CN108565386A - Lithium-sulfur cell diaphragm and preparation method thereof, lithium-sulfur cell and preparation method thereof - Google Patents
Lithium-sulfur cell diaphragm and preparation method thereof, lithium-sulfur cell and preparation method thereof Download PDFInfo
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- CN108565386A CN108565386A CN201810307112.XA CN201810307112A CN108565386A CN 108565386 A CN108565386 A CN 108565386A CN 201810307112 A CN201810307112 A CN 201810307112A CN 108565386 A CN108565386 A CN 108565386A
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
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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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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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
- 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
- H01M50/431—Inorganic 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
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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
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Abstract
The present invention provides a kind of lithium-sulfur cell diaphragms and preparation method thereof, lithium-sulfur cell and preparation method thereof, it is related to membrane technique field, the lithium-sulfur cell diaphragm includes support membrane, nitrating carbon adsorption conductive coating is compounded on the support membrane, the preparation method of the lithium-sulfur cell diaphragm includes the following steps：Nitrating carbon adsorption conductive coating is coated on support membrane, after drying, obtain lithium-sulfur cell diaphragm, it is substantially no barrier effect for more sulphions to alleviate traditional diaphragm, the technical issues of can not stopping polysulfide dissolution and shuttle phenomenon, by being compounded with nitrating carbon adsorption conductive coating on support membrane, polysulfide is attracted on diaphragm, carry out strong electric conductivity conversion, inhibit " the shuttle effect " of polysulfide, and reduce interfacial reaction resistance, effectively recycling anode and the dissolution sulphur at diaphragm interface, improve positive electrode active material utilization, limit the cross-film diffusion of polysulfide, to improve the cycle performance of lithium-sulfur cell.
Description
Technical field
The present invention relates to membrane technique fields, more particularly, to a kind of lithium-sulfur cell diaphragm and preparation method thereof, lithium sulphur electricity
Pond and preparation method thereof.
Background technology
With the increasingly exacerbation of energy crisis and environmental pollution, the rechargeable battery with excellent performance has become solution
One of the important means of above problem.Lithium ion battery has preferable cycle life, higher operating voltage and less
The advantages that pollution, therefore lithium ion battery is more and more widely used.However, lower battery energy density, higher
Battery cost and battery safety the problems such as limit lithium ion battery in electric vehicle and large-scale energy storage equipment etc.
Application.Study with high-energy density, long circulation life, good safety and low cost heavy-duty battery at
For the task of top priority.In order to meet the needs of social, develops the next-generation secondary cell with high-energy density and high security and compel
In the eyebrows and eyelashes.
Lithium-sulfur cell is due to it is with higher energy density, lower manufacturing cost and higher safety in recent years
Greatly cause the concern of society.Its theoretical energy density is up to 2600Wh/kg, significantly larger than now commercialized lithium from
Sub- battery.But lithium-sulfur cell reaction system is extremely complex, more lithium sulfide intermediate products in charge and discharge process are dissolved in electrolysis
Liquid can cause positive active material to lose, battery capacity is caused to decay, while polysulfide reaches meeting and lithium metal hair after cathode
Raw redox reaction, forms " shuttle effect ", reduces the coulombic efficiency of system.But polyethylene or polypropylene commercial at present
Diaphragm has relatively high porosity and a larger micro-pore diameter to ensure higher lithium ion conductivity, and more sulphions
Diameter be less than 1nm, so traditional diaphragm is substantially no barrier effect for more sulphions, can not stop more sulphur
Compound dissolves out and shuttle phenomenon.
In view of this, special propose the present invention.
Invention content
One of the objects of the present invention is to provide a kind of lithium-sulfur cell diaphragms, to stop to more sulphions, reduce more
Sulfide dissolves out and shuttle phenomenon.
Lithium-sulfur cell diaphragm provided by the invention, including support membrane are compounded with nitrating carbon adsorption-conduction on the support membrane
Coating.
Further, the nitrating carbon adsorption-conductive coating mainly by nitrating porous carbon-carbon nanotube-graphene and glues
Mixture is made；
Preferably, the mass ratio of the nitrating porous carbon-carbon nanotube-graphene and adhesive is (80-99)：(1-
20)。
Further, the nitrating porous carbon-carbon nanotube-graphene is mainly received by nanoporous carbon, graphene and carbon
Mitron is made；
Preferably, the mass ratio of the nanoporous carbon, graphene and carbon nanotube is (1-2)：(2-3)：(1-2).
Further, the nitrating porous carbon-carbon nanotube-graphene is mainly by amido modification nanoporous carbon, carboxyl
Graphite alkene and carboxylic carbon nano-tube are made；
Preferably, the preparation method of the nitrating porous carbon-carbon nanotube-grapheme material includes the following steps：
Amido modification nanoporous carbon, carboxylated graphene and carboxylic carbon nano-tube are mixed, condensation reaction is carried out, obtains
To nitrating porous carbon-carbon nanotube-graphene；
Preferably, condensation reaction carries out under activator effect；
Preferably, the activator is selected from n-hydroxysuccinimide, 1- ethyls -3- (3- dimethyl aminopropyls)-is carbonized
Diimine or N, at least one of N ' dicyclohexylcarbodiimides.
Further, the preparation method of the amido modification nanoporous carbon includes the following steps：
(a) by nanoporous carbon carboxylated, carboxylated nanoporous carbon is obtained；
(b) by carboxylated nanoporous phosphinylidyne chlorination, chloride nanoporous carbon is obtained；
(c) chloride nanoporous carbon is subjected to amido modification, obtains amido modification nanoporous carbon；
Preferably, in step (a), first nanoporous carbon and the mixed solution of sulfuric acid and nitric acid are flowed back, then will
Nanoporous carbon after reflux is reacted with the mixed solution of sulfuric acid and hydrogen peroxide, and reflux obtains carboxylated nanoporous carbon；
Preferably, in step (b), carboxylated nanoporous carbon and thionyl chloride are dissolved in organic solvent, carried out
Reaction, reflux obtain chloride nanoporous carbon；
Preferably, in step (c), chloride nanoporous carbon and ethylenediamine are dissolved in organic solvent, reacts, obtains
Nanoporous carbon is modified to amido.
