WO2015141952A1 - Batterie au lithium-soufre - Google Patents

Batterie au lithium-soufre Download PDF

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Publication number
WO2015141952A1
WO2015141952A1 PCT/KR2015/001788 KR2015001788W WO2015141952A1 WO 2015141952 A1 WO2015141952 A1 WO 2015141952A1 KR 2015001788 W KR2015001788 W KR 2015001788W WO 2015141952 A1 WO2015141952 A1 WO 2015141952A1
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Prior art keywords
sulfur battery
lithium sulfur
space forming
active material
positive electrode
Prior art date
Application number
PCT/KR2015/001788
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English (en)
Korean (ko)
Inventor
김철환
홍영진
정민영
최경린
김병주
박범우
강성환
이기대
Original Assignee
(주)오렌지파워
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Priority claimed from KR1020140092516A external-priority patent/KR20150109240A/ko
Application filed by (주)오렌지파워 filed Critical (주)오렌지파워
Publication of WO2015141952A1 publication Critical patent/WO2015141952A1/fr

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Definitions

  • the present invention relates to a lithium sulfur battery, and more particularly, to a lithium sulfur battery including a space forming layer formed on one or both surfaces of a positive electrode active material layer to support lithium polysulfide as a discharge product to prevent leakage into an electrolyte.
  • a lithium sulfur battery including a positive electrode.
  • Lithium sulfur batteries are in the spotlight as next generation high capacity battery candidates.
  • Lithium sulfur battery is a galvanic cell using lithium and sulfur-based compounds as an active material and using an electrolyte, and has characteristics of low cost and high energy density (2,600 Wh / kg).
  • the reaction formula at the time of discharge of a lithium sulfur battery is as follows.
  • Lithium sulfur battery uses an oxidation-reduction reaction in which the oxidation rate of S decreases as the SS bond is broken during the reduction reaction (discharge) and the SS bond is formed again as the oxidation number of S increases during the oxidation reaction (charging). Store and generate energy.
  • the dissolution of polysulfide increases the viscosity of the electrolyte, thereby lowering the ionic conductivity.
  • the polysulfide reacts with lithium metal through continuous charge / discharge reaction, when Li 2 S adheres to the surface of the lithium metal, the reaction activity is lowered and dislocation characteristics are decreased. There is a problem that goes bad.
  • elemental sulfur is generally an insulator that is not electrically conductive, and thus an electroconductive material must be used to provide a smooth electrochemical reaction site in order for an electrochemical reaction to occur.
  • sulfur is melted to prevent elution of polysulfide, which is a discharge product, by placing in mesoporous carbon having pores or mesopores of porous activated carbon having a very high surface area, or sulfur and polyacrylonitrile.
  • Efforts have been made to improve the cycle characteristics by producing a composite of sulfur and carbon by reacting at a high temperature, but have not yet achieved satisfactory results.
  • an object of the present invention is to provide a lithium sulfur battery including a positive electrode for a lithium sulfur battery having a new structure capable of preventing elution of polysulfide.
  • the present invention to solve the above problems,
  • a cathode active material layer comprising a cathode active material
  • the cathode active material layer includes a cathode active material, and the cathode active material is selected from the group consisting of elemental sulfur (S 8 ), a sulfur-based compound, and a combination thereof.
  • the space forming layer is a layer capable of providing an empty space for holding the polysulfide in order to prevent the polysulfide generated during charging and discharging of the lithium sulfur battery into the electrolyte. In other words, it serves as a buffer layer.
  • the space forming layer is characterized in that it comprises an average porosity of 10% to 90%.
  • the average porosity can be measured from the following equation.
  • the average porosity means the ratio of the voids in the total volume in the space forming layer, and can be obtained by the above formula using the density of the raw material, the volume of the space forming layer, and the weight of the space forming layer.
  • the space forming layer is characterized by having an electrical conductivity of 10 S / cm or more. Since the space forming layer of the present invention has a high electrical conductivity of 10 S / cm or more, it may serve as a current collector, and therefore, the positive electrode of the present invention does not necessarily need to further include a separate current collector.
  • the space forming layer is characterized in that made of porous carbon.
