WO2018034501A1 - Séparateur multicouche, revêtu d'une couche de catalyseur, pour batteries au lithium-soufre et batterie au lithium-soufre l'utilisant - Google Patents

Séparateur multicouche, revêtu d'une couche de catalyseur, pour batteries au lithium-soufre et batterie au lithium-soufre l'utilisant Download PDF

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WO2018034501A1
WO2018034501A1 PCT/KR2017/008938 KR2017008938W WO2018034501A1 WO 2018034501 A1 WO2018034501 A1 WO 2018034501A1 KR 2017008938 W KR2017008938 W KR 2017008938W WO 2018034501 A1 WO2018034501 A1 WO 2018034501A1
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separator
layer
lithium sulfur
carbon
sulfur battery
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PCT/KR2017/008938
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English (en)
Korean (ko)
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김용태
최지환
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부산대학교 산학협력단
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Priority claimed from KR1020170100382A external-priority patent/KR102011253B1/ko
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Publication of WO2018034501A1 publication Critical patent/WO2018034501A1/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
    • 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
    • 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
    • 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

  • Lithium secondary batteries have higher energy density and longer lifespan than nickel cadmium batteries and nickel-hydrogen batteries. They are widely used in various fields such as computers and mobile devices. They are also used as medium and large secondary battery materials for electric vehicles in the future. Is getting.
  • Separation membrane among the important parts of the lithium secondary battery prevents the short circuit of the positive electrode and the negative electrode of the battery, and the ion transfer is made to have a great effect on the battery stability. Recently, high energy density and lifespan of secondary batteries are required. Accordingly, the separator is also required to have high performance as well as high stability.
  • the positive electrode contains sulfur and lithium metal is used as the negative electrode.
  • the lithium sulfur battery is finally Li 2 S
  • the reduction of sulfur in combination with the lithium ions which have been moved from the cathode in the cathode during discharge - involves the reaction for forming a (2Li + + 2e + S ⁇ Li 2 S) and 1672 mAh / g) theoretical capacity.
  • the soluble polysulfide is dissolved in the electrolyte to reciprocate the positive electrode and the negative electrode, and insoluble Li 2 S and Li 2 S 2 generated in this process accumulate on the surface of the negative electrode and other separators, thereby degrading battery performance.
  • a shuttle mechanism problem occurs in which a decrease in battery capacity and cycle characteristics occurs.
  • the problem to be solved by the present invention is to provide a multi-layer separator for a lithium sulfur battery coated with a catalyst layer that can suppress the shuttle phenomenon in a lithium sulfur battery, improve the capacity and cycle characteristics of the battery and a lithium sulfur battery using the same. .
  • the present invention provides a separator for a lithium sulfur battery, wherein the amount of the catalyst layer is 2 to 4 mg / cm 2 per unit area.
  • the present invention provides a separator for a lithium sulfur battery, characterized in that the ratio of the catalyst material to the mixed amount 100% of the catalyst material and the carbon material is 10 to 30%.
  • the present invention is a lithium sulfur battery separator, wherein the separator is a laminate of a first separator membrane coated with a catalyst layer on top of the first base substrate layer and a second separator membrane coated with a carbon layer on the second base substrate layer. It provides a separator for lithium sulfur battery, characterized in that the form.
  • the present invention is a positive electrode and a negative electrode disposed opposite each other; A separator positioned between the anode and the cathode; And an electrolyte, wherein the separator provides a lithium sulfur battery including a base substrate layer and a catalyst layer coated on the base substrate layer.
  • the present invention provides a lithium sulfur battery, characterized in that the amount of the catalyst layer is 2 to 4 mg / cm2 per unit area.
  • the present invention is a positive electrode and a negative electrode disposed opposite each other; A separator positioned between the anode and the cathode; And an electrolyte, wherein the separator provides a base material layer and a lithium sulfur battery including a mixed layer of a catalyst material and a carbon material coated on the base material layer.
  • the present invention provides a lithium sulfur battery, characterized in that the ratio of the catalyst material to the mixed amount 100% of the catalyst material and the carbon material is 10 to 30%.
