WO2020226321A1 - Séparateur pour batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant - Google Patents

Séparateur pour batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant Download PDF

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Publication number
WO2020226321A1
WO2020226321A1 PCT/KR2020/005569 KR2020005569W WO2020226321A1 WO 2020226321 A1 WO2020226321 A1 WO 2020226321A1 KR 2020005569 W KR2020005569 W KR 2020005569W WO 2020226321 A1 WO2020226321 A1 WO 2020226321A1
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Prior art keywords
lithium
secondary battery
lithium secondary
separator
molybdenum disulfide
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PCT/KR2020/005569
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English (en)
Korean (ko)
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김명성
예성지
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주식회사 엘지화학
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Priority claimed from KR1020200050190A external-priority patent/KR20200127873A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2021532465A priority Critical patent/JP7275273B2/ja
Priority to EP20801464.7A priority patent/EP3883009A4/fr
Priority to CN202080007114.2A priority patent/CN113243060B/zh
Priority to US17/312,650 priority patent/US12107296B2/en
Publication of WO2020226321A1 publication Critical patent/WO2020226321A1/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
    • H01M50/489—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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
    • H01M50/491—Porosity
    • 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 separator for a lithium secondary battery and a lithium secondary battery including the same.
  • lithium secondary batteries As the scope of use of lithium secondary batteries has expanded to not only portable electronic devices and communication devices, but also electric vehicles (EVs) and electric storage systems (ESSs), the high capacity of lithium secondary batteries used as power sources has been improved. The demand is increasing.
  • EVs electric vehicles
  • ESSs electric storage systems
  • a lithium-sulfur battery uses a sulfur-based material containing a sulfur-sulfur bond as a positive electrode active material, and lithium metal, a carbon-based material in which lithium ions are inserted/deinserted, or lithium It is a secondary battery that uses silicon or tin, which forms an alloy with, as an anode active material.
  • sulfur which is the main material of the positive electrode active material, has a low weight per atom, rich in resources, easy supply and demand, inexpensive, non-toxic, and has the advantage of being an environmentally friendly material.
  • a lithium-sulfur battery is a lithium ion and the sulfur conversion (conversion) reaction at the anode - the theoretical discharge capacity resulting from (S 8 + 16Li + + 16e ⁇ 8Li 2 S) reached 1,675 mAh / g, a lithium metal as a negative electrode ( Theoretical capacity: 3,860 mAh/g) shows a theoretical energy density of 2,600 Wh/kg.
  • Li-MH battery 450Wh/kg
  • Li-FeS battery 480Wh/kg
  • Li-MnO 2 battery 1,000Wh/kg
  • Na-S battery 800Wh/kg
  • commercial lithium Since it has a very high value compared to the theoretical energy density of a secondary battery (LiCoO 2 /graphite), it is attracting attention as a high-capacity, eco-friendly, and inexpensive lithium secondary battery among secondary batteries being developed so far. Is losing.
  • lithium-sulfur battery when discharging, sulfur accepts electrons from the positive electrode and undergoes a reduction reaction, while the negative electrode undergoes an oxidation reaction in which lithium is ionized.
  • the positive electrode which is dissolved in the electrolyte and eluted from the positive electrode, so that the reversible capacity of the positive electrode is greatly reduced.
  • the dissolved lithium polysulfide diffuses to the negative electrode, causing various side reactions.
  • the lithium polysulfide causes a shuttle reaction, which greatly reduces charging and discharging efficiency.
  • Korean Patent Application Publication No. 2018-0020096 discloses that by including a separator on which a catalyst layer containing a transition metal compound is formed, it is possible to improve the capacity and cycle characteristics of a battery by suppressing the shuttle reaction due to elution of lithium polysulfide. have.
  • Korean Patent Application Publication No. 2016-0046775 provides a positive electrode coating layer made of an amphiphilic polymer on a portion of the positive electrode active part including a sulfur-carbon composite to prevent the elution of lithium polysulfide and facilitate the movement of lithium ions. It discloses that the cycle characteristics of a battery can be improved.
  • Korean Patent Laid-Open No. 2016-0037084 discloses that by coating graphene on a carbon nanotube aggregate containing sulfur, it blocks the dissolution of lithium polysulfide, and increases the conductivity of the sulfur-carbon nanotube composite and the loading amount of sulfur. Disclosed that you can.
  • the present inventors conducted various studies to solve the above problem. As a result, by introducing a coating layer containing molybdenum disulfide containing defects on the substrate of the separator, the problem of the elution of lithium polysulfide in the lithium-sulfur battery was solved and the negative electrode The present invention was completed by confirming that the lithium dendrite growth can be suppressed to improve the performance and lifespan of the lithium secondary battery.
  • an object of the present invention is to provide a separator for a lithium secondary battery that improves capacity and life characteristics of a lithium secondary battery by solving the problem caused by the elution of lithium polysulfide.
  • Another object of the present invention is to provide a lithium secondary battery including the separator.
  • the present invention is a porous substrate; And a coating layer formed on at least one surface of the porous substrate,
  • the coating layer provides a separator for a lithium secondary battery containing molybdenum disulfide containing defects.
