CN109244334A - A kind of preparation method of lithium-sulfur cell and its diaphragm and the diaphragm - Google Patents
A kind of preparation method of lithium-sulfur cell and its diaphragm and the diaphragm Download PDFInfo
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- CN109244334A CN109244334A CN201811282438.8A CN201811282438A CN109244334A CN 109244334 A CN109244334 A CN 109244334A CN 201811282438 A CN201811282438 A CN 201811282438A CN 109244334 A CN109244334 A CN 109244334A
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M50/411—Organic material
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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
- H01M50/44—Fibrous material
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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 discloses the preparation methods of a kind of lithium-sulfur cell and its diaphragm and the diaphragm, belong to lithium ion battery separator technical field.A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate is equipped with functional structure layer, the component of the functional structure layer includes filler, bonding agent, leads lithium ion function additive, wherein filler be MoS2, graphene, iron sulfide, the 15-80% that one of stratified materials such as TiS2, ZrS2 or more than one combination its additive amount are functional structure layer gross weight.A kind of lithium-sulfur cell of the invention, using above-mentioned functional membrane as diaphragm." the shuttle effect " of more lithium sulfides can effectively be inhibited using technical solution of the present invention, and improve the coulombic efficiency, capacity and conductivity of lithium-sulfur cell.
Description
Technical field
The invention belongs to lithium ion battery separator technical fields, more specifically to a kind of lithium-sulfur cell and its diaphragm
With the preparation method of the diaphragm.
Background technique
In recent years, more and more new-energy automobiles occur in people's daily life, and country also supports and pushes away energetically
Into the marketization and application of New-energy electric vehicle.Lithium-sulfur cell uses the sulphur of rich content on the earth, high capacity to be used as anode,
Lithium is as cathode, and negative reaction is that lithium loses electronics and becomes lithium ion when electric discharge, and anode reaction is sulphur and lithium ion and electron back
Sulfide, reaction equation should be generated are as follows: S8+16Li++16e-1=8Li2S.Since multielectron transfer reaction, lithium sulphur occurs
Battery has very high theoretical specific capacity, and theoretical energy density is (1675mAh/g), has agreed with the need of electric car well
It asks.Lithium-sulfur cell has had small-scale application in American-European countries at present, simultaneously because sulphur simple substance has, environmental pollution is small, nothing
The features such as malicious, at low cost and raw material sources are extensive, lithium-sulfur cell are inexpensive, high-energy density system most prospect important
Component units.
Wherein, diaphragm is an important component in lithium-sulfur cell, for separating anode and cathode, to avoid inside
Short circuit, while facilitating free lithium ion and transporting between the electrodes.But the more sulphur of the intermediate product generated when lithium-sulfur cell charge and discharge
Change lithium electrode and easily pass through diaphragm and shuttle from sulphur anode to cathode of lithium, form insulating layer on cathode of lithium, reduces cathode of lithium and diaphragm
Contact, makes the transmission of lithium ion be obstructed, and coulombic efficiency reduces, while more lithium sulfides are the product of sulphur positive active material, more sulphur
Changing lithium reduces active material from the loss of anode, and the utilization rate of sulphur reduces, and capacity is caused to decline, and this effect is referred to as " to wear
Shuttle effect ".The shuttle effect of lithium-sulfur cell significantly limits the performance of lithium-sulfur cell capacity, affects the reality of lithium-sulfur cell
Using.Inhibit the shuttle effect of lithium-sulfur cell, diaphragm plays vital effect.Good diaphragm should do not influence lithium from
Under the premise of sub- normal transmission, while stopping the shuttle of polysulfide, and plays the capacity of electrode to the maximum extent.
For the above problem existing for lithium-sulfur cell, researcher mainly studies and prepares functionality in membrane surface at present
Coating inhibits the shuttles of more lithium sulfides.Such as, the application case that Chinese Patent Application No. is 201610779324.9 discloses one kind
For the functional membrane and lithium-sulfur cell of lithium-sulfur cell, the functional layer of this application is covered on the surface of the diaphragm substrate, institute
Stating functional layer includes at least two layers of carbon nanotube layer and at least two layers of graphene oxide composite layer, at least two layers of carbon nanotube
Layer and at least two layers of graphene oxide composite layer, which are layered on top of each other, to be arranged alternately, and the graphene oxide composite layer includes multiple oxidations
Graphene film and multiple manganese dioxide nano particles, the multiple graphene oxide sheet mutually overlap, the multiple titanium dioxide
Manganese nano particle is uniformly adsorbed on the graphene oxide on piece.
For another example, the application case that Chinese Patent Application No. is 201410490800.6 discloses a kind of composite structured lithium sulphur
It is multiple to be equipped with resistance sulphur in diaphragm and positive interpolar including the cathode, diaphragm, anode successively overlapped for battery, the lithium-sulfur cell of this application
Layer is closed, which is prepared by the metal chalcogenide with electro-chemical activity；Described has electro-chemical activity
Metal chalcogenide include TiS2, MoS2, WS2, SnS2, CdS, TaSe2, TiSe2, MoSe2 etc..Above-mentioned two application case passes through
The setting of functionality resistance sulphur coating can inhibit " the shuttle effect " of more lithium sulfides to a certain extent, but its effect still need into
One step improves.Further, since existing diaphragm is usually that phase inversion method is used to prepare, mechanical strength is lower, battery high rate performance compared with
Difference.
Summary of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome that " the shuttle effect " of more lithium sulfides easily occurs existing for existing lithium-sulfur cell no
Foot provides the preparation method of a kind of lithium-sulfur cell and its diaphragm and the diaphragm.It can be effective using technical solution of the present invention
" the shuttle effect " for inhibiting more lithium sulfides, improves the coulombic efficiency and capacity of lithium-sulfur cell.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
First, a kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate
Equipped with functional structure layer, the component of the functional structure layer includes filler, bonding agent, leads lithium subfunction auxiliary agent, wherein filling
Agent is one of stratified materials such as MoS2, graphene, iron sulfide, TiS2, ZrS2, layer structure clay, nano lamellar clay
Or more than one its additive amount of combination is the 15-80% of functional structure layer gross weight.