  • the present invention is a positive electrode and a negative electrode disposed opposite each other; A separator positioned between the anode and the cathode; And an electrolyte, wherein the separator is formed by stacking a first separator coated with a catalyst layer on the first base substrate layer and a second separator coated with a carbon layer on the second base substrate layer.
  • a lithium sulfur battery Provided is a lithium sulfur battery.
  • polysulfide melts in the sulfur anode during charge and discharge, causing shuttle phenomena to move between the positive electrode and the negative electrode, which causes a big problem in the capacity and cycle characteristics of the battery.
  • the use of the separator according to the present invention acts to suppress such phenomena and improve the capacity and cycle characteristics of the battery by the catalytic material coated on the separator surface.
  • FIG. 1 is a schematic diagram showing a lithium sulfur battery according to the present invention.
  • FIG. 2 is a schematic graph showing an exemplary form of a separator according to the present invention.
  • 3 is a graph showing the capacity characteristics according to the catalyst loading amount per unit area.
  • Figure 4 is a graph showing the capacity characteristics according to the ratio of the catalyst material to the mixed amount of the catalyst material and the carbon material 100%.
  • FIG. 6 is a graph showing capacity characteristics of a battery according to a change in thickness of a carbon layer.
  • SEM 7 is an electron scanning microscope (SEM) image for comparing the structure of each carbon having a different specific surface area.
  • first, second, etc. are used to describe various components, these components are of course not limited by these terms. These terms are only used to distinguish one component from another. Therefore, of course, the first component mentioned below may be a second component within the technical spirit of the present invention.
  • spatially relative terms below “, “ beneath “, “ lower”, “ above “, “ upper” It can be used to easily describe a component's correlation with other components. Spatially relative terms are to be understood as including terms in different directions of components in use or operation in addition to the directions shown in the figures. For example, when flipping a component shown in the drawing, a component described as “below” or “beneath” of another component may be placed “above” the other component. Can be. Thus, the exemplary term “below” can encompass both an orientation of above and below. The components can be oriented in other directions as well, so that spatially relative terms can be interpreted according to the orientation.
  • FIG. 1 is a schematic diagram showing a lithium sulfur battery according to the present invention.
  • a lithium sulfur battery 100 includes a positive electrode 110 and a negative electrode 120 disposed to face each other; A separator 130 positioned between the anode 110 and the cathode 120; And electrolytes (not shown).
  • the positive electrode 110 is disposed on the positive electrode current collector 111 and the positive electrode current collector 111 and includes a positive electrode active material layer 112 including a positive electrode active material and optionally a conductive material and a binder. It may include.
  • the positive electrode current collector 111 may be any one that can be used as a current collector in the art, and specifically, foamed aluminum, expanded nickel, and the like having excellent conductivity may be used.
  • the cathode active material may include elemental sulfur (S 8 ), a sulfur-based compound, or a mixture thereof.
  • the conductive material may be used without limitation as long as the conductive material is a conductive material.
  • the conductive material may be a metallic conductive material such as a metal fiber or a metal mesh; Metallic powders such as copper, silver, nickel and aluminum; Or organic conductive materials, such as a polyphenylene derivative, can also be used.
  • the conductive material may be a carbon-based material having a porosity, and carbon black, graphite, graphene, activated carbon, carbon fiber, and the like may be used as the carbon-based material.
  • the conductive materials may be used alone or mixed, the conductive material is preferably included in 5 to 20% by weight based on the total weight of the positive electrode active material layer.
  • the content of the conductive material is less than 5% by weight, other conductivity enhancement effects are insignificant in the use of the conductive material, whereas if the content is more than 20% by weight, the content of the positive electrode active material is relatively small, which may lower the capacity characteristics.
  • the binder may include a thermoplastic resin or a thermosetting resin.
  • a thermoplastic resin for example, polyethylene, polypropylene, polytetrafluoro ethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, tetrafluoroethylene-perfluoroalkylvinylether copolymer, vinylidene fluoride-hexa Fluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-pentafluoro propylene copolymer, propylene-tetrafluoro Low ethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer,
  • the positive electrode 110 as described above may be prepared according to a conventional method, specifically, a composition for forming a positive electrode active material layer prepared by mixing a positive electrode active material, a conductive material and a binder on an organic solvent, is applied onto a current collector And it may be dried and optionally produced by compression molding on the current collector for the purpose of improving the electrode density.