Further, the nanoporous carbon in Ketjen black, acetylene black, mesoporous carbon or carbon molecular sieve at least one
Kind；
Preferably, the carboxylated graphene is selected from single layer carboxylated graphene and/or double multilayer carboxylated graphenes；
Preferably, the carboxylic carbon nano-tube is selected from single wall carboxylic carbon nano-tube and/or multi wall carboxylated carbon nanometer
Pipe.
Further, the support membrane be selected from polyethylene porous membrane, polypropylene porous film, polyethylene/polypropylene it is compound every
Film, dual coating adhesive polyethylene perforated membrane, dual coating adhesive polypropylene porous film, polyimide diaphragm or aramid fiber every
At least one of film；
Preferably, the thickness of the support membrane is 16-25 μm；
Preferably, the thickness of the nitrating carbon adsorption-conductive coating is 4-10 μm.
The second object of the present invention is to provide the preparation method of above-mentioned lithium-sulfur cell diaphragm, include the following steps：
Nitrating carbon adsorption-conductive coating is coated on support membrane, after dry, obtains lithium-sulfur cell diaphragm；
Preferably, nitrating porous carbon-carbon nanotube-graphene and adhesive are dissolved in solvent, slurry are made, by slurry
Coated on support membrane, after dry, lithium-sulfur cell diaphragm is obtained.
The third object of the present invention is to provide a kind of lithium-sulfur cell, including lithium-sulfur cell diaphragm provided by the invention, sulphur
Positive plate and lithium cathode sheet；
Preferably, the sulphur positive plate is mainly coated on plus plate current-collecting body by positive electrode and is prepared；
Preferably, the positive electrode includes positive electrode active materials, conductive agent and adhesive；
Preferably, the positive electrode active materials are sulphur carbon complex and/or sulphur；
Preferably, the lithium cathode sheet is in lithium electrode, Li-C Electrode, lithium alloy electrode or modified cladding lithium electrode
It is at least one.
The fourth object of the present invention is to provide the preparation method of above-mentioned lithium-sulfur cell, include the following steps：
Lithium-sulfur cell diaphragm is placed between sulphur positive plate and lithium cathode sheet, core is assembled into, is put into lithium-sulfur cell shell
In, electrolyte is injected, sealing obtains lithium-sulfur cell.
Lithium-sulfur cell diaphragm provided by the invention, by being compounded with nitrating carbon adsorption-conductive coating on support membrane so that
Polysulfide can be attracted on diaphragm, carry out strong electric conductivity conversion, be inhibited " the shuttle effect " of polysulfide, and can be
Anode builds current collector structure with diaphragm interface, reduces interfacial reaction resistance, while can also adsorb polysulfide, activates sulfur-bearing
Component, effectively recycling anode and the dissolution sulphur at diaphragm interface, improve positive electrode active material utilization, limit polysulfide
Cross-film diffusion, to improve the cycle performance of lithium-sulfur cell.
The preparation method of lithium-sulfur cell diaphragm provided by the invention, it is simple for process, it is easy to operate, industrialization can be suitable for
Big production.
Lithium-sulfur cell provided by the invention provides lithium-sulfur cell diaphragm by using the present invention and substitutes traditional microporous film
The diaphragm of structure, improves positive electrode active material utilization, limits the cross-film diffusion of polysulfide, to improve lithium sulphur electricity
The cycle performance in pond.
The preparation method of lithium-sulfur cell provided by the invention, it is simple for process, it is easy to operate, it is big raw that industrialization can be suitable for
Production.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph for nitrating porous carbon-carbon nanotube-graphene that the embodiment of the present invention 3 provides；
Fig. 2 is the lithium sulphur soft-package battery that the embodiment of the present invention 11 provides and the lithium sulphur soft-package battery charge and discharge that comparative example 8 provides
Electric curve；
Fig. 3 is the cycle of the lithium sulphur soft-package battery that the embodiment of the present invention 3 provides and the lithium sulphur soft-package battery that comparative example 2 provides
Performance curve.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below, it is clear that described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
The every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
According to an aspect of the present invention, the present invention provides a kind of lithium-sulfur cell diaphragm, including support membrane, on support membrane
It is compounded with nitrating carbon adsorption-conductive coating.
Lithium-sulfur cell diaphragm provided by the invention, by being compounded with nitrating carbon adsorption-conductive coating on support membrane so that
Polysulfide can be attracted on diaphragm, carry out strong electric conductivity conversion, inhibit " the shuttle effect " of polysulfide and can be
Anode builds current collector structure with diaphragm interface, reduces interfacial reaction resistance, while can also adsorb polysulfide, activates sulfur-bearing
Component, effectively recycling anode and the dissolution sulphur at diaphragm interface, improve positive electrode active material utilization, limit polysulfide
Cross-film diffusion, to improve the cycle performance of lithium-sulfur cell.
In the present invention, nitrating carbon adsorption-conductive coating meaning is the coating that nitrating carbon has both absorption and conducting function.
In the preferred embodiment of the present invention, nitrating carbon adsorption-conductive coating is mainly received by the porous carbon-to-carbon of nitrating
Mitron-graphene and adhesive are made.
It is coated on support membrane after nitrating porous carbon-carbon nanotube-graphene and adhesive mixing, forms nitrating carbon and inhale
Attached-conductive coating.
In the preferred embodiment of the present invention, the quality of nitrating porous carbon-carbon nanotube-graphene and adhesive
Than for (80-99)：(1-20).