Further, the bonding agent is butadiene-styrene latex, cinnamic acid, polyacrylamide, polyvinyl alcohol, polyethylene
Pyrrolidones, polyethylene glycol oxide, modified paraffin resin, carbomer, polyacrylic, urethane acrylate, polyacrylic acid
One of ester copolymer emulsion, polyurethane, carbamate or more than one combination；The dosage of the bonding agent is function knot
The 0.1-40% of structure layer gross weight, preferably 10-30%.
Further, the lithium ion function additive of leading is Nafion medium, and hydrocarbon backbone leads lithium ion high score
Sub- medium, modified poly-epoxy ethane, poly(ethylene glycol) diacrylate, poly(ethylene glycol) methyl ether acrylate, styrene sulphur
Hydrochlorate, vinylsulfonate, propyl acrylate sulfonate, acrylate-propyl (three halosulfonyl groups) acid imide, methacrylaldehyde-
Propyl (trifyl) acid imide, Li3N, one of La0.5Li0.5TiO3 and Li3.25Ge0.25P0.75S4 or one
Kind or more combination, additive amount be functional structure layer gross weight 0.5-45%, preferably 15-30%.
Further, the component of the functional structure layer further include one of following function additive or more than one
Combination: sodium carboxymethylcellulose, polyethylene oxide, polyethylene glycol oxide, methylcellulose, hydroxypropyl methyl cellulose, ethoxy
Cellulose, gelatin, sodium alginate, polyethylene glycol, polyvinylpyrrolidone, sodium n-alkylbenzenesulfonate, alkyl polyoxyethylene ether,
Sldium lauryl sulfate, dispersing agent NNO, dispersing agent MF, alkylsulfonate, additive amount are the 0.1- of functional structure layer gross weight
25%, preferably 0.1-14%.
Further, the filler is preferably MoS2 or graphene, and additive amount is preferably functional structure layer gross weight
40-60%；The porous membrane substrate selects polyethylene, polypropylene, polyethylene terephthalate, one in polyimides
Kind is several, preferably polyethylene or polypropylene material；The porous membrane substrate with a thickness of 5~100 μm, porosity is 20%~
80%, aperture is 15nm~20 μm.
Further, the porous membrane substrate and functional structure layer are combined into multi-layer honeycomb reticular structure, and diaphragm
With a thickness of 5~100 μm, porosity is 20%~80%, and air permeability is 0~300s/100cc, and intensity is more than or equal to 35Mpa,
Tortuosity >=20.
Further, the filler is MoS2, and porous membrane substrate carries out following modification: by barrier film base material with
Silane coupling agent high speed is blended uniformly, adds a certain amount of organic peroxide, stretches, that is, formed through twin-screw melting extrusion
Silane-modified porous membrane substrate.The silane coupling agent is preferably trimethacrylate acyloxy propyl trimethoxy silicane, institute
Stating organic peroxide is to have one of hydroperoxides, dialkyl peroxide, diacyl peroxide, peroxy esters or one
Kind or more combination, and silane coupling agent additive amount be functional structure layer gross weight 0.1-10%, preferably 0.5-5%.
Further, the one or both sides of the porous membrane substrate are equipped with functional structure layer, and the functional membrane is by porous
Film base material and functional structure layer are arranged alternately to form multi-layer compound structure.
Second, a kind of lithium-sulfur cell of the invention, using above-mentioned functional membrane as diaphragm.
Third, a kind of preparation method of functional membrane for lithium-sulfur cell of the invention, including following procedure: by function knot
The each component raw material and solvent of structure layer are mixed by high speed dispersion, are uniformly mixed and are formed solution；Then pass through spraying, leaching
Functional structure layer is coated on the one or both sides of porous membrane substrate by painting, intaglio plate coating, compound or vacuum filter subsidence style, it
After dry, cut, that is, the functional membrane for lithium-sulfur cell is prepared；Wherein porous membrane substrate is by its raw material melting extrusion
Afterwards, it is formed according to Thermal inactive, dry method tension, melt-blown or electrostatic spinning, preferably thermal phase separation process, wherein thermotropic phase
Separating technology parameter is as follows: extruder temperature: 170-220 DEG C；Melt temperature: 160-205 DEG C；Casting temperature: 10-60 DEG C；It draws
Stretch temperature: 70-130 DEG C；Stretching speed ratio: 4-8.5 times.
Further, the porous membrane substrate carries out following modification: porous membrane substrate raw material and silane is even
Join agent to be blended uniformly, add a certain amount of organic peroxide, stretched through twin-screw melting extrusion, is formed silane-modified more
Hole film base material；Then using MoS2 as filler, MoS2 is dispersed to be formed homogeneous phase solution, and by silane-modified porous membrane substrate
Dip-coating is in the solution of MoS2, by being dried up to the functional membrane.
3. beneficial effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result:
(1) surface of a kind of functional membrane for lithium-sulfur cell of the invention, hole film base material is equipped with functional structure layer, the function
The component of energy structure sheaf includes filler, bonding agent and leads lithium subfunction auxiliary agent, is carried out by the component to functional structure layer excellent
Change design, on the one hand can effectively inhibit the shuttle effect of lithium-sulfur cell, promotes battery efficiency >=10%, on the other hand also
It is able to solve the problem of existing lithium-sulfur cell conductivity difference, promotes battery performance, wherein lithium ion transport can promote >=20%, electricity
Performance boost >=10%.
(2) a kind of functional membrane for lithium-sulfur cell of the invention, by type to each component in functional structure layer and
Content optimizes, and under the collective effect of each component, so as to effectively inhibit shuttle effect, improves battery efficiency
On the basis of conductivity, additionally it is possible to effectively improve the function film strength and bonding force, wherein functional membrane strength enhancing >=
100%, battery security is obviously improved, functional membrane bonding force >=10N/m, hence it is evident that improve the assembly efficiency of battery with it is consistent
Property.
(3) a kind of functional membrane for lithium-sulfur cell of the invention, advanced optimizes, and selects MoS2 as filler,
And silane-modified processing is carried out to porous membrane substrate, so as to further increase the tortuosity and rejection rate of the functional membrane,
Effectively inhibit the shuttle effect of more lithium sulfides.
