described polymer quality being cast within non-woven fabrics preferably 2～10mg/cm3。
The preparation method of described a kind of graphene oxide compound nonwoven cloth, comprises the steps:
(1) by ball milling after graphene oxide or graphene oxide blend, binding agent and solvent mixing, serosity is obtained；
(2) serosity it is cast in non-woven fabrics base material inside or is coated in non-woven fabrics base material surface, after drying, obtaining graphite oxide
Alkene compound nonwoven cloth.
In step (2), described being dried can be vacuum dried at 50～60 DEG C.
Described graphene oxide compound nonwoven cloth can be applied in preparing lithium-sulfur cell, and described application is that described graphene oxide is multiple
Close non-woven fabrics as the barrier film in lithium-sulfur cell.
Described lithium-sulfur cell includes positive pole, negative pole and barrier film etc., and described barrier film is located between positive pole and negative pole.
For constituting the positive pole of nonaqueous electrolytic solution secondary battery, positive active material is properly added white carbon black, acetylene black etc. and leads
Electricity auxiliary agent, or Kynoar, the binding agent etc. such as poly(ethylene oxide), prepare anode mixture, by it with current collection materials such as aluminium foils
Expect to use as after coating on the banding molded body of core.But, the manufacture method of positive pole is not limited only to upper example.
In the nonaqueous electrolytic solution secondary battery that the present invention provides, use nonaqueous solvent (organic solvent) as nonaqueous electrolytic solution.
Nonaqueous solvent includes carbonates, ethers etc..
The invention has the beneficial effects as follows:
1, the graphene oxide composite diaphragm of the present invention is by non-woven fabrics and to be cast in nonwoven material inside or be coated on nonwoven surface
Graphene oxide or graphene oxide blend composition.Graphene oxide has the shared π bonding electron cloud and shape that negative electricity density is high
Film forming densification aperture is less, due to its electrostatic repulsion and microporous filter membrane effect, can effectively stop polysulfide ion just
Shuttling back and forth between negative pole, intercepts polysulfide ion in sulfur electrode side, effectively reduces the size in non-woven fabrics base material aperture simultaneously,
The micro-short circuit phenomenon preventing non-woven fabrics relatively big due to aperture and to occur.
2, the present invention passes through graphene oxide and the filming function of graphene oxide blend, can significantly improve the machine of non-woven fabrics
Tool intensity so that non-woven fabrics intensity reaches the standard of commercial Application.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 surface scan electromicroscopic photograph.
Fig. 2 is the surface electromicroscopic photograph of PET non-woven fabrics in the embodiment of the present invention 2.
Fig. 3 be the present invention be the profile scanning Electronic Speculum figure of graphene oxide composite diaphragm in embodiment 2.
The comparison diagram that Fig. 4 is graphene oxide composite diaphragm and common PE barrier film prevents polysulfide ion from permeating.
Graphene oxide compound nonwoven cloth and the common diaphragm of comparative example 1 that Fig. 5 is the embodiment of the present invention 1 are assembled lithium sulfur
Cycle performance of battery contrasts.Wherein curve a is graphene oxide compound nonwoven cloth, and curve b is PE barrier film.
Detailed description of the invention
Combine accompanying drawing below by way of specific embodiment technical scheme is further detailed and describes.
Embodiment 1
Graphene oxide 1g is put into deionized water and ethanol (1: 1, v: v) mixed solution 20g magnetic agitation 5h.With
Kynoar (PVDF) non-woven fabrics is base material, and gained solution and non-woven fabrics base material are made graphene oxide compound nonwoven cloth.
Gained serosity is coated uniformly on the one side of PVDF non-woven fabrics, and coat THICKNESS CONTROL is in 3 μm.With electric hot plate at 60 DEG C
Preheat, after solvent major part is volatilized, put into vacuum drying oven 60 DEG C drying the most thoroughly remove solvent, aoxidized
Graphene compound nonwoven cloth (graphene oxide compound nonwoven cloth stereoscan photograph is as shown in Figure 1).