  • the porous carbon not only provides a space for holding polysulfide through pores, but also forms a conductive network so that the space forming layer is conductive.
  • the space forming layer is carbon black, denka black, ketjen black, acetylene black, activated carbon powder, carbon molecular sieve, carbon nanotube, carbon fiber, activated carbon having fine pores, mesoporous It is characterized by consisting of any one selected from carbon, graphite, carbon paper, carbon felt, carbon cloth and combinations thereof.
  • the carbon fiber refers to a fiber having a carbon content of 90% or more that is produced by carbonizing and graphitizing a carbon precursor such as polyacrylonitrile (PAN), rayon, or pitch at a high temperature of 1500 ° C. or higher.
  • PAN polyacrylonitrile
  • the lithium sulfur battery positive electrode according to the present invention is further characterized by further comprising a mixed layer formed between the positive electrode active material layer and the space forming layer.
  • the mixed layer means a layer in which a positive electrode active material is filled in the space forming layer while the positive electrode active material layer is in contact with the space forming layer.
  • the mixed layer is characterized in that the positive electrode active material concentration gradient in the thickness direction from the positive electrode active material layer to the space forming layer.
  • the positive electrode for lithium sulfur battery it is possible to adjust the thickness and concentration gradient inclination of the mixed layer by the pressure applied when the positive electrode active material is applied or filled to the space forming layer.
  • the positive electrode active material slurry is applied onto the space forming layer, the positive electrode active material slurry is mixed into the space forming layer or when the space forming layer forming material is mixed and applied onto the positive electrode active material layer to the positive electrode active material layer.
  • a mixed layer may be naturally formed.
  • the ratio of the sum of the thicknesses of the mixed layer and the space forming layer with respect to the thickness of the positive electrode active material layer is 1: 0.01 to 1: 0.5. If the sum of the thicknesses of the mixed layer and the space forming layer is 0.01 or less, the effect of confining the lithium polysulfide by the space forming layer is less likely to occur. If the thickness is 0.5 or more, the movement of lithium ions is inhibited to deteriorate battery performance.
  • the positive electrode for a lithium sulfur battery according to the present invention may further include a protective film covering the positive electrode active material layer, the mixed layer, and the space forming layer.
  • the protective film is a film formed on the positive electrode active material layer, the mixed layer, and the space forming layer in order to prevent the polysulfide generated in the positive electrode active material layer from being discharged into the electrolyte during charging and discharging of the lithium sulfur battery.
  • the protective film is not formed only on one surface of the space forming layer, but is formed to cover the surface of the cathode active material layer constituting the anode, the space forming layer formed on one or both surfaces of the cathode active material layer, and the mixed layer.
  • the present invention forms a protective film to cover the front and side surfaces of the positive electrode active material layer, the space forming layer formed on one or both surfaces of the positive electrode active material layer, and the mixed layer.
  • a manufacturing method for forming a protective film is not particularly limited, but dip coating, spin coating, spraying using a solution containing a compound forming a protective film. Spray coating, roll to roll, bar ocating, slot die coating, printing or self-assembled monolayer (SAM) coating may be used.
  • SAM self-assembled monolayer
  • the protective film is characterized by an ionic conductivity of 1 ⁇ 10 ⁇ 6 S / cm or more.
  • the protective film is excellent in ionic conductivity and low electrical resistance can play a role as a separator, the lithium sulfur battery of the present invention does not necessarily need to include a separator between the positive electrode and the negative electrode.
  • the protective film comprises a polymer compound including at least one functional group selected from a carboxyl group, a carboxylate group, a cyan group, a phosphoric acid group, a phosphonate group, a sulfonic acid group, and a sulfonate group. It is characterized by.
  • the functional group selected from the carboxyl group, the carboxylate group, the cyan group, the phosphoric acid group, the phosphonic acid group, the sulfonic acid group, and the sulfonate group included in the high molecular compound forming the protective film may be subjected to poly reactivity with the polysulfide (Electric Repulsion).
  • the elution of sulfide into the electrolyte is suppressed, and the conductivity of lithium ions is improved to facilitate the diffusion of lithium ions in the lithium sulfur battery.