  • the organic solvent may be uniformly dispersed in the positive electrode active material, the binder, and the conductive material, and it is preferable to use one that is easily evaporated.
  • the organic solvent may be acetonitrile, methanol, ethanol, tetrahydrofuran, water, isopropyl alcohol and the like.
  • the negative electrode 120 may be disposed on the negative electrode current collector 121 and the negative electrode current collector 121, and may include a negative electrode active material layer 122 including a negative electrode active material and optionally a conductive material and a binder. have.
  • the negative electrode current collector 121 may be any one that can be used as a current collector in the art, and specifically, copper, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof. It may be selected from.
  • lithium metal and lithium alloy in the group consisting of a material capable of reversibly intercalating or deintercalating lithium ions as a negative electrode active material, a material capable of reacting with lithium ions to form a lithium-containing compound reversibly, lithium metal and lithium alloy May include being selected.
  • any carbon-based negative electrode active material generally used in lithium sulfur batteries may be used, and specific examples thereof include crystalline carbon and amorphous materials. Carbon or these can be used together.
  • representative examples of the material capable of reacting with the lithium ions to form a lithium-containing compound reversibly include tin oxide (SnO 2 ), titanium nitrate, silicon (Si), and the like, but are not limited thereto.
  • the alloy of the lithium metal may be an alloy of lithium with a metal of Si, Ge, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, or Cd.
  • the negative electrode 120 may further include a binder selectively with the negative electrode active material.
  • the binder may act as a paste for the negative electrode active material, mutual adhesion between the active materials, adhesion between the active material and the current collector, and a buffer effect on the expansion and contraction of the active material. Since the same may be the same, a detailed description thereof will be omitted.
  • the negative electrode 120 may be lithium or lithium alloy.
  • the lithium alloy may be an alloy of lithium with metals such as Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, and / or Sn.
  • the cathode 120 may be a thin film of lithium metal.
  • sulfur which is used as a cathode active material, may be converted into an inert material and adhered to a surface of the anode 120 of lithium or lithium alloy.
  • Such inactive sulfur is sulfur in a state in which sulfur can no longer participate in the electrochemical reaction of the anode through various electrochemical or chemical reactions.
  • inert sulfur formed on the surface of the lithium negative electrode may serve as a protective layer of the lithium negative electrode, and as a result, lithium metal and inert sulfur formed on the lithium metal, for example, lithium sulfide may be used as the negative electrode.
  • the lithium sulfur battery 100 includes a separator 130 positioned between the positive electrode 110 and the negative electrode 120.
  • the separator 130 functions to physically separate the anode 110 and the cathode 120, and includes a base base layer 132 and a catalyst layer 131 coated on the base base layer 132. do.
  • the base substrate layer 132 corresponds to a separator generally used in a conventional lithium sulfur battery, and the base substrate layer 132 may be a porous polymer film.
  • the base substrate layer 132 The porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer may be used alone or in combination thereof.
  • a conventional porous nonwoven fabric for example, a non-woven fabric made of high melting glass fibers, polyethylene terephthalate fibers, or the like may be used, but is not limited thereto.
  • the catalyst layer 131 may include Pt, Ir, Ru, Ni, Mn, Co, Fe, Ti, Re, Nb, V, S, W, Zr, Ta, and Mo metals, oxides, nitrides, and carbides of the metals. It may be made of at least one catalyst selected from the group consisting of phosphide, sulfide, but is not limited to the material of the catalyst layer 131 in the present invention.
  • the amount of the catalyst layer according to the present invention is preferably 2 to 4 mg / cm2 per unit area. This will be described later.
  • the soluble polysulfide is dissolved in the electrolyte to reciprocate the positive electrode and the negative electrode, and the insoluble Li 2 S and Li 2 S 2 generated in this process are different from the negative electrode surface and the like. Accumulation at the membrane interface leads to a problem of shuttle mechanisms in which battery performance decreases, that is, battery capacity and cycle characteristics decrease.
