CN110350130A - The asymmetric diaphragm of metal/sulfur rechargeable battery - Google Patents

The asymmetric diaphragm of metal/sulfur rechargeable battery Download PDF

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Publication number
CN110350130A
CN110350130A CN201910648327.2A CN201910648327A CN110350130A CN 110350130 A CN110350130 A CN 110350130A CN 201910648327 A CN201910648327 A CN 201910648327A CN 110350130 A CN110350130 A CN 110350130A
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coating
metal
diaphragm
rechargeable battery
sulfur rechargeable
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韦伟峰
马骋
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Central South University
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Central South University
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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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/604—Polymers containing aliphatic main chain polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of asymmetric diaphragms of metal/sulfur rechargeable battery, it is covered with different function coating respectively on the two sides of porous support materials, sulphur side of the positive electrode coating is the compound for including conductive carbon material, ion conductor polymer and binder containing polar functional group, and another side metal negative electrode side coating is the compound for including inorganic solid electrolyte and binder.The asymmetric diaphragm of functionalization of the invention can significantly inhibit the growth of shuttle and the side reaction of metal negative electrode interface and dendrite of polysulfide, diaphragm is improved to the wetability of electrolyte, mechanical strength, thermostabilization and high temperature dimensional stability, ensure that metal/sulfur rechargeable battery safe and stable operation.