In the typical but non-limiting embodiment of the present invention, nitrating porous carbon-carbon nanotube-graphene and bonding
The mass ratio of agent is 80:20、81:19|、82:18、83:17、84:16、85:15、86:14、87:13、88:12、89:11、90:
10、91:19、92:18、93:17、94:16、95:15、96:14、97:13、98:12 or 99:1.
In a preferred embodiment of the invention, adhesive is selected from polyacrylic acid (PAA), polytetrafluoroethylene (PTFE) (PTFE), gathers
Vinylidene chloride (PVDF), polyacrylamide (PAM), butadiene-styrene rubber (SBR), hydroxypropyl methyl cellulose (HPMC), Methyl cellulose
Plain (MC), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), acrylonitrile copolymer, sodium alginate, chitosan and chitosan spread out
At least one of biology.
Acrylonitrile copolymer includes but not limited to LA132, LA133 and LA135.
In the preferred embodiment of the present invention, the nitrating porous carbon-carbon nanotube-grapheme material mainly by
Nanoporous carbon, graphene and carbon nanotube are made.
Nanoporous carbon has good absorption property, can effectively adsorb polysulfide, graphene and carbon nanotube tool
There is good electric conductivity.
Nanoporous carbon-to-carbon nanotube-graphene alkene, more by nanometer made of nanoporous carbon, graphene and carbon nanotube
Hole carbon is supported on the face conduction that electronics is realized on graphene, and bridging connection will be carried out between nanoporous carbon using carbon nanotube
Together, the line conduction of electronics is realized so that physical absorption phase (nanoporous carbon), chemisorption phase (nitrogenous and oxygen functional group)
Same interface is coexisted between strong conductive phase (graphene and carbon nanotube) three, polysulfide is by after nanoporous carbon adsorption
It is converted completely using the strong electric conductivity of graphene and carbon nanotube.
In the preferred embodiment of the present invention, the mass ratio of nanoporous carbon, graphene and carbon nanotube is (1-
2)：(2-3)：(1-2).
By by nanoporous carbon, graphene and carbon nanotube coordinated so that nanoporous carbon-to-carbon nanotube-stone
The electric conductivity and absorption property of black alkene are more excellent.
In the preferred embodiment of the present invention, nanoporous carbon is that amido modifies nanoporous carbon, and graphene is
Carboxylated graphene, carbon nanotube are carboxylic carbon nano-tube.
It is raw material by selecting amido to modify nanoporous carbon, carboxylated graphene and carboxylic carbon nano-tube, in order to
Amido modifies nanoporous carbon, carboxylated graphene and carboxylic carbon nano-tube and carries out condensation reaction, prepares nanoporous carbon-to-carbon
Nanotube-graphene alkene.
In the preferred embodiment of the present invention, the preparation method of nitrating porous carbon-carbon nanotube-grapheme material
Include the following steps：
Amido modification nanoporous carbon, carboxylated graphene and carboxylic carbon nano-tube are mixed, condensation reaction is carried out, obtains
To nitrating porous carbon-carbon nanotube-graphene.
In present invention further optimization embodiment, by amido modification nanoporous carbon, carboxylated graphene and carboxylic
After the mixing of base carbon nano tube, condensation reaction activator is added and obtains the porous carbon-to-carbon of nitrating to accelerate condensation reaction process and receives
Mitron-graphene.
In a preferred embodiment of the invention,
In the still more preferably embodiment of the present invention, by amido modification nanoporous carbon, carboxylated graphene and
Carboxylic carbon nano-tube is placed in a reaction flask, and N is added, and N ' dicyclohexylcarbodiimides (DCC) heat in 90-100 DEG C of solvent
Flow back 48h, is filtered after reaction, washes away extra DCC and other by-products with absolute ethyl alcohol, be dried in vacuo and mixed at 60 DEG C
Nitrogen porous carbon-carbon nanotube-graphene.
In the preferred embodiment of the present invention, the preparation method of amido modification nanoporous carbon includes following step
Suddenly：
(a) by nanoporous carbon carboxylated, carboxylated nanoporous carbon is obtained；
(b) by carboxylated nanoporous phosphinylidyne chlorination, chloride nanoporous carbon is obtained；
(c) chloride nanoporous carbon is subjected to amido modification, obtains amido modification nanoporous carbon.
In preferred embodiment provided by the invention, amine will be carried out again after nanoporous carbon successively carboxylated, chloride
Base is modified, and amido modification nanoporous carbon is obtained.
In present invention further optimization embodiment, in step (a), first by nanoporous carbon and sulfuric acid and nitric acid
Mixed solution flow back, then the nanoporous carbon after reflux is reacted with the mixed solution of sulfuric acid and hydrogen peroxide, is returned
Stream obtains carboxylated nanoporous carbon.
In present invention further optimization embodiment, in step (b), by carboxylated nanoporous carbon and protochloride
Sulfone is dissolved in organic solvent, is reacted, and reflux obtains chloride nanoporous carbon.
In present invention further optimization embodiment, in step (c), by chloride nanoporous carbon and ethylenediamine
It is dissolved in organic solvent, reacts, obtain amido modification nanoporous carbon.
The typical but non-limiting preparation method of aminated modification nanoporous carbon provided by the invention, including walk as follows
Suddenly：
(1) by nanoporous carbon and H2SO4With HNO3Mixed solution (98%H2SO4:68%HNO3=3:1 (volume ratio))
In mass ratio 1:(200-300) is mixed, and the back flow reaction 4h under the conditions of 30-40 DEG C of supersonic oscillations is cooled to room temperature, and addition is gone
After ionized water dilution, filters and cleaned to filtrate pH=7 with deionized water；
(2) step (1) product is placed in H2SO4With H2O2Mixed solution (98%H2SO4:30%H2O2=4:1 (volume
Than)) in, it flows back at 70 DEG C after 0.5h, filters and cleaned to filtrate pH and be in neutrality with deionized water, product, which is placed in vacuum, to be dried
It is dried in vacuo in case for 24 hours, obtains carboxylated nanoporous carbon；
(3) step (2) product is placed in a reaction flask, excess thionyl chloride and organic solvent is added, is stirred at 70 DEG C
Reflux for 24 hours, is filtered, washed, dries and obtain the nanoporous carbon materials of chloride.