  • the catalyst layer 131 on the base substrate layer 132 corresponding to the separator generally used in the conventional lithium sulfur battery, the shuttle phenomenon in the lithium sulfur battery is suppressed, It is possible to improve the capacity and cycle characteristics of the.
  • the separator according to the present invention can be modified in the following form.
  • FIG. 2 is a schematic graph showing an exemplary form of a separator according to the present invention. At this time, Figure 2 shows an exemplary form of the separator in the basic assembly structure of the coin cell, but is not limited to the basic assembly structure of the coin cell in the present invention.
  • the separator according to the present invention may correspond to the form of a separator including a catalyst layer coated on an upper portion of the base substrate layer as in FIG. 1.
  • the amount of the catalyst layer according to the present invention is preferably 2 to 4 mg / cm2 per unit area.
  • Table 1 is a table showing catalyst loadings per unit area.
  • 3 is a graph showing the capacity characteristics according to the catalyst loading amount per unit area.
  • the amount of the catalyst layer is preferably 2 to 4 mg / cm 2 per unit area.
  • the separator according to the present invention may correspond to a separator coated with a mixed layer in which a catalyst material and a carbon material are mixed on the base substrate layer.
  • the carbon material may be any one selected from the group consisting of carbon black, carbon nanotubes, graphene, graphite, amorphous carbon, nano graphite, and combinations thereof, and specific products include super P and denka black. It may be (denka black) or ketjen black (ketjen black) and the like, but does not limit the material of the carbon material in the present invention.
  • the conductivity may be improved through the mixed layer in which the catalyst material and the carbon material are mixed, and the ratio of the catalyst material to 100% of the mixed amount of the catalyst material and the carbon material is preferably 10 to 30%.
  • Table 2 is a table showing the ratio of the catalyst material to 100% of the mixed amount of the catalyst material and the carbon material. However, in Table 2 below, the mixed amount of the catalyst material and the carbon material except for the binder content was based on 100%.
  • Figure 4 is a graph showing the capacity characteristics according to the ratio of the catalyst material to the mixed amount of the catalyst material and the carbon material 100%.
  • the ratio of the catalyst material to 100% of the mixed amount of the catalyst material and the carbon material is 10 to 30%. desirable.
  • the separation membrane according to the present invention includes a first separation membrane coated with a catalyst layer on an upper portion of a first base substrate layer and a second separation membrane coated with a carbon layer on an upper portion of a second base substrate layer. It may correspond to the stacked form of.
  • the material of the carbon layer may be any one selected from the group consisting of carbon black, carbon nanotubes, graphene, graphite, amorphous carbon, nano graphite, and combinations thereof, and specific products include super P, super P, Denka black or ketjen black may be used.
  • the material of the carbon layer is not limited in the present invention.
  • the carbon layer is a thick film, preferably 70 ⁇ m to 120 ⁇ m, and more preferably, the carbon layer is 75 ⁇ m to 110 ⁇ m.
  • the carbon layer is preferably 70 ⁇ m to 120 ⁇ m. This will be described later.
  • the carbon layer corresponds to a porous coating layer.
  • the electrolyte absorption rate (%) according to the following formula (1) of the carbon layer in the present invention is preferably 40 to 70%.
  • W 1 is the initial mass of the coating layer
  • W 2 is the mass after the electrolyte is impregnated in the coating layer.
  • the electrolyte absorption rate (%) is due to the porous characteristics of the carbon layer, and when the electrolyte absorption rate (%) is less than 40%, the pore amount in the carbon layer is too small to prevent material transfer, thereby reducing battery performance.
  • the electrolyte absorption rate (%) exceeds 70%, the carbon layer may not play a role of easily holding the polysulfide described later, the electrolyte absorption rate (%) of the carbon layer is preferably 40 to 70%. Do.
  • the electrolyte absorption rate will be described later.
  • the carbon layer has a porosity characteristic, while lithium is plated on the porous carbon layer, the specific surface area of the lithium anode is widened to induce uniform distribution of electrons, thereby inhibiting dendrite growth of lithium metal. And induce stable electrochemical reactions.