Description

The asymmetric diaphragm of metal/sulfur rechargeable battery
Technical field
The present invention relates to a kind of metal/sulfur rechargeable battery material, in particular to a kind of metal/sulfur rechargeable battery is with non-right Claim diaphragm.
Background technique
Metal/sulfur rechargeable battery has high energy density, low in cost, rich reserves and advantages of environment protection, quilt It is considered as current most potential high specific energy secondary cell system of new generation.However, its root problem is charge and discharge process Middle polysulfide is soluble to shuttle, uneven metal deposit induces dendritic growth and low-flash, low ignition point organic electrolysis liquid band The security risk come.Based on the above issues, domestic and international researchers are existed based on sulphur anode and metal cathode structure modification etc. Metal/sulfur rechargeable battery chemical property is improved to a certain extent.And as metal/sulfur rechargeable battery component part, Diaphragm plays isolation positive and negative electrode in the battery and adsorbs electrolyte and pass freely through the ion in electrolyte and electronic isolation Effect.The single commercial diaphragm of structure is difficult to inhibit the shuttle of polysulfide and dendritic growth at present, still needs to break through serial key Science and technology problem.Researcher's trial constructs a variety of nano materials, and (such as carbon material, laminated metal compound, metal are organic Frame etc.) modification composite diaphragm, alleviate to a certain extent polysulfide shuttle and dendrite pierce through diaphragm the problem of, however Current diaphragm cannot effectively solve the problems, such as polysulfide shuttle and dendritic growth simultaneously.
Summary of the invention
The present invention is intended to provide a kind of can effectively solve the problems, such as metal/sulphur two that polysulfide shuttles with dendritic growth simultaneously The asymmetric diaphragm of primary cell, the present invention is realized by following scheme.
Be covered with different coating respectively on the two sides of porous support materials, sulphur side of the positive electrode coating be include conductive carbon material, contain The ion conductor polymer of polar functional group and the compound of binder, another side metal negative electrode side coating include inoganic solids electricity Solve the compound of matter and binder.
Porous support materials can be one of porous support materials for being used for diaphragm in the prior art or a variety of, such as poly- Ethylene every, polypropylene, polypropylene-polyethylene-polypropylene, Kynoar, poly- (vinylidene-hexafluoroethylene), polytetrafluoroethyl-ne Alkene, polyacrylonitrile, polyimides, polysulfones, polycarbonate, polyurethane, cellulose, non-woven fabrics, glass fibre.
Conductive carbon material can be such as porous (nano-pore, micron openings, mesoporous, multistage with one or more in existing carbon material Hole) carbon material, carbonaceous mesophase spherules, carbon nanosheet, carbon nanotube, carbon nano-fiber, carbon quantum dot, graphene, fullerene, carbon Aeroge, polythiophene, polypyrrole, poly-dopamine etc., and by one or more hetero atoms (nitrogen, oxygen, sulphur, phosphorus, boron etc.) or The above-mentioned carbon material etc. of magnesium-yttrium-transition metal atom (iron, cobalt, manganese, nickel etc.) doping.
Ion conductor polymer containing polar functional group can be one of existing following polymer or a variety of, such as polyoxy Ethylene, polycarbonate, polyacrylonitrile, polyphosphate, polyvinyl alcohol, polysiloxanes, poly- boroxane, polyphosphazene and above-mentioned poly- Close the derivative etc. of object.
Inorganic solid electrolyte can be the existing inorganic based solid electrolyte for being used as secondary cell, such as stratiform Li3N, Ca-Ti ore type, Fast ion conductor (NASICON), lithium fast-ionic conductor (LISICON), carbuncle type (GARNET), LiPON type, oxide and sulfide type etc. are one or more, and the above-mentioned electricity by metallic atom (Al, Fe, Ti etc.) doping Solve material.
Binder can be for for one of binder compound in secondary cell positive and negative electrode or a variety of, such as poly- second Alkene pyrrole network alkanone, Kynoar, poly- (vinylidene-hexafluoroethylene), polyoxyethylene, polyvinyl alcohol, polyacrylonitrile, polypropylene Acid, sodium alginate, cyclodextrin, styrene-butadiene latex, polytetrafluoroethylene (PTFE), polyethyleneimine, polyimides, gathers sodium carboxymethylcellulose Etherimide.
Preferably, when sulphur side of the positive electrode coating is with a thickness of 50nm~50 μm, metal negative electrode side coating with a thickness of 50nm~ At 50 μm, diaphragm is more suitable for being applied in metal/sulfur rechargeable battery.
Preferably, in the compound of sulphur side of the positive electrode coating, conductive carbon material mass fraction is 5~90%, and ion conductor is poly- Closing amount of substance score is 5~90%, remaining is binder；In the coating composite of another side metal negative electrode side, inorganic solid electrolyte Matter mass fraction is 2~98%, remaining is binder.Such asymmetric coating composition design so that the performance of diaphragm more preferably.