  • polymer compound examples include a fluorine polymer, a benzimidazole polymer, a polyimide polymer, a polyetherimide polymer, a polyphenylene sulfide polymer, a polysulfone polymer, a polyether sulfone polymer, a polyether ketone polymer , Polyether-etherketone-based polymer or polyphenylquinoxaline-based polymer may include one or more selected from poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), polystyrene sulfonic acid, polystyrene Acids, sulfonated polyethersulfones, sulfonated polyetherketones, sulfonated polyetheretherketones, sulfonated polyarylethersulfones, sulfonated polysulfones, sulfonated polyimides, sulfonated polyphosphazene
  • the protective film is formed on the surface of the positive electrode active material and the space forming layer at a ratio of 0.1 to 5 parts by weight per 100 parts by weight of the positive electrode active material.
  • the protective film has a thickness of 0.1 to 20 ⁇ m.
  • the present invention also provides
  • a positive electrode for a lithium sulfur battery according to the present invention is a positive electrode for a lithium sulfur battery according to the present invention.
  • It provides a lithium sulfur battery comprising an electrolyte.
  • FIGS. 2 to 4 show the structure of a lithium sulfur battery according to the present invention.
  • the conventional lithium sulfur battery includes a current collector 10, a cathode active material layer 20 in which an elemental sulfur or a sulfur-based compound formed on the current collector 10 and a conductive material are mixed, a separator 60, And a cathode 70.
  • the cathode active material layer 200, the space forming layer 400, and the cathode active material layer 200 are formed in the space forming layer ( An anode including a mixed layer 300 formed by filling an anode active material in the space forming layer at a portion in contact with 400; Separator 600; Cathode 700; And an electrolyte.
  • the lithium sulfur battery manufactured according to an exemplary embodiment of the present invention not only effectively prevents the space forming layer from dissolving polysulfide into the electrolyte, but also separates the battery by the electrical conductivity of the space forming layer itself.
  • the space forming layer may serve as a current collector without including the whole.
  • the lithium sulfur battery manufactured according to the embodiment of the present invention shown in FIG. 2 has a completely different structure from the conventional lithium sulfur battery shown in FIG. 1, and may manufacture a lithium sulfur battery having reduced weight or volume. It works.
  • the stacking order and the number of stacking of the cathode active material layer 200 and the space forming layer 400 are not limited. That is, in the lithium sulfur battery manufactured by one embodiment of the present invention, the space forming layer may be formed on one surface or both surfaces of the cathode active material layer as shown in Figure 2 (b) and 2 (c). It may also be formed between the positive electrode active material layer as shown in Figure 2 (d).
  • the positive electrode may further include a separate current collector 100 as shown in FIG.
  • the positive electrode according to the present invention does not necessarily include a current collector by including a space forming layer exhibiting electrical conductivity, but a current collector may be additionally used as desired by a person skilled in the art.
  • the present invention also provides
  • a positive electrode for a lithium sulfur battery according to the present invention is a positive electrode for a lithium sulfur battery according to the present invention.
  • It provides a lithium sulfur battery comprising an electrolyte.
  • the positive electrode may further include a protective film 500.
  • the protective layer 500 should cover all of the front and side surfaces of the cathode active material layer 200, the mixed layer 300, and the space forming layer 400 to effectively prevent the dissolution of lithium polysulfide. Can be.
  • such a protective film not only prevents the dissolution of polysulfide into the electrolyte more effectively, but also can be used as a separator, so that the lithium sulfur battery according to the present invention is shown in FIG. As shown in, it may not include a separate separator between the positive electrode and the negative electrode.
  • the positive electrode when the positive electrode further comprises a protective film 500, the separator 600, the current collector 100 It is possible to include more as needed.
  • the electrolyte used in the lithium sulfur battery of the present invention may include a lithium salt as a supporting electrolyte salt and may include a non-aqueous organic solvent.
  • the organic solvent may be benzene, fluorobenzene, toluene, trifluorotoluene, xylene, cyclohexane, tetrahydrofuran, 2-methyl tetrahydrofuran, cyclohexanone, ethanol, isopropyl alcohol, dimethyl carbonate, ethyl Methyl carbonate, diethyl carbonate, methylpropyl carbonate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, dimethoxyethane, 1,3-dioxolane, diglyme, tetraglyme, ethylene carbonate At least one solvent selected from the group consisting of propylene carbonate, ⁇ -butyrolactone and sulfolane.