  • the electrolyte (not shown) of the lithium sulfur battery according to the present invention includes lithium salt dispersed in an organic solvent, and the positive electrode 110, the negative electrode 120, and the It is included in the lithium sulfur battery in a state impregnated with the separator 130.
  • the lithium salt may be used without particular limitation that is commonly applicable to lithium batteries.
  • the lithium salt is LiSCN, LiBr, LiI, LiNO 3 , LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiClO 4 , Li (Ph) 4 , LiC (CF 3 SO 2 ) 3 , Li [N (SO 2 CF 3 ) 2 ], LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2, and LiN (CF 3 CF 2 SO 2 ) 2 It may be one or more compounds selected from the group.
  • the concentration of the lithium salt may be determined in consideration of ionic conductivity and the like, and preferably, 0.2 to 4.0M, or 0.5 to 1.6M.
  • organic solvent a single solvent or a mixed solvent of two or more may be used.
  • a mixed solvent it may be advantageous to express the performance of the battery by selecting one or more solvents from two or more groups among the weak polar solvent group, the strong polar solvent group, and the lithium protective solvent group. .
  • the weak polar solvent is a solvent having a dielectric constant of less than 15 among aryl compounds, bicyclic ethers, and acyclic carbonates
  • the strong polar solvent is a solvent having a dielectric constant of greater than 15 among acyclic carbonate, sulfoxide, lactone, ketone, ester, sulfate, sulfide
  • the lithium protective solvent refers to a solvent that is stable to lithium metal and forms a solid electrolyte interface, such as a saturated ester, an unsaturated ester, a heterocyclic compound, and the like.
  • examples of the weak polar solvent include xylene, dimethoxyethane, 2-methyltetrahydrofuran, dimethyl carbonate, diethyl carbonate, toluene, dimethyl ether, diethyl ether, diglyme, tetraglyme, and the like. have.
  • the strong polar solvent is hexamethyl phosphoric triamide, gamma-butyrolactone, acetonitrile, ethylene carbonate, propylene carbonate, N-methylpyrrolidone, 3-methyl-2-oxazolidone, dimethyl formamide And sulfolane, dimethyl acetamide, dimethyl sulfoxide, dimethyl sulfate, ethylene glycol diacetate, dimethyl sulfite, ethylene glycol sulfite and the like.
  • lithium protective solvent examples include tetrahydrofuran, ethylene oxide, dioxolane, 3,5-dimethyl isoxazole, furan, 2-methylfuran, 1,4-oxane, 4-methyldioxolane and the like.
  • the electrolyte further includes additives (hereinafter, referred to as 'other additives') that can be generally used in the electrolyte for the purpose of improving the life characteristics of the battery, reducing the battery capacity, and improving the discharge capacity of the battery. can do.
  • additives hereinafter, referred to as 'other additives'
  • An elemental sulfur (S): conductor (carbon): binder was mixed at a weight ratio of 75: 20: 5 and ball milled for 1 hour to prepare a cathode active material slurry.
  • PVdF and NMP were used as the binder, and the content of PVdF in the binder was 5% by weight when the total binder was 100% by weight.
  • non-oxidized lithium metal foil was used, and a separator was disposed between the prepared positive electrode and the lithium metal foil as a counter electrode, thereby preparing a coin cell evaluation battery.
  • the separator was prepared by coating a catalyst layer of Pt on top of a base substrate layer made of polyethylene.
  • Example 2 In the same manner as in Example 1, except that the separator was prepared by coating a mixed layer of a Pt catalyst material and a carbon material of acetylene black (Denka black, Denki Kagaku Kogyo) on top of the base base layer made of polyethylene. Was carried out.
  • a mixed layer of a Pt catalyst material and a carbon material of acetylene black (Denka black, Denki Kagaku Kogyo)
  • a carbon layer of acetylene black (Denka black, Denki Kagaku Kogyo) was placed on top of the first separator membrane coated with Pt catalyst layer on the first base substrate layer made of polyethylene and the second base substrate layer made of polyethylene.
  • the same process as in Example 1 was carried out except that the laminate structure of the coated second separator was manufactured.