(4) a kind of lithium-sulfur cell of the invention is applied by optimizing to its membrane configuration on barrier film base material surface
Cloth functional structure layer to can either effectively inhibit the shuttle phenomenon of more lithium sulfides, while can also promote anode, diaphragm, bear
Boundary strength between pole promotes battery with two side terminals and electrical property and lithium ion transport ability, solves lithium-sulfur cell conductance
The low problem of rate.
(5) preparation method of a kind of functional membrane for lithium-sulfur cell of the invention, by the surface of porous membrane substrate
Functional structure layer is prepared to form the functional membrane of multi-layer honeycomb reticular structure, while the group of functional structure layer is grouped as and is matched
Than optimizing, so as to effectively inhibit the shuttle effect of lithium-sulfur cell, and be conducive to improve the battery of lithium-sulfur cell
Efficiency and conductivity, while can also ensure that gained is bonding between film strength and functional structure layer and porous membrane substrate
Property.
(6) preparation method of a kind of functional membrane for lithium-sulfur cell of the invention, by carrying out silicon to porous membrane substrate
Alkane modification, and using MoS2 as filler, by silane-modified porous membrane substrate dip-coating in the solution of MoS2, contained
The modified function film of MoS2 functional structure layer, to help to further increase the inhibitory effect to more lithium sulfide shuttle effects.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of lithium-sulfur cell functional membrane in embodiment 2；
Fig. 2 is the structural schematic diagram of lithium-sulfur cell functional membrane in embodiment 3.
Specific embodiment
A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate are equipped with
Functional structure layer, the component of the functional structure layer include filler, bonding agent and lead lithium subfunction auxiliary agent, and wherein filler is
One in the lamellar structures materials such as MoS2, graphene, iron sulfide, TiS2, ZrS2, layer structure clay, nano lamellar clay
Kind or more than one combination, preferably MoS2 or graphene, additive amount are the 15-80% of functional structure layer gross weight, preferably
For 40-60%.The bonding agent be butadiene-styrene latex, cinnamic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone,
Polyethylene glycol oxide, modified paraffin resin, carbomer, polyacrylic, urethane acrylate, polyacrylate copolymerization cream
One of liquid, polyurethane, carbamate or more than one combination, the dosage of bonding agent are functional structure layer gross weight
0.1-40%, preferably 10-30%.The lithium ion function additive of leading is Nafion medium, and hydrocarbon backbone leads lithium ion
Macromolecule medium, modified poly-epoxy ethane, poly(ethylene glycol) diacrylate, poly(ethylene glycol) methyl ether acrylate, benzene second
Alkene sulfonate, vinylsulfonate, propyl acrylate sulfonate, acrylate-propyl (three halosulfonyl groups) acid imide, propylene
Aldehyde-propyl (trifyl) acid imide, Li3N, one of La0.5Li0.5TiO3 and Li3.25Ge0.25P0.75S4
Or more than one combination, additive amount are the 0.5-45%, preferably 15-30% of functional structure layer gross weight.Pass through specific kind
Class and being added with for content function additive are conducive to further promote battery with two side terminals and electrical property and lithium ion transport ability,
Solve the problems, such as that lithium-sulfur cell conductivity is low.
Further optimize, the component of the functional structure layer further include one of following function additive or it is a kind of with
On combination: sodium carboxymethylcellulose, polyethylene oxide, polyethylene glycol oxide, methylcellulose, hydroxypropyl methyl cellulose, hydroxyl
Ethyl cellulose, gelatin, sodium alginate, polyethylene glycol, polyvinylpyrrolidone, sodium n-alkylbenzenesulfonate, alkyl polyoxy second
Alkene ether, sldium lauryl sulfate, dispersing agent NNO, dispersing agent MF, alkylsulfonate, additive amount are functional structure layer gross weight
0.1-25%, preferably 0.1-14%.
Porous membrane substrate of the invention can be selected polyethylene, polypropylene, polyethylene terephthalate, in polyimides
One or more, preferably polyethylene or polypropylene material, the porous membrane substrate with a thickness of 5~100 μm, porosity is
20%~80%, aperture is 15nm~20 μm.Wherein porous membrane substrate is by its raw material melting extrusion (dry method) or and paraffin oil
It is coextruded (wet process) film forming, then list drawing/Jia La or Thermal inactive (TISP)/stretching/extraction become more simultaneously by heating
Permeability film can also become porous film by melt-blown or electrostatic spinning；Preferably thermal phase separation process, wherein heat
Cause phase separation process parameter as follows: extruder temperature: 170-220 DEG C；Melt temperature: 160-205 DEG C；Casting temperature: 10-60
℃；Draft temperature: 70-130 DEG C；Stretching speed ratio: 4-8.5 times.And functional structure layer can be by spraying, dip-coating, intaglio plate coating, multiple
The modes such as conjunction or vacuum filter sedimentation are coated on the one or both sides of porous membrane substrate, dry later, cut, that is, use is prepared
In the functional membrane of lithium-sulfur cell.The functional membrane with a thickness of 5~100 μm, porosity is 20%~80%, air permeability is 0~
300s/100cc, intensity are more than or equal to 35Mpa, tortuosity >=20.The diaphragm of macromolecule nonwoven fabric construct when the present invention is also suitable
Base structure.
Specifically, can be in the one or both sides coating function structure sheaf of porous membrane substrate in the present invention, and the functional membrane
It can be arranged alternately by porous membrane substrate and functional structure layer and form multi-layer compound structure, such as the coated on one side function of porous membrane substrate
Energy structure sheaf, the outside of functional structure layer continue compound one layer of porous membrane substrate and form 3 layers of composite construction；Meanwhile it can be most
Compound layer function structure sheaf and one layer of porous membrane substrate are continued in the surface of outer layer porous membrane substrate, to form 5 layer function films
Composite construction, and so on, wherein optimal with 3 layers.