  • the electrolytic salt lithium salt is lithium trifluoromethansulfonimide (lithium trifluoromethansulfonimide), lithium triflate (lithium triflate), lithium perchlorate (lithium perclorate), lithium hexafluoro azenate (LiAsF 6 ), lithium trifluor Romethanesulfonate (CF 3 SO 3 Li), LiPF 6 , LiBF 4 or tetraalkylammonium, for example tetrabutylammonium tetrafluoroborate, or a liquid salt at room temperature, for example 1-ethyl-3-methyl
  • imidazolium salts such as imidazolium bis (perfluoroethyl sulfonyl) imide and the like can be used.
  • the electrolyte contains lithium salt at a concentration of 0.5 to 2.0 M.
  • the electrolyte may be used as a liquid electrolyte, or may be used in the form of a solid electrolyte separator.
  • the space forming layer may play a role as a current collector, and a protective film may play a role as a separator, thereby manufacturing a lithium sulfur battery that does not include a current collector and / or a separator.
  • the lithium sulfur battery including the positive electrode for a lithium sulfur battery including the space forming layer according to the present invention prevents the dissolution of polysulfide into the electrolyte by trapping the polysulfide generated during the charge and discharge in the space forming layer to initially charge the lithium sulfur battery. Discharge efficiency and lifespan characteristics can be improved.
  • FIG. 1 shows a schematic diagram of a structure of a conventional lithium sulfur battery.
  • FIGS. 2 to 4 show a schematic view of a lithium sulfur battery produced by one embodiment of the present invention.
  • Figure 5 shows the life characteristics results of the lithium sulfur battery produced by one embodiment of the present invention.
  • Figure 6 shows the results of the rate characteristic of the lithium sulfur battery produced according to an embodiment of the present invention.
  • Figure 9 shows the results of the rate characteristic of the lithium sulfur battery produced according to an embodiment of the present invention.
  • FIG. 10 is a graph showing charge and discharge efficiency measurement results of a lithium sulfur battery manufactured according to an embodiment of the present invention.
  • FIG 11 shows the life characteristics and rate characteristics results of the lithium sulfur battery manufactured according to one embodiment of the present invention.
  • the slurry was coated on an aluminum current collector and then dried in a vacuum oven at 80 ° C. for at least 12 hours.
  • a mixture of 70 wt% Ketjen Black and 30 wt% of polyvinylidene fluoride binder was applied to the dried slurry to a thickness of 50 ⁇ m, followed by drying in a vacuum oven at 80 ° C. for at least 12 hours to form a space forming layer.
  • a positive electrode plate was prepared by forming a mixed layer at an interface where the dried slurry and the mixture meet.
  • a lithium sulfur battery was manufactured using the prepared positive electrode plate and lithium foil negative electrode. At this time, 1 M LiTFSI was dissolved in a solvent in which 1,3-dioxolane and dimethoxyethane were mixed at a ratio of 1: 1.
  • Ketjen black and polyvinylidene fluoride binders were coated on an aluminum current collector to a thickness of 25 ⁇ m, and then dried to form a first space forming layer, and then coated with a cathode active material slurry on the first space forming layer, followed by drying. Thereafter, the lithium sulfur battery was manufactured in the same manner as in Example 1-1 except that the mixture was again coated on the dried active material slurry and then dried to form a second space forming layer.
  • Ketjen black and polyvinylidene fluoride binder were applied to an aluminum current collector to a thickness of 50 ⁇ m, and then dried to form a space forming layer, except that a cathode active material slurry was coated on the space forming layer.
  • a lithium sulfur battery was manufactured in the same manner as in Example 1-1.
  • a lithium sulfur battery was manufactured in the same manner as in Example 1-1 except that only a positive electrode active material slurry was applied on an aluminum current collector.
  • the lithium sulfur battery including the space forming layer of the present invention has excellent capacity and life characteristics.
  • Example 1-1 The C-rate characteristics of the lithium sulfur battery prepared in Example 1-1 and Comparative Example were evaluated and the results are shown in FIG. 6. As shown in Figure 6, the discharge characteristics according to the rate was evaluated to 0.1 C, 0.2 C, 0.5 C, 1.0 C.