(4) it takes step (3) product to be placed in a reaction flask, a certain amount of ethylenediamine is added, flow back and stir in 75 DEG C of organic solvents
Mix 48h, be filtered, washed, dry obtain amido modification porous carbon.
It takes step (4) product to be placed in a reaction flask, a certain amount of carboxylated graphene, carboxylic carbon nano-tube and DCC is added,
It is heated to reflux 48h in 90-100 DEG C of organic solvent, is filtered after reaction, extra DCC and other by-products are washed away with absolute ethyl alcohol
Object is dried in vacuo at 60 DEG C and obtains nitrating porous carbon-carbon nanotube-graphene.
In a preferred embodiment of the invention, organic solvent used by step (1) and step (2) is dimethyl methyl
Amide.
In a preferred embodiment of the invention, the organic solvent employed in step (5) is benzene and/or toluene.
In the preferred embodiment of the present invention, nanoporous carbon is selected from Ketjen black, acetylene black, mesoporous carbon or carbon point
At least one of son sieve.
In the preferred embodiment of the present invention, carboxylated graphene is selected from single layer carboxylated graphene and/or more
Layer carboxylated graphene；Wherein multilayer carboxylated graphene refers to that the number of plies is 2 layers or more of carboxylated graphene.
In the preferred embodiment of the present invention, carboxylic carbon nano-tube be selected from single wall carboxylic carbon nano-tube and/
Or multi wall carboxylic carbon nano-tube；Wherein multi wall carboxylic carbon nano-tube refers to that the number of plies is 2 layers or more of carboxylated carbon nanometer
Pipe.
In the preferred embodiment of the present invention, the thickness of support membrane is 16-25 μm, and nitrating carbon adsorption-conduction applies
The thickness of layer is 4-10 μm.
In the typical but non-limiting embodiment of the present invention, the thickness of support membrane is 16,17,18,19,20,21,
22、23、24、25μm。
In the typical case of the present invention but non-limiting embodiment, the thickness of nitrating carbon adsorption-conductive coating is 4,5,6,
7,8,9 or 10 μm.
In the preferred embodiment of the present invention, support membrane is selected from polyethylene porous membrane, polypropylene porous film, poly- second
Alkene/polypropylene composite materials diaphragm, dual coating adhesive polyethylene perforated membrane, dual coating adhesive polypropylene porous film, polyamides
At least one of imines diaphragm or aramid fiber diaphragm.
In a preferred embodiment of the invention, dual coating adhesive polyethylene perforated membrane, dual coating adhesive are poly-
Adhesive employed in propylene perforated membrane is selected from polyacrylic acid (PAA), polytetrafluoroethylene (PTFE) (PTFE), Vingon
(PVDF), polyacrylamide (PAM), butadiene-styrene rubber (SBR), hydroxypropyl methyl cellulose (HPMC), methylcellulose (MC), carboxylic
In methylcellulose (CMC), polyvinyl alcohol (PVA), acrylonitrile copolymer, sodium alginate, chitosan and chitosan derivatives
It is at least one.
According to the second aspect of the invention, the present invention provides the preparation methods of above-mentioned lithium-sulfur cell diaphragm, including such as
Lower step：
Nitrating carbon adsorption-conductive coating is coated on support membrane, after dry, obtains lithium-sulfur cell diaphragm.
The preparation method of lithium-sulfur cell diaphragm provided by the invention, it is simple for process, it is easy to operate, industrialization can be suitable for
Big production.
In a preferred embodiment of the invention, nitrating porous carbon-carbon nanotube-graphene and adhesive are dissolved in solvent
In, slurry is made, slurry is coated on support membrane, after dry, obtains lithium-sulfur cell diaphragm.
According to the third aspect of the present invention, the present invention provides a kind of lithium-sulfur cell, including confession provided by the invention
Lithium-sulfur cell diaphragm, sulphur positive plate and lithium cathode sheet.
Lithium-sulfur cell provided by the invention provides lithium-sulfur cell diaphragm by using the present invention and substitutes traditional microporous film
The diaphragm of structure, improves positive electrode active material utilization, limits the cross-film diffusion of polysulfide, to improve lithium sulphur electricity
The cycle performance in pond.
In the preferred embodiment of the present invention, sulphur positive plate is mainly coated on by positive electrode on plus plate current-collecting body
It is prepared.
In present invention further optimization embodiment, positive electrode includes positive electrode active materials, conductive agent and bonding
Agent.
In a preferred embodiment of the invention, positive electrode active materials are sulphur carbon complex and/or sulphur；Conductive agent is selected from stone
At least one of ink, carbon black, acetylene black, graphene, carbon fiber and carbon nanotube；Adhesive is selected from polyacrylic acid (PAA), gathers
Tetrafluoroethene (PTFE), Vingon (PVDF), polyacrylamide (PAM), butadiene-styrene rubber (SBR), hydroxypropyl methyl fiber
Plain (HPMC), methylcellulose (MC), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), acrylonitrile copolymer, alginic acid
At least one of sodium, chitosan and chitosan derivatives.
In the preferred embodiment of the present invention, lithium cathode sheet be selected from lithium electrode, Li-C Electrode, lithium alloy electrode or
At least one of modified cladding lithium electrode.
Lithium alloy electrode includes lithium-aluminium alloy electrode, lithium indium alloy electrode, lithium-tin alloy electrode, lithium magnesium alloy electrode, lithium
Silicon alloy electrode etc..