  • Example 2 It carried out similarly to Example 1 except having used the base base material layer which consists of polyethylene as said separator.
  • FIG. 5 (a) is a graph comparing a separator coated with a catalyst material and a general lithium sulfur battery (compare Example 1 with a comparative example), and FIG. 5 (b) shows a mixture of catalyst material and carbon at a predetermined ratio. After that, it is a graph comparing the coated membrane and a typical lithium sulfur battery (comparison of Example 2 and Comparative Example),
  • Figure 5 (c) is a carbon-coated membrane and a catalyst material-coated membrane after the production of each It is a graph which compared the general lithium sulfur battery with what was laminated
  • Example 3 it can be seen that the discharge capacity is significantly improved compared to the comparative example.
  • the cycle characteristics of the lithium sulfur battery can be improved, and in particular, in the present invention, the base substrate layer contains a carbon material or the carbon layer together with the catalyst layer.
  • the cycle characteristic of a lithium sulfur battery can be improved.
  • the battery performance is better when the carbon layer is included in the catalyst layer (Example 2) than when only the catalyst layer is coated on the base substrate layer (Example 1). Since the battery performance is more excellent in the case of coating the layer (Example 3), the following is to check the battery characteristics according to the coating thickness of the carbon layer of the separator.
  • An elemental sulfur (S): conductor (carbon): binder was mixed at a weight ratio of 75: 20: 5 and ball milled for 1 hour to prepare a cathode active material slurry.
  • non-oxidized lithium metal foil was used, and a separator was disposed between the prepared positive electrode and the lithium metal foil as a counter electrode, thereby preparing a coin cell evaluation battery.
  • the separator was prepared by coating a carbon layer of acetylene black (Denka black, Denki Kagaku Kogyo) on the base base layer made of polyethylene.
  • the capacity characteristics of the battery were measured while changing the thickness of the carbon layer to 75 ⁇ m, 90 ⁇ m, 110 ⁇ m, 35 ⁇ m, 55 ⁇ m, and 138 ⁇ m, respectively.
  • FIG. 6 is a graph showing capacity characteristics of a battery according to a change in thickness of a carbon layer.
  • the thickness of the carbon layer corresponds to 138 ⁇ m, it can be seen that the capacity characteristics of the battery is lower than when the thickness of the carbon layer is 75 ⁇ m, 90 ⁇ m, 110 ⁇ m, respectively.
  • the carbon layer is a thick film, preferably 70 ⁇ m to 120 ⁇ m, and more preferably, the carbon layer is 75 ⁇ m to 110 ⁇ m.
  • the carbon layer in the present invention is preferably 70 ⁇ m to 120 ⁇ m.
  • W 1 is the initial mass of the coating layer
  • W 2 is the mass after the electrolyte is impregnated in the coating layer.
  • Applicant compared the characteristics of the battery performance according to the electrolyte absorption rate of the carbon layer according to the present invention through the following experiment.
  • the present inventors experimented by making sheets of acetylene black (Denka black, Denki Kagaku Kogyo) having a large specific surface area and meso carbon micro beads (MCMB, Osaka Gas) having a small specific surface area, respectively.
  • acetylene black Denki Kagaku Kogyo
  • MCMB meso carbon micro beads
  • Electron scanning microscope (SEM) was observed to see the carbon structure of the Denka black and MCMB, and the electrolyte absorption experiment was performed to see the electrolyte absorption rate of each carbon sheet.
  • FIG. 7 is an electron scanning microscope (SEM) image for comparing the structure of each carbon having a different specific surface area.
  • SEM electron scanning microscope
  • Denka black powder has a constant particle size of about 0.1 ⁇ m, while MCMB powder has a particle size of 0.5 to 1 ⁇ m, it can be seen that the particle size is larger than denka black.
  • the Denka black sheet when the powder is produced in each sheet, the Denka black sheet has a particle size of less than about 0.1 ⁇ m, while maintaining the original particle size and shape, the parts are in the shape of agglomeration with each other.
  • the MCMB sheet is crushed particles show a much different particle size and shape than the original powder.