More optimized, filler of the invention selects MoS2, and porous membrane substrate can carry out following modification: by diaphragm
Substrate is blended uniformly with silane coupling agent high speed, adds a certain amount of organic peroxide, stretches through twin-screw melting extrusion,
Form silane-modified porous membrane substrate.Specifically, by silane-modified porous membrane substrate dip-coating in the solution containing MoS2,
- Si (OCH3) 3 in silane-modified perforated membrane hydrolyzes to form silanol group (- SiOH), then reacts with the hydroxyl on the surface MoS2,
Hydrogen bond is formed, is dehydrated and is condensed into-SiO-MoS2 covalent bond.Meanwhile the silanol of silane-modified each molecule of perforated membrane is mutually formed again
The film that oligomerisation forms reticular structure is closed, tridimensional network is staggered to form between porous fenestra with MoS2, so as to further
The tortuosity and rejection rate for increasing gained functional membrane, are conducive to improve the inhibitory effect to more lithium sulfide shuttle effects.
To further appreciate that the contents of the present invention, now in conjunction with specific embodiment, the present invention is described in detail.It needs to illustrate
, since length is limited herein, only enumerate section Example below, wherein filler, bonding agent, lead lithium subfunction auxiliary agent and
Type and proportion and the specific number of plies of functional membrane of other function auxiliary agent etc. are not limited to following specific embodiments.
Embodiment 1
A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate are equipped with
Functional structure layer, the component of the functional structure layer include filler, bonding agent and lead lithium subfunction auxiliary agent, and wherein filler is
MoS2, additive amount are the 40% of functional structure layer gross weight.The bonding agent is cinnamic acid, and the dosage of bonding agent is function
The 30% of structure sheaf gross weight.The lithium ion function additive of leading is modified poly-epoxy ethane, and additive amount is functional structure layer
The 30% of gross weight.
The preparation method of the functional membrane for lithium-sulfur cell of the present embodiment, including following procedure: by functional structure layer
Each component raw material is mixed with solvent (ethyl alcohol) by high speed dispersion, is uniformly mixed and is formed solution；Then pass through spraying side
Functional structure layer is coated on the one side of porous membrane substrate by formula, is dried later, the function for lithium-sulfur cell is prepared in slitting
It can film.The porous membrane substrate of the present embodiment is polyethylene terephthalate, and ethylene terephthalate raw material is melted and is squeezed
After out, formed by dry-stretch process, the porous membrane substrate with a thickness of 40 μm, porosity 50%, aperture be 15nm~
20 μm, final preparation gained functional membrane with a thickness of 50 μm, air permeability 50s/100cc, tortuosity 25.
Embodiment 2
A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate are equipped with
Functional structure layer, the component of the functional structure layer include filler, bonding agent and lead lithium subfunction auxiliary agent, and wherein filler is
Graphene, additive amount are the 48% of functional structure layer gross weight.The bonding agent is urethane acrylate, the use of bonding agent
Amount is the 27% of functional structure layer gross weight.The lithium ion function additive of leading is poly(ethylene glycol) methyl ether acrylate and benzene
Vinyl sulfonate, additive amount are the 25% of functional structure layer gross weight.
The preparation method of the functional membrane for lithium-sulfur cell of the present embodiment, including following procedure: by functional structure layer
Each component raw material is mixed with solvent (ethanol water) by high speed dispersion, is uniformly mixed and is formed solution；Then pass through
Functional structure layer is coated on the two sides of porous membrane substrate by vacuum filter subsidence style, is dried later, use is prepared in slitting
In the functional membrane (as shown in Figure 1) of lithium-sulfur cell, the functional membrane with a thickness of 10 μm, porosity 25%, tortuosity 28.This
The porous membrane substrate of embodiment is that polyimides is formed after polyimides raw material melting extrusion using electrostatic spinning process；It should
Porous membrane substrate with a thickness of 5 μm, porosity 20%, aperture is 15nm~20 μm.
Embodiment 3
A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate are equipped with
Functional structure layer, the component of the functional structure layer include filler, bonding agent and lead lithium subfunction auxiliary agent, and wherein filler is
Iron sulfide, additive amount are the 15% of functional structure layer gross weight.The bonding agent is butadiene-styrene latex, and the dosage of bonding agent is function
The 40% of energy structure sheaf gross weight.The lithium ion function additive of leading is (class) Nafion (DuPont Corporation) medium, is added
Dosage is the 45% of functional structure layer gross weight.
The preparation method of the functional membrane for lithium-sulfur cell of the present embodiment, including following procedure: by functional structure layer
Each component raw material is mixed with solvent (ethyl alcohol) by high speed dispersion, is uniformly mixed and is formed solution；Then pass through dip-coating side
Functional structure layer is coated on the one side of porous membrane substrate by formula, is dried later, the function for lithium-sulfur cell is prepared in slitting
Can film, the functional membrane with a thickness of 100 μm, porosity 80%, air permeability is 0~300s/100cc, tortuosity 26.This reality
The porous membrane substrate for applying example is that polyethylene is formed after polyethylene raw material melting extrusion using thermal phase separation process, wherein heat
Cause phase separation process parameter as follows: extruder temperature: 170 DEG C；Melt temperature: 160 DEG C；Casting temperature: 10 DEG C；Draft temperature:
70℃；Stretching speed ratio: 6 times.The porous membrane substrate with a thickness of 80 μm, porosity 70%, aperture is 15nm~20 μm.
The lithium-sulfur cell of the present embodiment, using above-mentioned functional membrane as diaphragm, and it specifically includes three-decker (such as Fig. 2
It is shown), i.e., continue to be coated with one layer of porous membrane substrate on the surface of functional structure layer.
Embodiment 4
A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate are equipped with
Functional structure layer, the component of the functional structure layer include filler, bonding agent and lead lithium subfunction auxiliary agent, and wherein filler is
TiS2 and layer structure clay, additive amount are the 80% of functional structure layer gross weight.The bonding agent is polyvinylpyrrolidine
Ketone and urethane acrylate, the dosage of bonding agent are the 10% of functional structure layer gross weight.Described leads lithium ion function additive
For styrene sulfonate, the combination of vinylsulfonate and propyl acrylate sulfonate, additive amount is functional structure layer gross weight
10%.