The preparation method of above-mentioned diaphragm is, will need respectively the composition of the compound coated in porous support materials two sides at After being distributed into slurry, using one kind of the various methods for the existing prepares coating such as being coated with, spray, filter out, in porous support materials Two sides be covered with corresponding coating respectively and be made again through dry, when preparation, can be wherein one side completion and cover after slurry-drying again The repetitive operation for carrying out another side is also possible to two sides and covers the mode that property is dried again after slurry.
Compared with prior art, the invention has the following advantages that
(1) diaphragm sulphur side of the positive electrode coating is ion/electron mixed conductor, is turned by physics confinement and chemisorption and charge It moves and transmits synergistic effect with ion, accelerate electrochemical reversible reaction of the polysulfide in coating, significantly suppress more vulcanizations The shuttle of object and the utilization rate and stability for promoting active material.
(2) diaphragm metal negative electrode side coating is ion conductor coating, can improve the intrinsic cellular structure of diaphragm, nano junction The aperture of structure and quick ion transport behavior realize the uniform correction of ion deposition behavior, it is suppressed that metal negative electrode interface pair The growth of reaction and dendrite.
(3) functionalization diaphragm of the invention not only inhibits polysulfide shuttle and dendritic growth, also improves it to electricity Wetability, mechanical strength, thermostabilization and the high temperature dimensional stability for solving liquid ensure that metal/sulfur rechargeable battery safety and stability fortune Row.
(4) diaphragm of the present invention has unsymmetric structure, and design operation method thereof is simple, and raw material sources are extensive, practical, It is easy to large scale preparation and technical transform.
Detailed description of the invention
1 lithium of Fig. 1 embodiment/sulfur rechargeable battery diaphragm scanning electron microscope (SEM) photograph
Dismantling obtains lithium metal surface scan microscopic comparison after Fig. 2 circulating battery
Specific embodiment
Embodiment 1
By superconduction carbon black, ion conductor polymer polyethylene alcohol ammonium phosphate and binder polyvinylpyrrolidone according to quality After 2:2:1 mixing, water/alcohol mixed solvent is added, a kind of coating paste is obtained after being sufficiently stirred, is then coated using scraper Method is coated uniformly on the one side of polypropylene porous support materials, is dried to obtain the diaphragm with single side coating；Later by nothing After machine solid electrolyte-phosphoric acid germanium aluminium lithium (LAGP) and binder Kynoar (PVDF) are mixed according to mass ratio 9:1, it is added Suitable dimethyl sulfoxide solvent obtains another coating paste after being sufficiently stirred, equally using scraper cladding process that it is uniform The another side with single side coated separator coated in above-mentioned preparation, then vacuum dried obtain can be used for lithium/sulfur rechargeable battery Asymmetric diaphragm.
This using above method preparation can be used for the asymmetric diaphragm of lithium/sulfur rechargeable battery, in the porous branch of polypropylene Timbering material close to sulphur side of the positive electrode coating be formed by superconduction carbon black, ammonium alcohol polyvinyl phosphate and polyvinylpyrrolidone it is compound Object, wherein superconduction carbon black, ammonium alcohol polyvinyl phosphate account for the 40% and 40% of coating gross mass respectively, remaining is binder polyethylene Pyrrolidones is the compound formed by LAGP and PVDF close to lithium an- ode side coating, and wherein LAGP and PVDF are accounted for respectively The 90% of coating gross mass and 10%；Diaphragm scanning electron microscope (SEM) photograph as shown in Figure 1 finds that the thickness of above-mentioned two finishing coat is 5 μ m。
Fig. 2 is lithium/sulfur rechargeable battery that the asymmetric diaphragm assembly of existing diaphragm and above method preparation is respectively adopted, It under 1C multiplying power after 200 circle of circulation, then disassembles to obtain the scanning electron microscope (SEM) photograph on lithium metal surface, figure a is corresponding using existing diaphragm The scanning electron microscope (SEM) photograph on lithium metal surface after circulating battery, figure b are the battery of the asymmetric diaphragm assembling prepared using the above method The scanning electron microscope (SEM) photograph on lithium metal surface after circulation, the lithium metal after it can be seen that the corresponding circulating battery of the existing diaphragm of use in figure a There is many crackles and dendrite in surface, and can be seen that from figure b, using the battery of the asymmetric diaphragm assembling of above method preparation Lithium metal surface still smoother after circulation shows that this asymmetric diaphragm effectively inhibits forming core and the growth of Li dendrite.
The asymmetric diaphragm that existing diaphragm and above method preparation is respectively adopted carries out inhibiting polysulfide shuttle experiment, dress The middle certain density polysulfide solution of the inside bottle subassembly is set, rufous is shown as, the big bottle in outside then assembles colourless molten Agent.Test result shows that existing diaphragm is difficult to that polysulfide is prevented to be diffused into big bottle from ampoule shuttle, molten in big bottle Agent color gradually starts to deepen, and uses the asymmetric diaphragm of above method preparation can be more by physical barrier and chemisorption Sulfide inhibits it to shuttle to the big bottle in outside in turn, and solvent remains colourless in big bottle.