Modified cladding lithium electrode includes inorganic matter cladding lithium electrode, Coated with Organic Matter lithium electrode and polymeric PTC materials lithium electrode
Etc. types.
According to the fourth aspect of the present invention, the present invention provides the preparation methods of above-mentioned lithium-sulfur cell, including walk as follows
Suddenly：
Lithium-sulfur cell diaphragm is placed between sulphur positive plate and lithium cathode sheet, core is assembled into, is put into lithium-sulfur cell shell
In, electrolyte is injected, sealing obtains lithium-sulfur cell.
The preparation method of lithium-sulfur cell provided by the invention, it is simple for process, it is easy to operate, it is big raw that industrialization can be suitable for
Production.
Technical solution provided by the invention is further described with reference to embodiment and comparative example.
Embodiment 1
A kind of lithium-sulfur cell diaphragm is present embodiments provided, the polypropylene porous film which is 25 μm by thickness is as branch
Support film and thickness are that 5 μm of nitrating carbon adsorption-conductive coatings are combined, and preparation method includes the following steps：
By nitrating porous carbon-carbon nanotube-graphene and Vingon adhesive according to mass ratio 9:1 is added N- methyl
Slurry is made in pyrrolidones, then which is coated in the surface of support membrane, it is compound to obtain lithium-sulfur cell diaphragm after dry
Diaphragm.
Wherein, nitrating porous carbon-carbon nanotube-graphene is prepared in accordance with the following steps：
By amido modification nanoporous carbon, carboxylated single-layer graphene and carboxylated double-walled carbon nano-tube in mass ratio 1:2:
1 is scattered in toluene solution, and DCC activation is added, and is heated to 100 DEG C of reflux 48h and obtains nitrating porous carbon-carbon nanotube-stone
Black alkene.
Wherein, amido modification nanoporous carbon is prepared in accordance with the following steps：
(1) acetylene black will be used as nanoporous carbon, by nanoporous carbon and H2SO4With HNO3Mixed solution (98%
H2SO4:68%HNO3=3:1, volume ratio) in mass ratio 1:200-300 is mixed, and is flowed back under the conditions of 30-40 DEG C of supersonic oscillations
4h is reacted, is cooled to room temperature, after deionized water dilution is added, filters and is cleaned to filtrate pH=7 with deionized water；
(2) step (1) product is placed in H2SO4With H2O2Mixed solution (98%H2SO4:30%H2O2=4:1 (volume
Than)) in, it flows back at 70 DEG C after 0.5h, filters and cleaned to filtrate pH and be in neutrality with deionized water, product, which is placed in vacuum, to be dried
It is dried in vacuo in case for 24 hours, obtains carboxylated nanoporous carbon；
(3) step (2) product is placed in a reaction flask, excess thionyl chloride and organic solvent is added, is stirred at 70 DEG C
Reflux for 24 hours, is filtered, washed, dries and obtain the nanoporous carbon materials of chloride.
(4) it takes step (3) product to be placed in a reaction flask, a certain amount of ethylenediamine is added, flow back and stir in 75 DEG C of organic solvents
Mix 48h, be filtered, washed, dry obtain amido modification porous carbon.
Embodiment 2
A kind of lithium-sulfur cell diaphragm is present embodiments provided, the polyethylene porous membrane which is 25 μm by thickness is as branch
Support film and thickness are that 10 μm of nitrating carbon adsorption-conductive coatings are combined, and preparation method is same as Example 1, difference
It is, nitrating porous carbon-carbon nanotube-graphene is by amido modification nanoporous carbon, carboxylated bilayer graphene and carboxylated
Single-walled carbon nanotube is according to quality 1:2:1 is made, and wherein amido modification nanoporous carbon uses Ketjen black and acetylene black (mass ratio
1:1) it is used as nanoporous carbon materials source.
Embodiment 3
Present embodiments provide a kind of lithium-sulfur cell diaphragm, the dual coating Vingon which is 25 μm by thickness
Polyethylene porous membrane as support membrane and thickness be that 10 μm of nitrating carbon adsorption-conductive coatings are combined, preparation method packet
Include following steps：By nitrating porous carbon-carbon nanotube-graphene, butadiene-styrene rubber and acrylonitrile according to mass ratio 94：3：3 are added
(the mass ratio 3 of deionized water and isopropanol in deionized water and isopropyl alcohol mixture:1) it is mixed and made into slurry in, then will
The slurry is coated in the surface of support membrane, and lithium-sulfur cell diaphragm is obtained after dry.
Wherein, nitrating porous carbon-carbon nanotube-graphene is by amido modification nanoporous carbon, carboxylated bilayer graphene
With carboxylated double-walled carbon nano-tube according to mass ratio be 1:2:1 is made, and preparation method and the nitrating that embodiment 1 provides are porous
The preparation method of carbon-to-carbon nanotube-graphene alkene is identical, the difference is that, amido is modified nanoporous carbon and is made using Ketjen black
For nanoporous carbon materials source.
Embodiment 4
Present embodiments provide a kind of lithium-sulfur cell diaphragm, the dual coating Vingon which is 25 μm by thickness
Polyethylene porous membrane as support membrane and thickness be that 10 μm of nitrating carbon adsorption-conductive coatings are combined, preparation method packet
Include following steps：By nitrating porous carbon-carbon nanotube-graphene, butadiene-styrene rubber and carboxymethyl cellulose according to mass ratio 92：5：
It is mixed and made into slurry in 3 addition deionized waters, then which is coated in the surface of support membrane, lithium sulphur electricity is obtained after dry
Pond diaphragm.
Wherein, nitrating porous carbon-carbon nanotube-graphene is by amido modification nanoporous carbon, three layer graphene of carboxylated
With four wall carbon nano tube of carboxylated according to mass ratio 1:2:1 is made, the nitrating porous carbon-that preparation method is provided with embodiment 1
The preparation method of carbon nanotube-graphene is identical, the difference is that, amido modifies nanoporous carbon and uses mesoporous carbon (CMK-
3) it is used as nanoporous carbon materials source.