  • Molybdenum disulfide including the defect may have a nanosheet shape.
  • Molybdenum disulfide including the defect may have a thickness of 1 to 20 nm.
  • Molybdenum disulfide containing the defect may be crystalline.
  • Molybdenum disulfide containing the defect has diffraction peaks that appear in the ranges of 14.0 ⁇ 0.2°, 33.1 ⁇ 0.2°, 39.4 ⁇ 0.2°, and 58.7 ⁇ 0.2°, respectively, when the diffraction angle (2 ⁇ ) is measured by X-ray diffraction (XRD). It may be included.
  • the defect may be one or more selected from the group consisting of point defects, line defects, and surface defects.
  • the coating layer may have a thickness of 0.1 to 10 ⁇ m.
  • the coating layer may be disposed to face the negative electrode of the lithium secondary battery.
  • the present invention provides a lithium secondary battery including the separator for the lithium secondary battery.
  • Molybdenum disulfide containing defects included in the coating layer of the separation membrane according to the present invention includes these by promoting the effect of inhibiting lithium polysulfide adsorption and lithium dendrite generation by imparting additional electrochemical catalytic activity to the edges of the defects. It improves the capacity and life characteristics of a lithium secondary battery, specifically a lithium-sulfur battery.
  • a lithium secondary battery provided with a separator on which a coating layer containing molybdenum disulfide containing the defects is formed does not cause a decrease in the capacity of sulfur, so that a high-capacity battery can be implemented, and it is possible to stably apply sulfur by high loading, as well as lithium-den Dry growth is prevented, and there are no problems such as short circuit or heat generation of the battery, improving battery stability.
  • such a lithium secondary battery has an advantage in that the charging/discharging efficiency of the battery is high and life characteristics are improved.
  • SEM scanning electron microscope
  • FIG. 3 is a graph showing the result of X-ray diffraction measurement of molybdenum disulfide containing defects according to Preparation Example 1 of the present invention.
  • FIG. 6 is a graph showing the evaluation result of the lithium polysulfide adsorption effect of molybdenum disulfide containing defects according to Preparation Example 1 of the present invention.
  • Example 7 is a scanning electron microscope (SEM) image of a separator according to Example 1 of the present invention.
  • porosity used in the present invention means the ratio of the volume occupied by pores to the total volume in a structure, and uses% as its unit, and can be used interchangeably with terms such as porosity and porosity. I can.
  • the measurement of the porosity is not particularly limited, for example, the size (micro) and mesopore volume by a BET (Brunauer-Emmett-Teller) measurement method or a mercury permeation method (Hg porosimeter). ) Can be measured.
  • Lithium-sulfur batteries have a high theoretical discharge capacity and theoretical energy density among various secondary batteries, and sulfur used as a positive electrode active material is in the spotlight as a next-generation secondary battery due to the advantage of being inexpensive and environmentally friendly due to its abundant reserves.
  • lithium polysulfide which is an intermediate product of the sulfur reduction reaction, lithium polysulfide (Li 2 S x , usually x> 4) with a high oxidation number of sulfur is a material with strong polarity and is easily dissolved in an electrolyte containing a hydrophilic organic solvent to react with the anode. There is a loss of sulfur that elutes out of the domain and no longer participates in the electrochemical reaction.
  • a material capable of suppressing the elution of lithium polysulfide is introduced into the anode or separator in the form of an additive or coating layer, the composition of the electrolyte is changed, or a protective layer or solid-electrolyte interphase (SEI) on the surface of the cathode is introduced.
  • SEI solid-electrolyte interphase
  • molybdenum disulfide (defect-rich MoS 2 ) containing a defect capable of adsorbing lithium polysulfide in order to secure an effect of improving the capacity and life characteristics of a lithium secondary battery by suppressing the elution of lithium polysulfide. It provides a separator for a lithium secondary battery having a coating layer comprising a.
  • the separator for a lithium secondary battery according to the present invention includes a porous substrate; And a coating layer formed on at least one surface of the porous substrate, wherein the coating layer includes molybdenum disulfide (defect-rich MoS 2 ) containing defects.
  • the coating layer includes molybdenum disulfide (defect-rich MoS 2 ) containing defects.
  • the porous substrate constituting the separator for a lithium secondary battery of the present invention enables transport of lithium ions between the positive electrode and the negative electrode while separating or insulating the negative electrode and the positive electrode from each other.
  • the separator of the present invention is porous and may be made of a non-conductive or insulating material.
  • the separator may be an independent member such as a film.
  • a porous polymer film may be used alone or by stacking them, and for example, a nonwoven fabric or a polyolefin-based porous film made of high melting point glass fibers, polyethylene terephthalate fibers, etc. may be used, but limited thereto. It does not become.
  • the material of the porous substrate is not particularly limited in the present invention, and any porous substrate commonly used in an electrochemical device may be used.
  • the porous substrate is a polyester such as polyethylene, polyolefin such as polypropylene, polyethylene terephthalate, polybutyleneterephthalate, and polyamide.