The preparation method of the functional membrane for lithium-sulfur cell of the present embodiment, including following procedure: by functional structure layer
Each component raw material is mixed with solvent (ethanol water) by high speed dispersion, is uniformly mixed and is formed solution；Then pass through
Functional structure layer is coated on the two sides of porous membrane substrate by plate gravure coating method, is dried later, slitting is prepared for lithium
The functional membrane of sulphur battery, the functional membrane with a thickness of 20 μm, porosity 70%, air permeability 300s/100cc, intensity is greater than
Equal to 35Mpa, tortuosity 30.The porous membrane substrate of the present embodiment is polypropylene, after pp material melting extrusion, according to
Thermal phase separation process is formed, and wherein thermal phase separation process parameter is as follows: extruder temperature: 190 DEG C；Melt temperature: 185
℃；Casting temperature: 25 DEG C；Draft temperature: 90 DEG C；Stretching speed ratio: 4 times.
Embodiment 5
A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate are equipped with
Functional structure layer, the component of the functional structure layer include filler, bonding agent and lead lithium subfunction auxiliary agent, and wherein filler is
ZrS2, additive amount are the 75% of functional structure layer gross weight.The bonding agent is carbomer, polyacrylic and amino first
The combination of acid esters, the dosage of bonding agent are the 25% of functional structure layer gross weight.It is described lead lithium ion function additive be Li3N and
The combination of Li3.25Ge0.25P0.75S4, additive amount are the 15% of functional structure layer gross weight.
The preparation method of the functional membrane for lithium-sulfur cell of the present embodiment, including following procedure: by functional structure layer
Each component raw material and solvent are mixed by high speed dispersion, are uniformly mixed and are formed solution；Then pass through spraying method for function
Energy structure sheaf is coated on the one side of porous membrane substrate, dries later, cuts, that is, the functional membrane for lithium-sulfur cell is prepared,
Functional membrane with a thickness of 8 μm, porosity 65%, air permeability 260s/100cc, intensity is more than or equal to 35Mpa, and tortuosity is
32.The porous membrane substrate of the present embodiment is polyethylene and polypropylene, after polyethylene and pp material melting extrusion, according to heat
Phase separation process is caused to be formed, wherein thermal phase separation process parameter is as follows: extruder temperature: 220 DEG C；Melt temperature: 205 DEG C；
Casting temperature: 60 DEG C；Draft temperature: 130 DEG C；Stretching speed ratio: 8.5 times.
The lithium-sulfur cell of the present embodiment, using above-mentioned functional membrane as diaphragm, and it specifically includes five-layer structure, i.e., more
The surface of hole film base material is successively compounded with functional structure layer, porous membrane substrate, functional structure layer and porous membrane substrate.
Embodiment 6
A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate are equipped with
Functional structure layer, the component of the functional structure layer include filler, bonding agent and lead lithium subfunction auxiliary agent, and wherein filler is
MoS2 and graphene, additive amount are the 60% of functional structure layer gross weight.The bonding agent is carbomer, the use of bonding agent
Amount is the 27% of functional structure layer gross weight.The lithium ion function additive of leading is modified poly-epoxy ethane and acrylate-the third
Base (three halosulfonyl groups) acid imide, additive amount are the 25% of functional structure layer gross weight.
The preparation method of the functional membrane for lithium-sulfur cell of the present embodiment, including following procedure: by functional structure layer
Each component raw material and solvent are mixed by high speed dispersion, are uniformly mixed and are formed solution；Then pass through plate gravure coating method
Functional structure layer is coated on to the one side of porous membrane substrate, is dried later, cuts, that is, the function for lithium-sulfur cell is prepared
Film.The functional membrane with a thickness of 25 μm, porosity 65%, intensity is more than or equal to 35Mpa, tortuosity 28.The present embodiment
Porous membrane substrate is polyethylene, after polyethylene raw material melting extrusion, is formed according to thermal phase separation process, wherein thermotropic phase point
Separating process parameter is as follows: extruder temperature: 210 DEG C；Melt temperature: 195 DEG C；Casting temperature: 45 DEG C；Draft temperature: 80 DEG C；It draws
Stretch speed ratio: 6 times.
The lithium-sulfur cell of the present embodiment, using above-mentioned functional membrane as diaphragm, and it specifically includes three-decker.
Embodiment 7
A kind of functional membrane for lithium-sulfur cell of the invention, including porous membrane substrate, the surface of porous membrane substrate are equipped with
Functional structure layer, the component of the functional structure layer include filler, bonding agent and lead lithium subfunction auxiliary agent, and wherein filler is
MoS2 and nano lamellar clay, additive amount are the 30% of functional structure layer gross weight.The bonding agent is polyurethane, bonding agent
Dosage be functional structure layer gross weight 35%.The lithium ion function additive of leading is modified poly-epoxy ethane, poly- (second two
Alcohol) diacrylate, styrene sulfonate and acrylate-propyl (three halosulfonyl groups) acid imide, additive amount is function
The 35% of structure sheaf gross weight.
The preparation method of the functional membrane for lithium-sulfur cell of the present embodiment, including following procedure: by functional structure layer
Each component raw material and solvent are mixed by high speed dispersion, are uniformly mixed and are formed solution；Then pass through dip coating manner for function
Energy structure sheaf is coated on the two sides of porous membrane substrate, dries later, cuts, that is, the functional membrane for lithium-sulfur cell is prepared.
The porous membrane substrate of the present embodiment is polyethylene terephthalate, by polyethylene terephthalate raw material melting extrusion
Afterwards, porous membrane substrate is formed according to dry-stretch process.
Embodiment 8
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the component of the functional structure layer include filler, bonding agent and other function additives, and wherein filler is
Graphene, additive amount are the 55% of functional structure layer gross weight.The bonding agent is butadiene-styrene latex, and the dosage of bonding agent is function
The 20% of energy structure sheaf gross weight；Other function auxiliary agent is sodium carboxymethylcellulose and polyethylene glycol, sodium carboxymethylcellulose, poly- second
The dosage of glycol is respectively the 20% of functional structure layer gross weight, 5%.