Embodiment 2
By nitrogen-doped carbon nanometer pipe, ion conductor polymer poly ethylene oxide and binder sodium carboxymethylcellulose according to quality After 2:2:1 mixing, the mixed solvent of ethyl alcohol and water is added, a kind of coating paste is obtained after being sufficiently stirred, then uses scraper Cladding process is coated uniformly on the one side of glass fibre porous support materials；Later by the inorganic solid electrolyte of sulfide type N3PS4After being mixed with binder polyoxyethylene according to mass ratio 1:49, suitable N-Methyl pyrrolidone solvent is added, sufficiently stirs Another coating paste is obtained after mixing, and the above-mentioned porous branch for having been coated with a finishing coat is coated uniformly on using scraper cladding process The another side of timbering material, then vacuum dried obtain can be used for the asymmetric diaphragm of sodium/sulfur rechargeable battery.
This using above method preparation can be used for the asymmetric diaphragm of sodium/sulphur electricity secondary cell, porous in polypropylene Backing material close to sulphur side of the positive electrode coating be formed by nitrogen-doped carbon nanometer pipe, polyoxyethylene and sodium carboxymethylcellulose it is compound Object, wherein nitrogen-doped carbon nanometer pipe, polyoxyethylene account for the 40% and 40% of coating gross mass respectively, remaining is binder, through sweeping Retouch Electronic Speculum detection, the coating with a thickness of 1 μm；It is the inorganic solid electrolyte of sulfide type close to metallic sodium negative side coating Na3PS4The compound formed with polyoxyethylene, wherein the inorganic solid electrolyte Na of sulfide type3PS4Distinguish with polyoxyethylene Account for the 2% and 98% of coating gross mass, detected through scanning electron microscope, the coating with a thickness of being 5 μm.
Embodiment 3
The graphene, ion conductor polymer poly siloxanes and binder polyimides of nitrogen will be adulterated according to mass ratio 1: After 18:1 mixing, dimethyl sulfoxide solvent is added, a kind of coating paste is obtained after being sufficiently stirred, it is then using spray coating method that it is equal The even one side coated in cellulose porous support materials；Later by the inorganic solid electrolyte lithium lanthanum zirconium oxygen LLZTO of oxide type After mixing with binder polyvinyl alcohol according to mass ratio 9:1, suitable dimethyl sulfoxide solvent is added, is obtained after being sufficiently stirred another Its even application is overlayed on the another of the above-mentioned porous support materials for having formed a finishing coat using spray coating method by a kind of coating paste Face, then vacuum dried obtain can be used for the asymmetric diaphragm of lithium/sulfur rechargeable battery.
This using above method preparation can be used for the asymmetric diaphragm of lithium/sulphur electricity secondary cell, porous in cellulose Backing material is the compound formed by graphene, polysiloxanes and polyimides close to sulphur side of the positive electrode coating, wherein graphene, Polysiloxanes accounts for the 5% and 90% of coating gross mass respectively, coating with a thickness of 500nm；It is close to lithium an- ode side coating Compound that the inorganic solid electrolyte lithium lanthanum zirconium oxygen (LLZTO) and polyvinyl alcohol of oxide type are formed, wherein sulfide type Inorganic solid electrolyte lithium lanthanum zirconium oxygen (LLZTO) and polyvinyl alcohol account for the 90% and 10% of coating gross mass respectively, the coating With a thickness of 1 μm.
Embodiment 4
The carbon nanosheet, ion conductor polymer poly acrylonitrile and binder Kynoar of nitrogen will be adulterated according to mass ratio 18:1:1 mixing after, be added dimethyl sulfoxide solvent, a kind of coating paste is obtained after being sufficiently stirred, then using spray coating method by its It is coated uniformly on the one side of polytetrafluoroethylstephanoporate stephanoporate backing material；Later by the inorganic solid electrolyte sodium zirconium silicon of NASICON type Phosphorus oxygen (Na3Zr2Si2PO12) and binder polyoxyethylene according to mass ratio 49:1 mixing after, suitable dimethyl sulfoxide solvent is added, Another coating paste is obtained after being sufficiently stirred, its even application is overlayed on using spray coating method and above-mentioned has formed the more of a finishing coat The another side of hole backing material, then vacuum dried obtain can be used for the asymmetric diaphragm of sodium/sulfur rechargeable battery.
This using above method preparation can be used for the asymmetric diaphragm of sodium/sulphur electricity secondary cell, in polyethylene porous Backing material is that hear that your nanometer sheet, polyacrylonitrile and Kynoar are formed by N doping compound close to sulphur side of the positive electrode coating Object, wherein carbon nanosheet, polysiloxanes account for the 90% and 5% of coating gross mass respectively, coating with a thickness of 500nm；Close to sodium Metal negative electrode side coating is the inorganic solid electrolyte Na of NASICON type3Zr2Si2PO12The compound formed with polyoxyethylene, The inorganic solid electrolyte Na of middle sulfide type3Zr2Si2PO12Account for the 98% and 2% of coating gross mass respectively with polyoxyethylene, it should Coating with a thickness of 1 μm.