  • polyamide polyacetal, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylene sulfide polyphenylenesulfide), polyethylenenaphthalate, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, cellulose, nylon (nylon), polyparaphenylene benzobisoxazole (poly(p-phenylene benzobisoxazole)) and polyarylate (polyarylate) may include at least one material selected from the group consisting of.
  • the thickness of the porous substrate is not particularly limited, but may be 1 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
  • the thickness range of the porous substrate is not limited to the above-described range, when the thickness is too thin than the above-described lower limit, mechanical properties are deteriorated and the separator may be easily damaged during battery use.
  • the average diameter and pores of the pores present in the porous substrate are also not particularly limited, but may be 0.001 to 50 ⁇ m and 10 to 95%, respectively.
  • the coating layer is formed on at least one surface of the aforementioned porous substrate, and includes molybdenum disulfide (defect-rich MoS 2 ) containing defects.
  • Molybdenum disulfide (defect-rich MoS 2 ) containing the defect solves the problem of loss of sulfur and capacity loss caused by elution of lithium polysulfide in conventional lithium-sulfur batteries by adsorbing lithium polysulfide
  • molybdenum disulfide (defect-rich MoS 2 ) containing the defect is a side reaction on the negative electrode surface caused by the shuttle effect of lithium polysulfide by constraining lithium polysulfide to the coating layer of the separator, for example, the negative electrode It is possible to improve the coulomb efficiency and lifespan of the battery by reacting with the lithium metal used as a lithium metal to form a high resistance layer of Li 2 S at the interface or by solving the problem of lithium dendrite growth in which lithium is deposited at the negative electrode interface. .
  • molybdenum disulfide (defect-rich MoS 2 ) containing the defect has a layered structure, and in-plane carrier mobility of 200 to 500 cm 2 /Vs Because it represents the lithium ion insertion (intercalation) / deintercalation (deintercalation) is easy as well as the movement of ions is easy. This reduces the interfacial resistance of the lithium metal and promotes a constant flow of lithium on the surface of the lithium metal, thereby controlling the speed of movement of electrons on the surface of the lithium metal and promoting a uniform distribution of lithium ions, effectively inhibiting the growth of lithium dendrites. I can.
  • molybdenum disulfide is a material having adsorption capacity for lithium polysulfide, and has been used in lithium-sulfur batteries, but molybdenum disulfide used at this time is molybdenum disulfide (defect-free MoS 2 ) without defects in its crystal structure.
  • the molybdenum disulfide included in the coating layer of the present invention includes an artificially formed defect, and the defect additionally provides an'active edge site' to the molybdenum disulfide, so that the lithium polysulfide of the above-described
  • the defect By imparting electrochemical catalytic activity that can promote the elution and lithium dendrite growth inhibition effect, it has improved adsorption of lithium polysulfide and prevention of lithium dendrite formation than that of conventionally used defect-free molybdenum disulfide (defect-free MoS 2 ). Therefore, the capacity and life characteristics of a lithium secondary battery including the same can be remarkably improved.
  • a disordered atomic arrangement on the surface of molybdenum disulfide including the defect is included as a defect, and may be expressed as MoS 2-x (0 ⁇ x ⁇ 0.5) in the chemical formula.
  • the defect can secure an additional open space due to the chemical structure of molybdenum disulfide, and this open space facilitates the movement of ions, thereby including the defect.
  • Molybdenum disulfide can exhibit improved electrochemical reactivity compared to molybdenum disulfide without defects.
  • Molybdenum disulfide containing the above defects will be described later as being manufactured by the manufacturing method presented in the present invention.
  • Molybdenum disulfide containing defects prepared according to the manufacturing method of the present invention is in the shape of a nanosheet having a thickness of 1 to 20 nm, preferably 1 to 10 nm, and the molybdenum disulfide of the nanosheet shape is regularly or irregularly in various sizes. It includes defects formed.
  • the defect may be a structural defect as an inherent defect formed during the production of molybdenum disulfide, and may be, for example, at least one selected from the group consisting of point defects, line defects, and surface defects. Specifically, the defect may be at least one selected from the group consisting of point defects such as vacancy and interstitial atoms, line defects such as dislocaiton, and surface defects such as grain boundaries.
  • Molybdenum disulfide including the defect may include a plurality of defects. Separation distances between the plurality of defects may correspond to each other or may be different from each other. The plurality of defects may correspond to each other or may have different sizes.
  • Molybdenum disulfide containing the defects of the present invention may be crystalline. This can be confirmed through X-ray diffraction (XRD) measurement.
  • XRD X-ray diffraction
  • a significant or effective peak means a peak that is detected repeatedly in a substantially the same pattern in XRD data without being significantly affected by the analysis conditions or the person performing the analysis. It may be 1.5 times or more compared to the (backgound level), and preferably refers to a peak having a height, intensity, intensity, etc. of 2 times or more, more preferably 2.5 times or more.
  • Molybdenum disulfide containing the defect was obtained by X-ray diffraction (XRD) analysis using a Cu-K ⁇ X-ray wavelength, diffraction angles (2 ⁇ ) of 14.0 ⁇ 0.2°, 33.1 ⁇ 0.2°, 39.4 ⁇ 0.2°, and 58.7 ⁇ 0.2°. Effective peaks each appearing in the range of ° are included, which mean diffraction peaks corresponding to (002), (100, 101), (103) and (110) crystal planes, respectively, from which disulfide including defects of the present invention It can be seen that molybdenum is crystalline.