  • the charge and discharge efficiency of the comparative example drops to 90% after 40 cycles, while in Examples 1-1 to 1-3, 94% to 98% may be maintained.
  • a lithium sulfur battery was manufactured in the same manner as in Example 1-1 except that 100 ⁇ m thick carbon paper was used instead of the mixture of Ketjen black and polyvinylidene fluoride binder.
  • a lithium sulfur battery was manufactured in the same manner as in Example 2-1, except that the cathode active material slurry was coated on the carbon paper formed on the cathode active material layer once more.
  • a lithium sulfur battery was manufactured in the same manner as in Example 1-3, except that 100 ⁇ m thick carbon paper was used instead of the mixture of Ketjen black and polyvinylidene fluoride binder.
  • the lithium sulfur battery including the space forming layer of the present invention has excellent capacity and life characteristics.
  • the charge and discharge efficiency of the comparative example drops to 88% after 50 cycles, while in Examples 2-1 to 2-3, 94% to 99% may be maintained.
  • a slurry for the positive electrode active material was coated on a 100 ⁇ m thick carbon paper and dried to prepare a positive electrode active material layer formed on the space forming layer.
  • Nafion 117 (DuPont) solution was spray coated to a thickness of 4 ⁇ m to prepare a cathode plate.
  • the Nafion 117 (DuPont) solution was prepared to be a 15 wt% Nafion 117 (DuPont) solution using a mixed solvent of 1-propanol and water.
  • a lithium sulfur battery was manufactured using the positive electrode plate and the lithium foil negative electrode.
  • the space forming layer was arranged in the order of the cathode active material layer-mixed layer-space forming layer
  • 1M LiTFSI was dissolved in 1,3-dioxolane and dimethoxyethane in a ratio of 1: 1 and used.
  • the lithium sulfur battery of the present invention may show excellent life characteristics and rate characteristics.
  • the lithium sulfur battery according to the present invention includes a lithium sulfur battery positive electrode including a space forming layer, thereby trapping polysulfide generated during charging and discharging in the space forming layer to prevent the dissolution of polysulfide into the electrolyte, thereby preventing the initial stage of the lithium sulfur battery.
  • the charging and discharging efficiency and lifespan characteristics can be improved.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne une batterie au lithium-soufre comprenant une électrode positive pour batterie au lithium-soufre comportant une couche de formation d'espace, et plus spécifiquement une batterie au lithium-soufre comprenant une électrode positive pour batterie au lithium-soufre dans laquelle une couche de formation d'espace sert de couche tampon. Dans la batterie au lithium-soufre comprenant une électrode positive pour batterie au lithium-soufre comportant une couche de formation d'espace selon la présente invention, du polysulfure produit au moment de la charge et de la décharge est maintenu dans la couche de formation d'espace pour empêcher l'élution du polysulfure dans un électrolyte, ce qui permet d'améliorer les caractéristiques d'efficacité de charge et de décharge initiale et de durée de vie de la batterie au lithium-soufre, et la couche de formation d'espace peut être utilisée comme collecteur de courant, ce qui permet de fabriquer une batterie au lithium-soufre ayant un poids ou un volume réduit.