Embodiment 2
Graphene oxide 1g and perfluorinated sulfonic resin 1g is put into deionized water and ethanol (1: 1, v: v) mixed solution 50g
Magnetic agitation 10h.With polyethylene terephthalate (PET) non-woven fabrics as base material, by gained solution and non-woven fabrics base material
Make graphene oxide compound nonwoven cloth.Gained serosity is uniformly cast in the inside of PET non-woven fabrics, pours into a mould polymeric material
Amount is 5mg/cm3.Preheat at 60 DEG C with electric hot plate, after the volatilization of equal solvent major part, put into vacuum drying oven 60 DEG C baking
Do and the most thoroughly remove solvent, obtain graphene oxide compound nonwoven cloth.
Fig. 2 is the surface scan Electronic Speculum figure of PET non-woven fabrics.Fig. 3 is the profile scanning of graphene oxide compound nonwoven cloth
Electronic Speculum figure.
Embodiment 3
Graphene oxide 0.5g and polyacrylonitrile (PAN) 0.5g is put into N-methyl ketopyrrolidine and acetone (1: 1, v: v)
Magnetic agitation 20h in mixed solution 100g.With polyethylene terephthalate (PET) non-woven fabrics as base material, by gained
Solution is coated.Gained serosity is uniformly cast in the inside of PET non-woven fabrics, and cast polymer quality is 10mg/cm3。
Preheat at 60 DEG C with electric hot plate, put into vacuum drying oven 60 DEG C drying after the volatilization of equal solvent major part and the most thoroughly remove
Solvent, obtains graphene oxide compound nonwoven cloth.
The comparison diagram that Fig. 4 is graphene oxide compound nonwoven cloth and common PE barrier film prevents polysulfide ion from permeating.
Embodiment 4
Graphene oxide 1.5g and polyethylene glycol oxide (PEO) 1g is put into deionized water and ethanol (1: 1, v: v) mixing
Magnetic agitation 20h in solution 100g.With Kynoar-hexafluoropropene (PVDF-HFP) non-woven fabrics as base material, by gained
Solution and non-woven fabrics base material make graphene oxide compound nonwoven cloth.Gained serosity is coated uniformly on PVDF-HFP nonwoven
The one side of cloth, coat THICKNESS CONTROL is in 5 μm..Preheat at 60 DEG C with electric hot plate, after the volatilization of equal solvent major part
Put into vacuum drying oven 60 DEG C drying and the most thoroughly remove solvent, obtain graphene oxide compound nonwoven cloth.
Embodiment 5
Graphene oxide and 1g and poly-dopamine (PDB) nano-particle 1g are put into N-methyl ketopyrrolidine and acetone (1:
1, v: v) magnetic agitation 20h in mixed solution 10g.With polyethylene terephthalate (PET) non-woven fabrics as base material,
Gained solution and non-woven fabrics base material are made graphene oxide compound nonwoven cloth.Gained serosity is coated uniformly on PVDF nonwoven
The one side of cloth, coat THICKNESS CONTROL is in 5 μm..Preheat at 60 DEG C with electric hot plate, after the volatilization of equal solvent major part
Put into vacuum drying oven 60 DEG C drying and the most thoroughly remove solvent, obtain graphene oxide compound nonwoven cloth.
Comparative example 1
Lithium-sulfur cell, has commercialization barrier film between positive electrode and negative material.
Graphene oxide compound nonwoven cloth and the common diaphragm of comparative example 1 that Fig. 5 is the embodiment of the present invention 1 are assembled lithium sulfur
Cycle performance of battery contrasts.Wherein curve a is graphene oxide compound nonwoven cloth, and curve b is PE barrier film.
Embodiment 6
Lithium-sulfur cell, including positive electrode and negative material, has embodiment 1 to prepare between positive electrode and negative material
Graphene oxide compound nonwoven cloth.The cycle performance of battery that testing example 6 obtains with comparative example 1, as shown in Figure 5.
It can be seen that use the cycle performance of battery of graphene oxide compound nonwoven cloth that the present invention obtains, ratio uses prior art
The cycle performance of battery of barrier film be obviously improved.
Embodiment 7
Lithium-sulfur cell, including positive electrode and negative material, has embodiment 2 to prepare between positive electrode and negative material
Graphene oxide compound nonwoven cloth.