  • Molybdenum disulfide containing the defect can be confirmed that the Mo:S atomic ratio is 1:1.7 as a result of Energy Dispersive X-ray Spectrometer (EDS) analysis, through which the defect of the present invention
  • EDS Energy Dispersive X-ray Spectrometer
  • molybdenum disulfide containing it can be seen that it is a compound represented by MoS 2-x (0 ⁇ x ⁇ 0.5).
  • the coating layer may be disposed facing the negative electrode or the positive electrode, and is not particularly limited in the present invention.
  • the lithium secondary battery of the present invention contains lithium metal as a negative electrode active material
  • the coating layer is preferably disposed facing the negative electrode. At this time, the coating layer is formed facing the negative electrode, thereby suppressing side reactions between lithium polysulfide and lithium metal diffused from the positive electrode containing sulfur, as well as preventing the growth of lithium dendrites, thereby increasing the life and stability of the battery.
  • the thickness of the coating layer is not particularly limited, and has a range that does not increase the internal resistance of the battery while securing the above-described effects.
  • the thickness of the coating layer may be 0.1 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, more preferably 0.1 to 1 ⁇ m.
  • the thickness of the coating layer is less than the above range, the function as a coating layer cannot be performed.
  • the thickness of the coating layer exceeds the above range, interfacial resistance may increase, resulting in an increase in internal resistance during battery operation.
  • the manufacturing method of the separator for a lithium secondary battery presented in the present invention is not particularly limited, and a known method or various methods of modifying it may be used by a person skilled in the art.
  • the method of manufacturing a separator for a lithium secondary battery As an example, the method of manufacturing a separator for a lithium secondary battery,
  • the preparation of molybdenum disulfide including the defect in step (a) may be performed by reaction of a molybdenum precursor and a sulfur precursor.
  • step of preparing molybdenum disulfide including the defect of step (a)
  • (a-3) It may include drying the molybdenum disulfide formed in the step (a-2).
  • the molybdenum precursor of step (a-1) refers to a material capable of forming molybdenum disulfide (MoS 2 ) by reacting with a sulfur precursor.
  • the molybdenum precursor is sodium molybdate (Na 2 MoO 4 ), ammonium tetrathiomolybdate ((NH 4 ) 2 MoS 4 ), ammonium heptamolybdate tetrahydrate ((NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O), molybdenum trioxide (MoO 3 ) and molybdenum chloride (MoCl 5 )
  • ammonium heptamolybdate tetrahydrate may be preferably used.
  • Types of the sulfur precursor include thiourea (CH 4 N 2 S), sodium thiosulfate (Na 2 S 2 O 3 ), sodium sulfide (Na 2 S), and hydrogen sulfide (H 2 S).
  • thiourea CH 4 N 2 S
  • sodium thiosulfate Na 2 S 2 O 3
  • sodium sulfide Na 2 S
  • hydrogen sulfide H 2 S.
  • thiourea may be preferably used.
  • the molybdenum precursor and the sulfur precursor are added to an aqueous solvent such as deionized water, and vigorously stirred for 10 minutes to 1 hour to prepare a mixed solution.
  • an aqueous solvent such as deionized water
  • the molar ratio of molybdenum and sulfur based on the mixed solution may be 1:2 or higher, preferably 1:3 to 1:5. If the proportion of sulfur is less than the above range, a sufficient amount of molybdenum disulfide may not be prepared based on the reactant added. When the molar ratio of molybdenum and sulfur falls within the above-described range, a sufficient amount of sulfur not only reduces Mo(VI) to Mo(IV), but also stabilizes the morphology of molybdenum disulfide in a nanosheet shape to be described later. Will function.
  • the prepared mixed solution is introduced into a hydrothermal synthesis reactor such as an autoclave to form molybdenum disulfide.
  • the hydrothermal synthesis reaction may be performed at a temperature of 180 to 240° C. for 10 to 24 hours, and preferably at a temperature of 200 to 220° C., and a synthesis reaction may be performed for 16 to 20 hours.
  • the reaction product may be slowly cooled to room temperature, and the final product may be washed several times using water and ethanol. Through this process, residual ionic components or impurities remaining in the final product can be removed.
  • the final product of the hydrothermal synthesis is dried at 60 to 80°C to obtain molybdenum disulfide.
  • the drying is preferably performed under vacuum conditions for 6 to 12 hours.
  • Molybdenum disulfide prepared according to the manufacturing method including steps (a-1) to (a-3) is molybdenum disulfide containing defects by adding a sulfur precursor having a predetermined molar ratio or more as described above.
  • step (b) of preparing a coating composition containing molybdenum disulfide containing defects manufactured by the above-described manufacturing method is performed.
  • the coating composition may further include a solvent other than molybdenum disulfide including the defects described above, and the solvent is not particularly limited as long as it is capable of dissolving molybdenum disulfide including the defect.