Embodiment 5
Present embodiments provide a kind of lithium-sulfur cell diaphragm, the difference of diaphragm provided in this embodiment and embodiment 3
It is, nitrating porous carbon-carbon nanotube-graphene is by amido modification nanoporous carbon, carboxylated bilayer graphene and carboxylated
Double-walled carbon nano-tube is 1 according to mass ratio:3:1 is made.
Embodiment 6
Present embodiments provide a kind of lithium-sulfur cell diaphragm, the difference of diaphragm provided in this embodiment and embodiment 3
It is, nitrating porous carbon-carbon nanotube-graphene is by amido modification nanoporous carbon, carboxylated bilayer graphene and carboxylated
Double-walled carbon nano-tube is 2 according to mass ratio:3:2 are made.
Embodiment 7
Present embodiments provide a kind of lithium-sulfur cell diaphragm, the difference of diaphragm provided in this embodiment and embodiment 3
It is, nitrating porous carbon-carbon nanotube-graphene is by amido modification nanoporous carbon, carboxylated bilayer graphene and carboxylated
Double-walled carbon nano-tube is 6 according to mass ratio:1:4 are made.
Embodiment 8
Present embodiments provide a kind of lithium-sulfur cell diaphragm, the difference of diaphragm provided in this embodiment and embodiment 3
It is, nitrating carbon adsorption-conductive coating is 50 by mass ratio:25:25 nitrating porous carbon-carbon nanotube-graphene, butylbenzene rubber
Glue and acrylonitrile are made.
Comparative example 1
This comparative example provides a kind of lithium-sulfur cell diaphragm, which is 25 μm of polyethylene porous membranes as support by thickness
The acetylene black coating that film and thickness are 10 μm is combined, and preparation method includes the following steps：By acetylene black and vinylidene chloride
According to mass ratio 9:It is mixed and made into slurry in 1 addition N-Methyl pyrrolidone, then which is coated in the surface of support membrane,
Lithium-sulfur cell diaphragm is obtained after drying.
Comparative example 2
This comparative example provides a kind of lithium-sulfur cell diaphragm, which is 25 μm of polyethylene porous membranes as support by thickness
The graphite ene coatings that film and thickness are 10 μm are combined, and preparation method includes the following steps：By single-layer graphene and inclined chlorine
Ethylene is according to mass ratio 9:1 plus N-Methyl pyrrolidone in be mixed and made into slurry, then by the slurry be coated in support membrane table
Face obtains lithium-sulfur cell diaphragm after dry.
Comparative example 3
This comparative example provides a kind of lithium-sulfur cell diaphragm, which is 25 μm of polyethylene porous membranes as support by thickness
The carbon nanotube coating that film and thickness are 10 μm is combined, and preparation method includes the following steps：By double-walled carbon nano-tube with
Vinylidene chloride is according to mass ratio 9:1 plus N-Methyl pyrrolidone in be mixed and made into slurry, then by the slurry be coated in support membrane
Surface, obtain lithium-sulfur cell diaphragm after dry.
Comparative example 4
This comparative example provides a kind of lithium-sulfur cell diaphragm, which is commercialized lithium-sulfur cell on the market
Celgard2500 diaphragms.
Embodiment 9
Embodiment 9 provides a kind of lithium sulphur soft-package battery, including sulphur positive plate, lithium an- ode and embodiment 1 provide
Lithium-sulfur cell diaphragm is placed between sulphur positive plate and lithium an- ode, is assembled into core by lithium-sulfur cell diaphragm, is put into lithium sulphur electricity
In the shell of pond, electrolyte is injected, sealing obtains lithium-sulfur cell, wherein electrolyte is by 1mol/L bis trifluoromethyl sulfonic acid Asia amide
(the two volume ratio is 1 to the mixed solution of lithium, 0.1mol/L lithium nitrates and dioxolanes (DOL) and glycol dimethyl ether (DME):
1) it is made；Sulphur positive plate is coated on aluminium foil by positive electrode and is prepared, and positive electrode is by bright sulfur, acetylene black and gathers inclined chloroethene
Alkene is according to mass ratio 8:1:1 mixes.
Embodiment 10
Embodiment 10 provides a kind of lithium sulphur soft-package battery, and difference lies in using embodiment with embodiment 9 for the present embodiment
The 2 lithium-sulfur cell diaphragms provided are as diaphragm.
Embodiment 11
Embodiment 11 provides a kind of lithium sulphur soft-package battery, and difference lies in using embodiment with embodiment 9 for the present embodiment
The 3 lithium-sulfur cell diaphragms provided are as diaphragm.
Embodiment 12
Embodiment 12 provides a kind of lithium sulphur soft-package battery, and difference lies in using embodiment with embodiment 9 for the present embodiment
The 4 lithium-sulfur cell diaphragms provided are as diaphragm.
Embodiment 13
Embodiment 13 provides a kind of lithium sulphur soft-package battery, and difference lies in using embodiment with embodiment 9 for the present embodiment
The 5 lithium-sulfur cell diaphragms provided are as diaphragm.
Embodiment 14
Embodiment 14 provides a kind of lithium sulphur soft-package battery, and difference lies in using embodiment with embodiment 9 for the present embodiment
The 6 lithium-sulfur cell diaphragms provided are as diaphragm.
Embodiment 15
Embodiment 15 provides a kind of lithium sulphur soft-package battery, and difference lies in using embodiment with embodiment 9 for the present embodiment
The 7 lithium-sulfur cell diaphragms provided are as diaphragm.
Embodiment 16
Embodiment 16 provides a kind of lithium sulphur soft-package battery, and difference lies in using embodiment with embodiment 9 for the present embodiment
The 8 lithium-sulfur cell diaphragms provided are as diaphragm.