Embodiment 8
Lithium-sulfur cell, including positive electrode and negative material, has embodiment 3 to prepare between positive electrode and negative material
Graphene oxide compound nonwoven cloth.
Embodiment 9
Lithium-sulfur cell, including positive electrode and negative material, has embodiment 4 to prepare between positive electrode and negative material
Graphene oxide compound nonwoven cloth.
Embodiment 10
Lithium-sulfur cell, including positive electrode and negative material, has embodiment 5 to prepare between positive electrode and negative material
Graphene oxide compound nonwoven cloth.
With the lithium-sulfur cell of compound nonwoven cloth of the present invention, there is capacity high, cycle performance and the characteristic such as high rate performance is superior.
The compound mechanical strength that improve non-woven fabrics base material of graphene oxide, effectively reduces non-woven fabrics base material aperture simultaneously
Size, prevents the generation of non-woven fabrics micro-short circuit.
Claims (10)
1. a graphene oxide compound nonwoven cloth, it is characterised in that be provided with non-woven fabrics base material, pours into a mould inside non-woven fabrics base material
Serosity, or in non-woven fabrics base material surface-coated slurry layer；Described serosity is by graphene oxide or graphene oxide blend, viscous
Knot agent and solvent composition, described graphene oxide blend is made up of graphene oxide, polymer and inorganic matter, described polymerization
Thing is selected from perfluorinated sulfonic resin, polyimides, polyetheramides, polyethylene glycol oxide, poly(ethylene oxide), polrvinyl chloride, gathers
At least one in mpd-i resin, polyethylene terephthalate；Described inorganic matter is selected from oxygen
SiClx or aluminium oxide；The mass ratio of described graphene oxide or graphene oxide blend and non-woven fabrics base material is 1:
(0.1～10), described graphene oxide or graphene oxide blend are (19～4) with the mass ratio of binding agent: 1；Described molten
Agent is (199～4) with the mass ratio of binding agent and the gross mass of graphene oxide or graphene oxide blend: 1.
2. a kind of graphene oxide compound nonwoven cloth, it is characterised in that the thickness of described slurry layer is
1～20 μm.
3. a kind of graphene oxide compound nonwoven cloth, it is characterised in that the thickness of described slurry layer is
1～5 μm.
4. a kind of graphene oxide compound nonwoven cloth, it is characterised in that described non-woven fabrics base material is selected from poly-
Tetrafluoroethene, Kynoar, polrvinyl chloride, poly(isophthaloyl metaphenylene diamine) resin, poly terephthalic acid second two
One in alcohol ester.
5. a kind of graphene oxide compound nonwoven cloth, it is characterised in that described binding agent is selected from poly-inclined
Fluorothene, Kynoar-hexafluoropropylene copolymer, polymethyl methacrylate, polyacrylonitrile, polyimides, poly-
In vinylpyrrolidone, poly(ethylene oxide), polyvinyl alcohol, sodium carboxymethyl cellulose, butadiene-styrene rubber, gelatin at least
A kind of.
6. a kind of graphene oxide compound nonwoven cloth, it is characterised in that described binding agent accounts for described oxidation
Graphene and graphene oxide blend, binding agent and the 0.5% of solvent gross mass～20%.
7. as claimed in claim 1 a kind of graphene oxide compound nonwoven cloth, it is characterised in that described in be cast in inside non-woven fabrics
Polymer quality be 2～10mg/cm3。
The preparation method of a kind of graphene oxide compound nonwoven cloth the most as claimed in claim 1, it is characterised in that include walking as follows
Rapid:
(1) by ball milling after graphene oxide or graphene oxide blend, binding agent and solvent mixing, serosity is obtained；
(2) serosity it is cast in non-woven fabrics base material inside or is coated in non-woven fabrics base material surface, after drying, obtaining graphite oxide
Alkene compound nonwoven cloth.
The preparation method of a kind of graphene oxide compound nonwoven cloth the most as claimed in claim 8, it is characterised in that in step (2)
In, described being dried is to be vacuum dried at 50～60 DEG C.
10. a kind of graphene oxide compound nonwoven cloth is applied in preparing lithium-sulfur cell, described application
It is that described graphene oxide compound nonwoven cloth is as the barrier film in lithium-sulfur cell.
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