Claims (4)

1. a kind of asymmetric diaphragm of metal/sulfur rechargeable battery, it is characterised in that: be covered with respectively on the two sides of porous support materials Different coating is on one side sulphur side of the positive electrode coating, ion conductor polymer and bonding including conductive carbon material, containing polar functional group The compound of agent；Another side is metal negative electrode side coating, the compound including inorganic solid electrolyte and binder.
2. the asymmetric diaphragm of metal/sulfur rechargeable battery as described in claim 1, it is characterised in that: the sulphur side of the positive electrode applies Layer with a thickness of 50nm~50 μm, metal negative electrode side coating with a thickness of 50nm~50 μm.
3. the asymmetric diaphragm of metal/sulfur rechargeable battery as claimed in claim 1 or 2, it is characterised in that: the sulphur side of the positive electrode In the compound of coating, conductive carbon material mass fraction is 5~90%, and ion conductor polymer quality score is 5~90%, Remaining is binder.
4. the asymmetric diaphragm of metal/sulfur rechargeable battery as claimed in claim 1 or 2, it is characterised in that: the metal negative electrode In the coating composite of side, inorganic solid electrolyte mass fraction is 2~98%, remaining is binder.
CN201910648327.2A 2019-07-18 2019-07-18 The asymmetric diaphragm of metal/sulfur rechargeable battery Pending CN110350130A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111416090A (en) * 2020-03-10 2020-07-14 上海电力大学 Perovskite oxide modified diaphragm material for lithium-sulfur battery and lithium-sulfur battery
CN112490585A (en) * 2020-11-27 2021-03-12 南京林业大学 Ceramic diaphragm for lithium metal battery and preparation method thereof
CN112820867A (en) * 2021-02-18 2021-05-18 南通国轩新能源科技有限公司 Preparation method of Zn-based MOF electrode material coated ternary cathode material

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CN105489815A (en) * 2016-01-15 2016-04-13 中南大学 Interlayer used for all-solid-state lithium sulfur battery and all-solid-state lithium sulfur battery
CN105845965A (en) * 2016-06-03 2016-08-10 宁波莲华环保科技股份有限公司 Ionic conductive polymer diaphragm for lithium-sulphur battery, and preparation method and application thereof
CN107204414A (en) * 2016-03-18 2017-09-26 东北师范大学 It is a kind of that the method that barrier film prepares high-performance lithium-sulfur cell is modified based on rich nitrogen molecular
CN107665966A (en) * 2016-07-27 2018-02-06 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell
CN107925042A (en) * 2016-01-28 2018-04-17 株式会社Lg化学 Lithium-sulfur cell membrane, its manufacture method with the composite coating comprising poly-dopamine and include its lithium-sulfur cell
CN109891652A (en) * 2016-11-21 2019-06-14 株式会社Lg化学 Lithium-sulfur cell

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105489815A (en) * 2016-01-15 2016-04-13 中南大学 Interlayer used for all-solid-state lithium sulfur battery and all-solid-state lithium sulfur battery
CN107925042A (en) * 2016-01-28 2018-04-17 株式会社Lg化学 Lithium-sulfur cell membrane, its manufacture method with the composite coating comprising poly-dopamine and include its lithium-sulfur cell
CN107204414A (en) * 2016-03-18 2017-09-26 东北师范大学 It is a kind of that the method that barrier film prepares high-performance lithium-sulfur cell is modified based on rich nitrogen molecular
CN105845965A (en) * 2016-06-03 2016-08-10 宁波莲华环保科技股份有限公司 Ionic conductive polymer diaphragm for lithium-sulphur battery, and preparation method and application thereof
CN107665966A (en) * 2016-07-27 2018-02-06 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell
CN109891652A (en) * 2016-11-21 2019-06-14 株式会社Lg化学 Lithium-sulfur cell

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111416090A (en) * 2020-03-10 2020-07-14 上海电力大学 Perovskite oxide modified diaphragm material for lithium-sulfur battery and lithium-sulfur battery
CN112490585A (en) * 2020-11-27 2021-03-12 南京林业大学 Ceramic diaphragm for lithium metal battery and preparation method thereof
CN112820867A (en) * 2021-02-18 2021-05-18 南通国轩新能源科技有限公司 Preparation method of Zn-based MOF electrode material coated ternary cathode material

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