Comparative example 5
Comparative example 5 provides a kind of lithium sulphur soft-package battery, and difference lies in using comparative example 1 with embodiment 9 for this comparative example
The lithium-sulfur cell diaphragm of offer is as diaphragm.
Comparative example 6
Comparative example 6 provides a kind of lithium sulphur soft-package battery, and difference lies in using comparative example 2 with embodiment 9 for this comparative example
The lithium-sulfur cell diaphragm of offer is as diaphragm.
Comparative example 7
Comparative example 7 provides a kind of lithium sulphur soft-package battery, and difference lies in using comparative example 3 with embodiment 9 for this comparative example
The lithium-sulfur cell diaphragm of offer is as diaphragm.
Comparative example 8
Comparative example 8 provides a kind of lithium sulphur soft-package battery, and difference lies in using comparative example 4 with embodiment 9 for this comparative example
The lithium-sulfur cell diaphragm of offer is as diaphragm.
Test example 1
Nitrating porous carbon-carbon nanotube-graphene prepared by embodiment 3 is scanned electron microscope analysis, Fig. 1 is the present invention
The scanning electron microscope (SEM) photograph for nitrating porous carbon-carbon nanotube-graphene that embodiment 3 provides, as shown in Figure 1, the porous carbon-to-carbon of nitrating is received
In mitron-graphene, nanoporous carbon is dispersed between carbon nanotube and graphene, close with carbon nanotube and graphene
Crosslinking, without apparent agglomeration.
Test example 2
The lithium sulphur soft-package battery that embodiment 11 provides and the lithium sulphur soft-package battery that comparative example 8 provides are subjected to charge-discharge performance
Test, Fig. 2 are that the lithium sulphur soft-package battery that the embodiment of the present invention 11 provides and the lithium sulphur soft-package battery charge and discharge that comparative example 8 provides are bent
Line；Figure it is seen that the specific discharge capacity for the lithium sulphur soft-package battery that comparative example 8 provides is substantially less than the offer of embodiment 11
Lithium sulphur soft-package battery, after this illustrates that lithium-sulfur cell provides lithium-sulfur cell diaphragm using the present invention, positive electrode active material utilization is aobvious
It writes and improves, the cross-film diffusion of polysulfide is significantly restrained, and specific discharge capacity significantly improves.
Test example 3
The cycle performance of the lithium sulphur soft-package battery that embodiment 11 provides and the lithium sulphur soft-package battery that comparative example 8 provides is surveyed
Examination, Fig. 3 are the lithium sulphur soft-package battery that the embodiment of the present invention 11 provides and the lithium sulphur soft-package battery cyclic curve that comparative example 8 provides；
Figure it is seen that in identical cycle-index, the discharge capacity for the lithium sulphur soft-package battery that embodiment 11 provides is significantly higher than
The lithium sulphur soft-package battery that comparative example 8 provides, after this illustrates that lithium-sulfur cell provides lithium-sulfur cell diaphragm using the present invention, positive-active
Material utilization significantly improves, and the cross-film diffusion of polysulfide is significantly restrained, and specific discharge capacity and cycle performance significantly carry
It is high.
Test example 4
Electrochemistry of the lithium sulphur soft-package battery that embodiment 9-16 and comparative example 5-8 are provided respectively under 0.5C current densities
Can, test result is as shown in table 1.
1 lithium sulphur soft-package battery electrochemical performance data table of table
The comparison of embodiment 9-16 and comparative example 8 can be seen that lithium sulphur soft-package battery using provided by the invention from table 1
After lithium-sulfur cell diaphragm, initial discharge specific capacity, cycle performance are significantly improved than 2500 diaphragms of commercialized Celgard,
After this illustrates that lithium-sulfur cell provides lithium-sulfur cell diaphragm using the present invention, positive electrode active material utilization significantly improves, vulcanize more
The cross-film diffusion of object is significantly restrained, and the cycle performance of lithium-sulfur cell significantly improves.
It can be seen that from the comparison of embodiment 9-16 and comparative example 5-7 through the porous carbon-to-carbon of compound nitrating on support membrane
Lithium-sulfur cell diaphragm ratio is on support membrane made of nitrating carbon adsorption-conductive coating made of nanotube-graphene alkene and adhesive
Composite carbon nanometer tube coating and the composite graphite ene coatings system on support membrane on diaphragm, support membrane made of compound acetylene black coating
At diaphragm can more effectively improve the initial discharge specific capacity and cycle performance of battery.
It can be seen that using nanoporous carbon, graphene and carbon nanometer by the comparison of embodiment 9-14 and embodiment 15
The mass ratio of pipe is (1-2)：(2-3)：Lithium sulphur diaphragm made of nitrating porous carbon-carbon nanotube-graphene made of (1-2) is more
The initial discharge specific capacity and cycle performance of battery can be improved.
Nitrating porous carbon-carbon nanotube-graphene is can be seen that by the comparison of embodiment 9-14 and embodiment 16 and is glued
The mass ratio of mixture is (80-99)：When (1-20), manufactured lithium sulphur diaphragm can more improve battery initial discharge specific capacity and
Cycle performance.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of lithium-sulfur cell diaphragm, which is characterized in that including support membrane, nitrating carbon adsorption-is compounded on the support membrane and is led
Electrocoat.
2. lithium-sulfur cell diaphragm according to claim 1, which is characterized in that the nitrating carbon adsorption-conductive coating is main
It is made of nitrating porous carbon-carbon nanotube-graphene and adhesive；
Preferably, the mass ratio of the nitrating porous carbon-carbon nanotube-graphene and adhesive is (80-99)：(1-20).
3. lithium-sulfur cell diaphragm according to claim 2, which is characterized in that the nitrating porous carbon-carbon nanotube-graphite
Alkene is mainly made of nanoporous carbon, graphene and carbon nanotube；
Preferably, the mass ratio of the nanoporous carbon, graphene and carbon nanotube is (1-2)：(2-3)：(1-2).