  • the MCMB sheet is in the form of aggregates as a whole, despite the use of the same amount of binder as Denka black, it can be seen that the pores are not visible and blocked.
  • MCMB carbon has a larger particle size than Denka black carbon, it is thought that large spherical MCMB carbon particles aggregate together and show no pores.
  • each sheet is expected to have a large difference in the pores, and the electrolyte absorption rate of each sheet to determine how much the carbon sheets absorb the electrolyte because the electrolyte absorption rate can be different if the porosity is different. was measured.
  • the electrolyte absorption rate was measured by taking out each carbon sheet after being impregnated in the electrolyte for a certain time and weighed, and was calculated by the above Equation (1).
  • the initial weight of Denka black sheet was 0.0198g and the initial weight of MCMB sheet was 0.0464g. After the impregnation of each carbon sheet in electrolyte, the weight was taken out and the weight of Denka black sheet was 0.0428g, MCMB. The weight of the sheet was 0.0482g.
  • the absorbency of Denka black-sheet was about 53.73% and the MCMB-sheet was about 3.73%.
  • Denka black sheet has about 14 times better electrolyte absorption than MCMB sheet, and MCMB sheet, which appears to have a specific surface area and no pores, does not absorb electrolyte well.
  • FIG. 8 illustrates a case where the carbon sheet is not included in the separator
  • FIG. 9 illustrates a case where the Denka black sheet is included in the separator
  • FIG. 10 illustrates a case where the MCMB sheet is included in the separator.
  • the initial capacity showed a discharge capacity of 1002 mAh / g, which is 59% of the theoretical capacity, and 547 mAh / g, which is 54% of the initial discharge, at 50 cycles.
  • the initial capacity is 1491 mAh / g, which is 89% of the theoretical capacity, and 1062 mAh / g, which is 71% of the initial discharge capacity at 50 cycles. .
  • the separator includes an MCMB sheet
  • an initial capacity of 106 mAh / g which is 6.3% of theoretical capacity
  • a discharge capacity of 239 mAh / g which is higher than the initial discharge capacity
  • the MCMB sheet has a much lower electrolyte absorption rate than the Denka black sheet. Therefore, in the case of the MCMB sheet having a low electrolyte absorption rate, the MCMB sheet may interfere with the movement of lithium ions to react with sulfur. It seems to have had an adverse effect.
  • the electrolyte absorption rate (%) is due to the porosity of the carbon layer.
  • the electrolyte absorption rate (%) is less than 40%, the amount of pores in the carbon layer is so small that material transfer is hindered.
  • the performance decreases and the electrolyte absorption rate (%) exceeds 70% the carbon layer cannot play a role of catching polysulfide, so the electrolyte absorption rate (%) of the carbon layer is 40 to 70%. Is preferably.

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Abstract

La présente invention concerne une batterie au lithium-soufre comprenant : une électrode positive et une électrode négative qui sont disposées de manière à se faire face l'une à l'autre; un séparateur positionné entre l'électrode positive et l'électrode négative; et un électrolyte, le séparateur comprenant une couche de substrat de base et une couche de catalyseur revêtue sur la couche de substrat de base. L'utilisation du séparateur selon la présente invention a pour effet d'inhiber ces phénomènes et permet d'améliorer les propriétés de capacité et de cycle de la batterie en raison d'une substance catalytique appliquée sur la surface du séparateur.
PCT/KR2017/008938 2016-08-17 2017-08-17 Séparateur multicouche, revêtu d'une couche de catalyseur, pour batteries au lithium-soufre et batterie au lithium-soufre l'utilisant WO2018034501A1 (fr)

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CN113285177A (zh) * 2020-02-03 2021-08-20 河北金力新能源科技股份有限公司 改性锂硫电池隔膜浆料及其制备方法、应用
CN113540691A (zh) * 2020-03-31 2021-10-22 比亚迪股份有限公司 一种锂离子电池隔膜及其制备方法、锂离子电池
CN113649043A (zh) * 2021-08-17 2021-11-16 大连理工大学 一种高负载Mn-N活性位点掺杂碳材料催化剂的制备方法及其在锂硫电池上的应用

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