  • the solvent may be a mixed solvent of water and alcohol, or a mixture of one or more organic solvents, and in this case, the alcohol may be a lower alcohol having 1 to 6 carbon atoms, preferably methanol, ethanol, propanol, isopropanol, etc. have.
  • polar solvents such as acetic acid, dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP) dimethyl sulfoxide (DMSO), etc., Acetonitrile, ethyl acetate, methyl acetate, fluoroalkane, pentane, 2,2,4-trimethylpentane, decane, cyclohexane, cyclopentane, diisobutylene, 1-pentene, 1-chlorobutane, 1-chloropentane , o-xylene, diisopropyl ether, 2-chloropropane, toluene, 1-chloropropane, chlorobenzene, benzene, diethyl ether, diethyl sulfide, chloroform, dichloromethane, 1,2-dichloroethane, aniline,
  • Non-polar solvents such as diethylamine, ether, carbon tetrach
  • the content of the solvent may be contained at a level having a concentration that can facilitate coating, and the specific content varies depending on the coating method and apparatus.
  • molybdenum disulfide containing the defects may be dispersed in a solvent and then mixed to prepare a coating composition, at which time the concentration of the final coating composition is adjusted to be in the range of 0.1 to 10% by weight (solid content). Then carry out the coating.
  • step (c) of applying the above-described coating composition to at least one surface of the porous substrate is performed.
  • step (c) is not particularly limited in the present invention, and any known wet coating method may be used.
  • any known wet coating method may be used.
  • a method of uniformly dispersing using a doctor blade, etc., die casting, comma coating, screen printing, vacuum filtration coating, etc. Method, etc. are mentioned.
  • a drying process for removing the solvent may be further performed.
  • the drying process is performed at a temperature and time at a level that can sufficiently remove the solvent, and the conditions may vary depending on the type of solvent, and thus are not specifically mentioned in the present invention.
  • drying may be performed in a vacuum oven at 30 to 200° C., and drying methods such as hot air, hot air, drying by low humid air, and vacuum drying may be used.
  • it does not specifically limit about the drying time, it is normally performed in the range of 30 seconds-24 hours.
  • the thickness of the finally formed coating layer can be adjusted.
  • the present invention provides a lithium secondary battery including the separator.
  • the lithium secondary battery includes a positive electrode; cathode; It includes a separator and an electrolyte interposed therebetween, and includes the separator according to the present invention as the separator.
  • the lithium secondary battery may be a lithium-sulfur battery containing sulfur as a positive electrode active material.
  • the positive electrode may include a positive electrode current collector and a positive electrode active material applied to one or both surfaces of the positive electrode current collector.
  • the positive electrode current collector supports a positive electrode active material and is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • a positive electrode active material for example, copper, stainless steel, aluminum, nickel, titanium, palladium, calcined carbon, copper or stainless steel surface treated with carbon, nickel, silver, etc., aluminum-cadmium alloy, and the like may be used.
  • the positive electrode current collector may form fine irregularities on its surface to enhance the bonding strength with the positive electrode active material, and various forms such as films, sheets, foils, meshes, nets, porous bodies, foams, and nonwoven fabrics may be used.
  • the positive electrode active material may include a positive electrode active material and optionally a conductive material and a binder.
  • a sulfur-based compound specifically, elemental sulfur or a sulfur-based compound is included as the positive electrode active material.
  • the sulfur element may include inorganic sulfur (S 8 ).
  • inorganic sulfur (S 8 ) may be used.
  • the sulfur-based compound alone has no electrical conductivity, it is used in combination with a conductive material.
  • the positive electrode active material may be a sulfur-carbon composite.
  • carbon is a porous carbon material, providing a skeleton through which sulfur, which is a positive electrode active material, can be uniformly and stably fixed, and complements the electrical conductivity of sulfur so that an electrochemical reaction can proceed smoothly.
  • the porous carbon material may generally be prepared by carbonizing precursors of various carbon materials.
  • the porous carbon material includes irregular pores therein, the average diameter of the pores is in the range of 1 to 200 nm, and the porosity or porosity may be in the range of 10 to 90% of the total volume of the porosity. If the average diameter of the pores is less than the above range, the pore size is only at the molecular level and impregnation of sulfur is impossible. Conversely, if the pore size exceeds the above range, the mechanical strength of the porous carbon is weakened, which is preferable to be applied to the manufacturing process of the electrode. Not.
  • the porous carbon material may be spherical, rod-shaped, needle-shaped, plate-shaped, tube-shaped, or bulk-shaped, and may be used without limitation as long as it is commonly used in lithium-sulfur batteries.
  • the porous carbon material may have a porous structure or a high specific surface area, so long as it is commonly used in the art.
  • the porous carbon material graphite; Graphene; Carbon blacks such as denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Carbon nanotubes (CNT) such as single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT); Carbon fibers such as graphite nanofibers (GNF), carbon nanofibers (CNF), and activated carbon fibers (ACF); It may be one or more selected from the group consisting of natural graphite, artificial graphite, expanded graphite, and activated carbon, but is not limited thereto.
  • the porous carbon material may be a carbon nanotube.