Embodiment 9
A kind of functional membrane for lithium-sulfur cell of the present embodiment, substantially with embodiment 8, difference mainly exists composition
In: filler is ZrS2 in the present embodiment, and additive amount is the 70% of functional structure layer gross weight, and bonding agent is cinnamic acid, is glued
The dosage for connecing agent is the 15% of functional structure layer gross weight；Other function auxiliary agent includes polyethylene oxide and polyvinylpyrrolidone,
Polyethylene oxide, the dosage of polyvinylpyrrolidone are respectively the 10% of functional structure layer gross weight, 5%.
Embodiment 10
A kind of functional membrane for lithium-sulfur cell of the present embodiment, substantially with embodiment 8, difference mainly exists composition
In: filler is TiS2 in the present embodiment, and additive amount is the 80% of functional structure layer gross weight.The bonding agent is polypropylene
The combination of amide and polyvinyl alcohol, the dosage of bonding agent are the 19% of functional structure layer gross weight；Other function auxiliary agent is polyoxygenated
The combination of ethylene, methylcellulose, sodium n-alkylbenzenesulfonate and alkyl polyoxyethylene ether, wherein polyethylene glycol oxide, methyl are fine
The total amount of dimension element is the 0.9% of functional structure layer gross weight, and the total amount of sodium n-alkylbenzenesulfonate and alkyl polyoxyethylene ether is function
The 0.1% of energy structure sheaf gross weight.
Embodiment 11
A kind of functional membrane for lithium-sulfur cell of the present embodiment, substantially with embodiment 8, difference mainly exists composition
In: filler is iron sulfide in the present embodiment, and additive amount is the 60% of functional structure layer gross weight.The bonding agent is poly- ammonia
Ester acrylate, the dosage of bonding agent are the 18% of functional structure layer gross weight；Other function auxiliary agent be hydroxypropyl methyl cellulose,
The combination of hydroxyethyl cellulose, gelatin, sldium lauryl sulfate, dispersing agent NNO and alkylsulfonate, dosage are functional structure layer
The 22% of gross weight.
Embodiment 12
A kind of functional membrane for lithium-sulfur cell of the present embodiment, substantially with embodiment 8, difference mainly exists composition
In: filler is the combination of MoS2 and iron sulfide in the present embodiment, and additive amount is the 78% of functional structure layer gross weight.Described
Bonding agent is carbamate, and the dosage of bonding agent is the 3% of functional structure layer gross weight；Other function auxiliary agent is gelatin and seaweed
The combination of sour sodium, dosage are the 19% of functional structure layer gross weight.
Embodiment 13
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the component of the functional structure layer include filler, bonding agent, lead lithium ion function additive and other function
Auxiliary agent, wherein filler is graphene, and additive amount is the 15% of functional structure layer gross weight.Lithium ion function additive is led to be modified
Polyethylene oxide, additive amount are the 40% of functional structure layer gross weight；Bonding agent is Polyacrylate Emulsion, bonding agent
Dosage is the 20% of functional structure layer gross weight；Other function auxiliary agent includes hydroxypropyl methyl cellulose, gelatin, sodium alginate and alkane
Base polyoxyethylene ether, hydroxypropyl methyl cellulose, gelatin, sodium alginate total amount be functional structure layer gross weight 20%, alkyl
The dosage of polyoxyethylene ether is the 5% of functional structure layer gross weight.The preparation method of the functional membrane of the present embodiment is the same as embodiment 3.
Embodiment 14
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the component of the functional structure layer include filler, bonding agent, lead lithium ion function additive and other function
Auxiliary agent, wherein filler is TiS2, and additive amount is the 80% of functional structure layer gross weight.The bonding agent is modified paraffin tree
Rouge, the dosage of bonding agent are the 10% of functional structure layer gross weight；The lithium ion function additive of leading includes poly(ethylene glycol) two
Acrylate, poly(ethylene glycol) methyl ether acrylate and styrene sulfonate, additive amount are functional structure layer gross weight
9%.Other function auxiliary agent includes sodium alginate, sldium lauryl sulfate and dispersing agent MF, and the dosage of sodium alginate is functional structure
The 0.5% of layer gross weight；The total amount of sldium lauryl sulfate and dispersing agent MF is the 0.5% of functional structure layer gross weight.
Embodiment 15
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the component of the functional structure layer include filler, bonding agent, lead lithium ion function additive and other function
Auxiliary agent, wherein filler is MoS2, and additive amount is the 63% of functional structure layer gross weight.The bonding agent is carbomer,
The dosage of bonding agent is the 3% of functional structure layer gross weight；Leading lithium ion function additive is propyl acrylate sulfonate, additive amount
It is the 33% of functional structure layer gross weight；Other function auxiliary agent includes methylcellulose and hydroxypropyl methyl cellulose, and dosage is
The 1% of functional structure layer gross weight.
The preparation method of the functional membrane for lithium-sulfur cell of the present embodiment, including following procedure: by functional structure layer
Each component raw material and solvent are mixed by high speed dispersion, are uniformly mixed and are formed solution；Then pass through plate gravure coating method
Functional structure layer is coated on to the one side of porous membrane substrate, is dried later, cuts, that is, the function for lithium-sulfur cell is prepared
Film.The porous membrane substrate of the present embodiment is to be formed according to thermal phase separation process, by after its raw material melting extrusion wherein thermotropic phase
Separating technology parameter is as follows: extruder temperature: 185 DEG C；Melt temperature: 165 DEG C；Casting temperature: 25 DEG C；Draft temperature: 80 DEG C；
Stretching speed ratio: 4 times.
The lithium-sulfur cell of the present embodiment, using above-mentioned functional membrane as diaphragm, and it specifically includes three-decker.
Embodiment 16
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the component of the functional structure layer includes filler, bonding agent and leads lithium ion function additive, wherein filling
Agent is MoS2, and additive amount is the 55% of functional structure layer gross weight.The bonding agent is carbomer, and the dosage of bonding agent is
The 17% of functional structure layer gross weight；The lithium ion function additive of leading includes modified poly-epoxy ethane, propyl acrylate sulfonic acid
Salt and vinylsulfonate, additive amount are the 28% of functional structure layer gross weight.The function for lithium-sulfur cell of the present embodiment
The preparation process of film is as follows:
(1) modification of porous membrane substrate: polyethylene raw material is blended uniformly with silane coupling agent, is added a certain amount of
Organic peroxide, stretched through twin-screw melting extrusion, form silane-modified porous membrane substrate；The thickness of the porous membrane substrate
Degree is 25 μm, porosity 30%, and aperture is 15nm~20 μm.Silane coupling agent uses trimethacrylate acyl-oxygen in the present embodiment
Base propyl trimethoxy silicane, additive amount are the 3% of functional structure layer gross weight, and organic peroxide is to have hydroperoxides.