4. lithium-sulfur cell diaphragm according to claim 3, which is characterized in that the nitrating porous carbon-carbon nanotube-graphite
Alkene is mainly made of amido modification nanoporous carbon, carboxylated graphene and carboxylic carbon nano-tube；
Preferably, the preparation method of the nitrating porous carbon-carbon nanotube-graphene includes the following steps：
Amido modification nanoporous carbon, carboxylated graphene and carboxylic carbon nano-tube are mixed, condensation reaction is carried out, is mixed
Nitrogen porous carbon-carbon nanotube-graphene；
Preferably, condensation reaction carries out under activator effect；
Preferably, the activator is selected from n-hydroxysuccinimide or 1- ethyls -3- (3- dimethyl aminopropyls)-carbonizations two
Imines or N, at least one of N ' dicyclohexylcarbodiimides.
5. lithium-sulfur cell diaphragm according to claim 3, which is characterized in that the preparation of the amido modification nanoporous carbon
Method includes the following steps：
(a) by nanoporous carbon carboxylated, carboxylated nanoporous carbon is obtained；
(b) by carboxylated nanoporous phosphinylidyne chlorination, chloride nanoporous carbon is obtained；
(c) chloride nanoporous carbon is subjected to amido modification, obtains amido modification nanoporous carbon；
Preferably, in step (a), first nanoporous carbon and the mixed solution of sulfuric acid and nitric acid are flowed back, then will reflux
Nanoporous carbon afterwards is reacted with the mixed solution of sulfuric acid and hydrogen peroxide, and reflux obtains carboxylated nanoporous carbon；
Preferably, in step (b), carboxylated nanoporous carbon and thionyl chloride is dissolved in organic solvent, reacted,
Reflux obtains chloride nanoporous carbon；
Preferably, in step (c), chloride nanoporous carbon and ethylenediamine is dissolved in organic solvent, is reacted, is obtained
Nanoporous carbon is modified to amido.
6. lithium-sulfur cell diaphragm according to claim 3, which is characterized in that the nanoporous carbon is selected from Ketjen black, second
At least one of acetylene black, mesoporous carbon or carbon molecular sieve；
Preferably, the carboxylated graphene is selected from single layer carboxylated graphene and/or multilayer carboxylated graphene；
Preferably, the carboxylic carbon nano-tube is selected from single wall carboxylic carbon nano-tube and/or multi wall carboxylic carbon nano-tube.
7. according to claim 1-6 any one of them lithium-sulfur cell diaphragms, which is characterized in that the support membrane is selected from polyethylene
Perforated membrane, polypropylene porous film, polyethylene/polypropylene composite diaphragm, dual coating adhesive polyethylene perforated membrane, dual coating
At least one of adhesive polypropylene porous film, polyimide diaphragm or aramid fiber diaphragm；
Preferably, the thickness of the support membrane is 16-25 μm；
Preferably, the thickness of the nitrating carbon adsorption-conductive coating is 4-10 μm.
8. according to the preparation method of claim 1-7 any one of them lithium-sulfur cell diaphragms, which is characterized in that including walking as follows
Suddenly：
Nitrating carbon adsorption-conductive coating is coated on support membrane, after dry, obtains lithium-sulfur cell diaphragm；
Preferably, nitrating porous carbon-carbon nanotube-graphene and adhesive are dissolved in solvent, slurry is made, slurry is coated
In on support membrane, after dry, lithium-sulfur cell diaphragm is obtained.
9. a kind of lithium-sulfur cell, which is characterized in that including claim 1-7 any one of them lithium-sulfur cells diaphragm, sulphur anode
Piece and lithium cathode sheet；
Preferably, the sulphur positive plate is mainly coated on plus plate current-collecting body by positive electrode and is prepared；
Preferably, the positive electrode includes positive electrode active materials, conductive agent and adhesive；
Preferably, the positive electrode active materials are sulphur carbon complex and/or sulphur；
Preferably, the lithium cathode sheet is selected from lithium electrode, Li-C Electrode, copper lithium combination electrode, lithium alloy electrode or modified cladding
At least one of lithium electrode.
10. a kind of preparation method of lithium-sulfur cell, which is characterized in that include the following steps：
Lithium-sulfur cell diaphragm is placed between sulphur positive plate and lithium cathode sheet, core is assembled into, is put into lithium-sulfur cell shell, is noted
Enter electrolyte, seals, obtain lithium-sulfur cell.
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| CN112010282A (en) * | 2020-08-20 | 2020-12-01 | 山东科技大学 | Sulfur-carbon composite cathode material and preparation method and application thereof |
| KR20220047070A (en) * | 2020-10-08 | 2022-04-15 | 고려대학교 산학협력단 | Lithium-sulfur battery cathode using fabric material, lithium-sulfur battery including the same, and manufacturing method thereof |
| KR102448549B1 (en) | 2020-10-08 | 2022-09-28 | 고려대학교 산학협력단 | Lithium-sulfur battery cathode using fabric material, lithium-sulfur battery including the same, and manufacturing method thereof |
| CN113571841A (en) * | 2021-07-22 | 2021-10-29 | 哈尔滨师范大学 | Lithium-sulfur battery composite diaphragm and preparation method thereof |
| CN113571841B (en) * | 2021-07-22 | 2023-08-01 | 哈尔滨师范大学 | Lithium-sulfur battery composite diaphragm and preparation method thereof |
| KR20230017381A (en) * | 2021-07-27 | 2023-02-06 | 성균관대학교산학협력단 | Separator for a lithium sulfur battery coated with porous composite, manufacturing method thereof, lithium sulfur battery comprising the same |
| CN113725558A (en) * | 2021-07-29 | 2021-11-30 | 长沙矿冶研究院有限责任公司 | Modified diaphragm of lithium-sulfur battery and preparation method thereof |
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