  • the sulfur-carbon composite may contain 60 to 90 parts by weight of sulfur, preferably 65 to 85 parts by weight, more preferably 70 to 80 parts by weight, based on 100 parts by weight of the sulfur-carbon composite.
  • the sulfur content is less than the above-described range, the specific surface area increases as the content of the porous carbon material in the sulfur-carbon composite is relatively increased, so that the content of the binder increases when preparing the slurry.
  • Increasing the amount of the binder used may eventually increase the sheet resistance of the positive electrode and act as an insulator to prevent electron pass, thereby deteriorating the performance of the battery.
  • the positive electrode active material may further include at least one additive selected from a transition metal element, a group IIIA element, a group IVA element, a sulfur compound of these elements, and an alloy of these elements and sulfur.
  • the transition metal element is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Os, Ir, Pt, Au, or Hg and the like are included, and the group IIIA element includes Al, Ga, In, and Ti, and the group IVA element may include Ge, Sn, and Pb.
  • the positive electrode active material may be included in an amount of 50 to 95 parts by weight, preferably 70 to 90 parts by weight, based on 100 parts by weight of the positive electrode slurry composition.
  • the content of the positive electrode active material is less than the above range, it is difficult to sufficiently exhibit the electrochemical reaction of the positive electrode, and on the contrary, when the content of the positive electrode active material exceeds the above range, the content of the conductive material and binder described below is relatively insufficient, and the resistance of the positive electrode increases, There is a problem that the physical properties of the anode are deteriorated.
  • the positive electrode may further include a conductive material, and the conductive material is a material that serves as a path through which electrons move from a current collector to the positive electrode active material by electrically connecting the electrolyte and the positive electrode active material.
  • the conductive material is a material that serves as a path through which electrons move from a current collector to the positive electrode active material by electrically connecting the electrolyte and the positive electrode active material.
  • any one having conductivity can be used without limitation.
  • a carbon-based material having a porosity may be used as the conductive material, and examples of such a carbon-based material include carbon black, graphite, graphene, activated carbon, carbon fiber, etc., and metallic fibers such as metal mesh; Metallic powders such as copper, silver, nickel, and aluminum; Or an organic conductive material such as a polyphenylene derivative.
  • the conductive materials may be used alone or in combination.
  • the conductive material may be included in an amount of 1 to 10 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the positive electrode slurry composition. If the content of the conductive material is less than the above range, the non-reacting portion of sulfur in the positive electrode increases, resulting in a decrease in capacity. On the contrary, if it exceeds the above range, it is preferable to determine an appropriate content within the above-described range since it adversely affects the high-efficiency discharge characteristics and charge/discharge cycle life.
  • the positive electrode may further include a binder, and the binder further enhances binding strength between components constituting the positive electrode and between them and a current collector, and any binder known in the art may be used.
  • the binder may include a fluororesin binder including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE); A rubber-based binder including styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, and styrene-isoprene rubber; Cellulose-based binders including carboxyl methyl cellulose (CMC), starch, hydroxy propyl cellulose, and regenerated cellulose; Poly alcohol-based binder; Polyolefin-based binders including polyethylene and polypropylene; Polyimide binder; Polyester binder; And a silane-based binder; one, two or more mixtures or copolymers selected from the group consisting of may be used.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • a rubber-based binder including styrene-butadiene rubber (SBR), acrylon
  • the binder may be included in an amount of 1 to 10 parts by weight, preferably about 5 parts by weight, based on 100 parts by weight of the positive electrode slurry composition. If the content of the binder is less than the above range, the physical properties of the positive electrode may be deteriorated and the positive electrode active material and the conductive material may be eliminated, and if the content of the binder exceeds the above range, the ratio of the active material and the conductive material in the positive electrode may be relatively reduced, thereby reducing the battery capacity. It is desirable to determine the appropriate content within one range.
  • the positive electrode can be manufactured by a conventional method known in the art. For example, after preparing a slurry by mixing and stirring a solvent, a binder, a conductive material, and a dispersant as necessary in a positive electrode active material, it is applied (coated) to a current collector of a metal material, compressed, and dried to prepare a positive electrode have.
  • a positive electrode active material, a binder, and a conductive material may be uniformly dispersed.
  • water is most preferred as an aqueous solvent, and in this case, water may be distilled water or deionzied water.
  • the present invention is not limited thereto, and if necessary, lower alcohol that can be easily mixed with water may be used. Examples of the lower alcohol include methanol, ethanol, propanol, isopropanol, butanol, and the like, and preferably, they may be used by mixing with water.
  • the porosity of the positive electrode, specifically the positive electrode active material layer, prepared by the above-described composition and manufacturing method may be 60 to 75%, preferably 60 to 70%.
  • the filling degree of the positive electrode slurry composition including the positive electrode active material, the conductive material, and the binder becomes too high, so that a sufficient electrolyte solution capable of showing ionic conduction and/or electrical conduction between the positive electrode active materials is provided. Since it cannot be maintained, the output characteristics or cycle characteristics of the battery may be deteriorated, and there is a problem that the overvoltage and discharge capacity of the battery are severely reduced.