(2) using MoS2 as filler, by MoS2 and bonding agent, lithium ion function additive is led and solvent is mixed and is uniformly dispersed
Homogeneous phase solution is formed, then by silane-modified porous membrane substrate dip-coating in the above-mentioned solution containing MoS2, by drying process
Up to the functional membrane, gained functional membrane with a thickness of 30 μm, porosity 50%, air permeability 300s/100cc, intensity is big
In equal to 35Mpa, tortuosity 38.The lithium-sulfur cell of the present embodiment, using above-mentioned functional membrane as diaphragm, and it is specifically included
Three-decker.
Embodiment 17
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the component of the functional structure layer include filler, bonding agent and other auxiliary agents, and wherein filler is
MoS2, additive amount are the 65% of functional structure layer gross weight.The bonding agent is butadiene-styrene latex, and the dosage of bonding agent is function
The 15% of structure sheaf gross weight；Other auxiliary agents include sodium carboxymethylcellulose (CMC), polyethylene oxide, hydroxypropyl methyl cellulose
And alkyl polyoxyethylene ether, sodium carboxymethylcellulose (CMC), polyethylene oxide, the total amount of hydroxypropyl methyl cellulose are function
The 15% of structure sheaf gross weight；The dosage of alkyl polyoxyethylene ether is the 5% of functional structure layer gross weight.
Substantially with embodiment 16, difference mainly exists the preparation process of the functional membrane for lithium-sulfur cell of the present embodiment
In: porous membrane substrate uses polypropylene in the present embodiment, and the additive amount of silane coupling agent is the 5% of functional structure layer gross weight, institute
Stating organic peroxide is dialkyl peroxide.Functional membrane obtained by the present embodiment with a thickness of 80 μm, porosity 60%, thoroughly
Manner is 170s/100cc, and intensity is more than or equal to 35Mpa, tortuosity 36.The lithium-sulfur cell of the present embodiment, using above-mentioned function
Film is as diaphragm, and it specifically includes five-layer structure.
Embodiment 18
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the component of the functional structure layer includes filler, bonding agent, lead lithium ion function additive and other are helped
Agent, wherein filler is MoS2, and additive amount is the 40% of functional structure layer gross weight.The bonding agent is carbamate,
The dosage of bonding agent is the 15% of functional structure layer gross weight；Leading lithium ion function additive is methacrylaldehyde-propyl (trifluoro methylsulfonyl
Base) acid imide, additive amount is the 25% of functional structure layer gross weight；Other auxiliary agents include hydroxyethyl cellulose, sodium alginate, gather
Vinylpyrrolidone, alkyl polyoxyethylene ether, dispersing agent MF and alkylsulfonate, the total amount of hydroxyethyl cellulose, sodium alginate
It is the 15% of functional structure layer gross weight；Polyvinylpyrrolidone, alkyl polyoxyethylene ether, dispersing agent MF and alkylsulfonate it is total
Amount is the 5% of functional structure layer gross weight.
Substantially with embodiment 16, difference mainly exists the preparation process of the functional membrane for lithium-sulfur cell of the present embodiment
In: porous membrane substrate uses polyethylene and polypropylene in the present embodiment, and silane coupling agent additive amount is functional structure layer gross weight
0.5%, the organic peroxide is diacyl peroxide.The lithium-sulfur cell of the present embodiment, using above-mentioned functional membrane conduct
Diaphragm, and it specifically includes seven-layer structure.The aperture of functional membrane obtained by the present embodiment is 15nm~20 μm, final preparation gained function
Can film with a thickness of 50 μm, air permeability 50s/100cc, tortuosity 34.
Embodiment 19
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the component of the functional structure layer includes filler, bonding agent, lead lithium ion function additive and other are helped
Agent, wherein filler is MoS2, and additive amount is the 60% of functional structure layer gross weight.The bonding agent is polyurethane, bonding
The dosage of agent is the 6% of functional structure layer gross weight；The lithium ion function additive of leading is vinylsulfonate and acrylic acid third
Sulfonated ester, additive amount are the 30% of functional structure layer gross weight.Other auxiliary agents include methylcellulose, hydroxypropyl methyl fiber
Element, gelatin, polyethylene glycol, sodium n-alkylbenzenesulfonate, dispersing agent NNO and sldium lauryl sulfate, dosage are functional structure layer
The 4% of gross weight.
Substantially with embodiment 16, difference mainly exists the preparation process of the functional membrane for lithium-sulfur cell of the present embodiment
In: porous membrane substrate uses polyethylene and polypropylene in the present embodiment, and the organic peroxide is to have hydroperoxides and mistake
The mixture of oxygen ester, silane coupling agent additive amount are the 10% of functional structure layer gross weight.
Embodiment 20
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the group of functional structure layer are grouped as same embodiment 1, and difference essentially consists in: perforated membrane base in the present embodiment
Material is modified processing in advance, and modified technique is with embodiment 16, and wherein silane coupling agent additive amount is functional structure layer gross weight
0.1%.It can be further improved relative to embodiment 1 suppression to more lithium sulfide shuttle effects using the functional membrane of the present embodiment
Effect processed, which is 15nm~20 μm, with a thickness of 50 μm, tortuosity 30.
Embodiment 21
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the group of functional structure layer are grouped as same embodiment 3, and difference essentially consists in: perforated membrane base in the present embodiment
Material is modified processing in advance, and modified technique is the same as embodiment 17.Use the functional membrane of the present embodiment can be with relative to embodiment 3
The inhibitory effect to more lithium sulfide shuttle effects is further increased, which is 15nm~20 μm, bent with a thickness of 5 μm
Folding degree is 35.