PCT/KR2015/001788 2014-03-19 2015-02-25 Batterie au lithium-soufre WO2015141952A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR20140032077 2014-03-19
KR10-2014-0032077 2014-03-19
KR10-2014-0092516 2014-07-22
KR1020140092516A KR20150109240A (ko) 2014-03-19 2014-07-22 리튬 설퍼 전지용 양극 및 이를 포함하는 리튬 설퍼 전지
KR1020140097923A KR20150109241A (ko) 2014-03-19 2014-07-31 리튬 설퍼 전지
KR10-2014-0097923 2014-07-31

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105374982A (zh) * 2015-12-11 2016-03-02 中国电子科技集团公司第十八研究所 一种锂硫电池的电极结构及加工工艺
WO2017053142A1 (fr) * 2015-09-25 2017-03-30 Board Of Regents, The University Of Texas System Cathodes carbone-soufre multicouches
CN108140899A (zh) * 2015-10-14 2018-06-08 株式会社杰士汤浅国际 非水电解质二次电池
CN110380051A (zh) * 2019-07-05 2019-10-25 合肥国轩高科动力能源有限公司 一种锂离子电池正极浆料及制备方法和锂离子电池正极片
US10756333B2 (en) 2016-08-10 2020-08-25 Lg Chem, Ltd. Cathode active material comprising polyimide, manufacturing method thereof, and lithium-sulfur battery comprising same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050022567A (ko) * 2003-08-27 2005-03-08 대한민국 (경상대학교 총장) 그라파이트 나노섬유 막을 적용한 리튬/유황 이차전지
KR20070004670A (ko) * 2004-02-06 2007-01-09 폴리플러스 배터리 컴퍼니 보호된 활성 금속 전극 및 비수성 중간층 구조물을 가진배터리 전지 구조
JP2012238448A (ja) * 2011-05-11 2012-12-06 Sony Corp 二次電池、二次電池の製造方法、二次電池用正極、二次電池用正極の製造方法、電池パック、電子機器、電動車両、電力システムおよび電力貯蔵用電源
KR20130119432A (ko) * 2010-10-07 2013-10-31 바텔리 메모리얼 인스티튜트 재충전형 리튬-황 전지 전극용 그래핀-황 나노복합체
KR101365679B1 (ko) * 2012-08-16 2014-02-20 부산대학교 산학협력단 리튬-설퍼 전지용 양극의 제조 방법 및 리튬 설퍼 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050022567A (ko) * 2003-08-27 2005-03-08 대한민국 (경상대학교 총장) 그라파이트 나노섬유 막을 적용한 리튬/유황 이차전지
KR20070004670A (ko) * 2004-02-06 2007-01-09 폴리플러스 배터리 컴퍼니 보호된 활성 금속 전극 및 비수성 중간층 구조물을 가진배터리 전지 구조
KR20130119432A (ko) * 2010-10-07 2013-10-31 바텔리 메모리얼 인스티튜트 재충전형 리튬-황 전지 전극용 그래핀-황 나노복합체
JP2012238448A (ja) * 2011-05-11 2012-12-06 Sony Corp 二次電池、二次電池の製造方法、二次電池用正極、二次電池用正極の製造方法、電池パック、電子機器、電動車両、電力システムおよび電力貯蔵用電源
KR101365679B1 (ko) * 2012-08-16 2014-02-20 부산대학교 산학협력단 리튬-설퍼 전지용 양극의 제조 방법 및 리튬 설퍼 전지

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017053142A1 (fr) * 2015-09-25 2017-03-30 Board Of Regents, The University Of Texas System Cathodes carbone-soufre multicouches
CN108140899A (zh) * 2015-10-14 2018-06-08 株式会社杰士汤浅国际 非水电解质二次电池
EP3364486A4 (fr) * 2015-10-14 2019-05-22 GS Yuasa International Ltd. Batterie rechargeable à électrolyte non aqueux
EP3364490A4 (fr) * 2015-10-14 2019-06-05 GS Yuasa International Ltd. Batterie rechargeable à électrolyte non aqueux
US10892513B2 (en) 2015-10-14 2021-01-12 Gs Yuasa International Ltd. Nonaqueous electrolyte secondary battery
US11196078B2 (en) 2015-10-14 2021-12-07 Gs Yuasa International, Ltd. Nonaqueous electrolyte secondary battery
CN105374982A (zh) * 2015-12-11 2016-03-02 中国电子科技集团公司第十八研究所 一种锂硫电池的电极结构及加工工艺
US10756333B2 (en) 2016-08-10 2020-08-25 Lg Chem, Ltd. Cathode active material comprising polyimide, manufacturing method thereof, and lithium-sulfur battery comprising same
CN110380051A (zh) * 2019-07-05 2019-10-25 合肥国轩高科动力能源有限公司 一种锂离子电池正极浆料及制备方法和锂离子电池正极片
CN110380051B (zh) * 2019-07-05 2022-05-17 合肥国轩高科动力能源有限公司 一种锂离子电池正极浆料及制备方法和锂离子电池正极片

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