  • the porosity of the positive electrode exceeds 75% and has an excessively high porosity, there is a problem that the physical and electrical connection with the current collector is lowered, resulting in a decrease in adhesion and difficulty in reaction, and the increased porosity is filled with an electrolyte solution. Since there is a problem that the energy density of may be lowered, it is appropriately adjusted within the above range.
  • the negative electrode is a material capable of reversibly intercalating or deintercalating lithium (Li + ) as a negative active material, a material capable of reversibly forming a lithium-containing compound by reacting with lithium ions, lithium metal or lithium It may contain an alloy.
  • the material capable of reversibly intercalating or deintercalating lithium ions may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof.
  • a material capable of reversibly forming a lithium-containing compound by reacting with the lithium ions (Li + ) may be, for example, tin oxide, titanium nitrate, or silicon.
  • the lithium alloy is, for example, lithium (Li) and sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium ( It may be an alloy of a metal selected from the group consisting of Ca), strontium (Sr), barium (Ba), radium (Ra), aluminum (Al), and tin (Sn).
  • the negative active material may be lithium metal, and specifically, may be in the form of a lithium metal thin film or lithium metal powder.
  • the negative electrode current collector is as described in the positive electrode current collector.
  • the negative electrode may further include additives such as a binder, a conductive material and a thickener, and is not particularly limited as long as it is a conventional one used in manufacturing the negative electrode.
  • the binder and the conductive material are as described in the positive electrode.
  • the separator is as described above.
  • the electrolyte contains lithium ions, and is for causing an electrochemical oxidation or reduction reaction at the anode and the cathode through this.
  • the electrolyte may be a non-aqueous electrolyte or a solid electrolyte that does not react with lithium metal, but is preferably a non-aqueous electrolyte, and includes an electrolyte salt and an organic solvent.
  • the electrolyte salt contained in the non-aqueous electrolyte solution is a lithium salt.
  • the lithium salt may be used without limitation as long as it is commonly used in an electrolyte for a lithium secondary battery.
  • LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, ( CF 3 SO 2 ) 2 NLi, LiN(SO 2 F) 2 , lithium chloroborane, lithium lower aliphatic carboxylic acid, lithium 4-phenyl borate, lithium imide, and the like may be used.
  • the concentration of the lithium salt depends on several factors such as the exact composition of the electrolyte solvent mixture, the solubility of the salt, the conductivity of the dissolved salt, the charging and preconditioning of the battery, the working temperature and other factors known in the lithium battery field, from 0.2 to 2 M, Specifically, it may be 0.4 to 2 M, more specifically 0.4 to 1.7 M. If the concentration of the lithium salt is less than 0.2 M, the conductivity of the electrolyte may be lowered, resulting in deterioration of electrolyte performance, and if the concentration of the lithium salt exceeds 2 M, the viscosity of the electrolyte may increase, thereby reducing the mobility of lithium ions.
  • organic solvents included in the non-aqueous electrolyte those commonly used in electrolytes for lithium secondary batteries can be used without limitation, for example, ether, ester, amide, linear carbonate, cyclic carbonate, etc., alone or in combination of two or more Can be used. Among them, representatively, an ether-based compound may be included.
  • the ether compound may include an acyclic ether and a cyclic ether.
  • the acyclic ether includes dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, ethylpropyl ether, dimethoxyethane, diethoxyethane, methoxyethoxyethane, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methylethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, At least one selected from the group consisting of tetraethylene glycol methylethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, and polyethylene glycol methylethyl ether may be used, but is not limited thereto.
  • the cyclic ether is 1,3-dioxolane, 4,5-dimethyl-dioxolane, 4,5-diethyl-dioxolane, 4-methyl-1,3-dioxolane, 4-ethyl-1, 3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, 2-methyl-1,3 -Dioxolane, 2-vinyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2-methoxy-1,3-dioxolane, 2-ethyl-2-methyl-1, 3-dioxolane, tetrahydropyran, 1,4-dioxane, 1,2-dimethoxy benzene, 1,3-dimethoxy benzen
  • esters in the organic solvent methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ - Any one selected from the group consisting of valerolactone and ⁇ -caprolactone or a mixture of two or more of them may be used, but the present invention is not limited thereto.
  • linear carbonate compound examples include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, and ethylpropyl carbonate, or any one of them.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylmethyl carbonate
  • methylpropyl carbonate methylpropyl carbonate
  • ethylpropyl carbonate methylpropyl carbonate
  • ethylpropyl carbonate methylpropyl carbonate
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate , 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and any one selected from the group consisting of halides thereof, or a mixture of two or more thereof.
  • halides include, for example, fluoroethylene carbonate (FEC), but are not limited thereto.
  • the injection of the non-aqueous electrolyte may be performed at an appropriate step in the manufacturing process of the electrochemical device according to the manufacturing process and required physical properties of the final product. That is, it can be applied before assembling the electrochemical device or at the final stage of assembling the electrochemical device.
  • the lithium secondary battery according to the present invention in addition to winding, which is a general process, lamination and stacking of a separator and an electrode and folding are possible.