Embodiment 22
A kind of functional membrane for lithium-sulfur cell of the present embodiment, including porous membrane substrate, the surface of porous membrane substrate are set
Functional structure sheaf, the group of functional structure layer are grouped as same embodiment 5, and difference essentially consists in: perforated membrane base in the present embodiment
Material is modified processing in advance, and for modified technique with embodiment 5, which is 15nm~20 μm, bent with a thickness of 50 μm
Folding degree is 37.
Claims (10)
1. the surface of a kind of functional membrane for lithium-sulfur cell, including porous membrane substrate, porous membrane substrate is equipped with functional structure layer,
It is characterized by: the component of the functional structure layer includes filler, bonding agent and leads lithium ion function additive, wherein filler
For in the lamellar structures materials such as MoS2, graphene, iron sulfide, TiS2, ZrS2, layer structure clay, nano lamellar clay
One or more kinds of combinations, additive amount are the 15-80% of functional structure layer gross weight.
2. a kind of functional membrane for lithium-sulfur cell according to claim 1, it is characterised in that: the bonding agent is fourth
Atrolactamide, cinnamic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, modified paraffin resin, card
One of wave resin, polyacrylic, urethane acrylate, Polyacrylate Emulsion, polyurethane, carbamate
Or more than one combination；The dosage of the bonding agent is the 0.1-40%, preferably 10-30% of functional structure layer gross weight.
3. a kind of functional membrane for lithium-sulfur cell according to claim 1, it is characterised in that: described leads lithium ion function
Energy auxiliary agent is Nafion medium, and hydrocarbon backbone leads lithium ion macromolecule medium, modified poly-epoxy ethane, poly(ethylene glycol) dipropyl
Olefin(e) acid ester, poly(ethylene glycol) methyl ether acrylate, styrene sulfonate, vinylsulfonate, propyl acrylate sulfonate, third
Olefin(e) acid ester-propyl (three halosulfonyl groups) acid imide, methacrylaldehyde-propyl (trifyl) acid imide, Li3N,
One of La0.5Li0.5TiO3 and Li3.25Ge0.25P0.75S4 or more than one combination, additive amount are function knot
The 0.5-45% of structure layer gross weight, preferably 15-30%.
4. the functional membrane according to any one of claim 1-3 for lithium-sulfur cell, it is characterised in that: the function knot
The component of structure layer further includes one of following function additive or more than one combination: sodium carboxymethylcellulose, polycyclic oxygen second
Alkane, polyethylene glycol oxide, methylcellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, gelatin, sodium alginate, poly- second two
Alcohol, polyvinylpyrrolidone, sodium n-alkylbenzenesulfonate, alkyl polyoxyethylene ether, sldium lauryl sulfate, dispersing agent NNO, diffusion
Agent MF, alkylsulfonate, additive amount are the 0.1-25%, preferably 0.1-14% of functional structure layer gross weight.
5. a kind of functional membrane for lithium-sulfur cell according to any one of claim 1-3, it is characterised in that: described to fill out
Filling agent is preferably MoS2 or graphene, and additive amount is preferably the 40-60% of functional structure layer gross weight；The porous membrane substrate choosing
With one or more of polyethylene, polypropylene, polyethylene terephthalate, polyimides, preferably polyethylene or poly-
Propylene material；The porous membrane substrate with a thickness of 5~100 μm, porosity is 20%~80%, and aperture is 15nm~20 μm；Institute
State porous membrane substrate and functional structure layer be combined into multi-layer honeycomb reticular structure, and diaphragm with a thickness of 5~100 μm, hole
Rate is 20%~80%, and air permeability is 0~300s/100cc, and intensity is more than or equal to 35Mpa, tortuosity >=20.
6. a kind of functional membrane for lithium-sulfur cell according to any one of claim 1-3, it is characterised in that: described to fill out
Filling agent is preferably MoS2, and porous membrane substrate carries out following modification: barrier film base material is blended with silane coupling agent high speed
It is even, organic peroxide is added, is stretched through twin-screw melting extrusion, that is, forms silane-modified porous membrane substrate；The silicon
Alkane coupling agent is preferably trimethacrylate acyloxy propyl trimethoxy silicane, and the organic peroxide is to have hydroperoxidation
One of object, dialkyl peroxide, diacyl peroxide, peroxy esters or more than one combination, and silane coupling agent
Additive amount is the 0.1-10%, preferably 0.5-5% of functional structure layer gross weight.
7. a kind of functional membrane for lithium-sulfur cell according to any one of claim 1-3, it is characterised in that: described more
The one or both sides of hole film base material are equipped with functional structure layer, and the functional membrane is arranged alternately by porous membrane substrate and functional structure layer
Form multi-layer compound structure.
8. a kind of lithium-sulfur cell, it is characterised in that: the lithium-sulfur cell is made using functional membrane of any of claims 1-7
For diaphragm.
9. a kind of preparation method of such as functional membrane of any of claims 1-7 for lithium-sulfur cell, feature exist
In including following procedure: each component raw material and solvent of functional structure layer being mixed by high speed dispersion, are uniformly mixed
Form solution；Then functional structure layer is coated on by spraying, dip-coating, intaglio plate coating, compound or vacuum filter subsidence style
The one or both sides of porous membrane substrate, are dried later, the functional membrane for lithium-sulfur cell is prepared in slitting；It is wherein porous
Film base material is to be formed after its raw material melting extrusion according to Thermal inactive, dry method tension, melt-blown or electrostatic spinning, preferably
Thermal phase separation process, wherein thermal phase separation process parameter is as follows: extruder temperature: 170-220 DEG C；Melt temperature: 160-
205℃；Casting temperature: 10-60 DEG C；Draft temperature: 70-130 DEG C；Stretching speed ratio: 4-8.5 times.
10. a kind of preparation method of functional membrane for lithium-sulfur cell according to claim 9, it is characterised in that: described
Porous membrane substrate carries out following modification: porous membrane substrate raw material being blended uniformly with silane coupling agent, is added certain
The organic peroxide of amount is stretched through twin-screw melting extrusion, forms silane-modified porous membrane substrate；Then using MoS2 as
Filler disperses MoS2 to form homogeneous phase solution, and by silane-modified porous membrane substrate dip-coating in the solution of MoS2, by
It is dried up to the functional membrane.
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