  • the shape of the lithium secondary battery is not particularly limited and may be in various shapes such as a cylindrical shape, a stacked type, and a coin type.
  • the present invention provides a battery module including the lithium secondary battery as a unit cell.
  • the battery module can be used as a power source for medium and large-sized devices that require high temperature stability, long cycle characteristics, and high capacity characteristics.
  • Examples of the medium and large-sized devices include a power tool that is driven by an electric motor; Electric vehicles including electric vehicles (EV), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf cart; Power storage systems, etc., but are not limited thereto.
  • Electric vehicles including electric vehicles (EV), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
  • Electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf cart; Power storage systems, etc., but are not limited thereto.
  • the mixed solution was placed in an autoclave made of stainless steel with a Teflon surface treatment, and hydrothermal synthesis reaction was performed at 220° C. for 18 hours.
  • a 20 ⁇ m polyethylene (porosity 68%) film was prepared as a porous substrate.
  • a coating composition containing 1% by weight of molybdenum disulfide containing defects obtained in Preparation Example 1 was applied to ethanol to form a coating layer on the porous substrate, and then dried at 60° C. for 12 hours to a thickness of 1 ⁇ m. This formed separator was prepared.
  • the prepared positive electrode slurry composition was applied on an aluminum current collector, dried at 50° C. for 12 hours, and compressed with a roll press to prepare a positive electrode.
  • the loading amount of the obtained positive electrode was 5.9 mAh/cm 2, and the porosity was 68%.
  • LiTFSI bis(trifluoromethanesulfonyl)imide
  • LiNO 3 lithium nitrate
  • the prepared positive electrode and the negative electrode were positioned to face each other, and the coating layer of the separator was placed to face the negative electrode therebetween, and 0.1 ml of the prepared electrolyte was injected to prepare a lithium secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the coating layer of the separator was disposed to face the positive electrode during battery manufacturing.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that a coating layer was not formed on the separator and a porous substrate was used as it is.
  • a plurality of disordered atomic arrangements are found on the surface of molybdenum disulfide including nanosheet-shaped defects, and it can be confirmed that a plurality of defects (arrows) exist.
  • XRD X-ray diffraction
  • EDS Energy Dispersive X-ray Spectrometer
  • the absorbance of the molybdenum disulfide containing defects according to Preparation Example 1 and the carbon nanotubes used as a conventional lithium-polysulfide adsorption material for lithium polysulfide (Li 2 S 6 ) solution was measured.
  • an Agilent 8453 of Agilent was used as a UV-Vis spectrophotometer. The lower the measured absorbance is, the better the adsorption effect on lithium polysulfide is, and the results obtained at this time are shown in FIG. 6.
  • the separation membrane prepared in Example 1 was observed with a scanning electron microscope (SEM). As a scanning electron microscope, Hitachi's S-4800 was used. The results obtained at this time are shown in FIG. 7.
  • the batteries prepared in Examples and Comparative Examples were discharged and charged three times at a current density of 0.1 C, and then discharged and charged three times at a current density of 0.2 C, followed by 0.5 C discharge and 0.3 C charge. While measuring the discharge capacity and coulomb efficiency, the battery life characteristics were evaluated. The results obtained at this time are shown in FIG. 8.
  • Example 1 in which the coating layer was arranged to face the cathode was superior to that of the Example in which the coating layer was arranged to face the anode have.
  • lithium polysulfide in which molybdenum disulfide including defects contained in the coating layer is eluted from the positive electrode is adsorbed to the coating layer, thereby inhibiting the growth of lithium dendrites. Therefore, it can be seen that the capacity characteristics of the lithium secondary battery are excellent and the life characteristics are also improved.

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

La présente invention concerne un séparateur pour une batterie rechargeable au lithium et une batterie rechargeable au lithium le comprenant et, plus particulièrement, un séparateur pour une batterie rechargeable au lithium, comprenant : un substrat poreux ; et une couche de revêtement formée sur au moins une surface du substrat poreux, la couche de revêtement comprenant du bisulfure de molybdène comprenant un défaut. Un séparateur pour une batterie rechargeable au lithium de la présente invention adsorbe le polysulfure de lithium et inhibe la croissance de dendrite de lithium au moyen d'une couche de revêtement comprenant du bisulfure de molybdène comprenant un défaut, et améliore ainsi la capacité et l'état de santé de la batterie rechargeable au lithium.
PCT/KR2020/005569 2019-05-03 2020-04-28 Séparateur pour batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant WO2020226321A1 (fr)

Priority Applications (4)

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JP2021532465A JP7275273B2 (ja) 2019-05-03 2020-04-28 リチウム二次電池用分離膜及びこれを含むリチウム二次電池
EP20801464.7A EP3883009A4 (fr) 2019-05-03 2020-04-28 Séparateur pour batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant
CN202080007114.2A CN113243060B (zh) 2019-05-03 2020-04-28 锂二次电池用隔膜和包含所述隔膜的锂二次电池
US17/312,650 US12107296B2 (en) 2019-05-03 2020-04-28 Separator for lithium secondary battery and lithium secondary battery comprising same

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