WO2020226329A1 - Séparateur fonctionnel comportant des sites catalytiques introduits en son sein, procédé de fabrication associé, et batterie secondaire au lithium le comprenant - Google Patents

Séparateur fonctionnel comportant des sites catalytiques introduits en son sein, procédé de fabrication associé, et batterie secondaire au lithium le comprenant Download PDF

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WO2020226329A1
WO2020226329A1 PCT/KR2020/005615 KR2020005615W WO2020226329A1 WO 2020226329 A1 WO2020226329 A1 WO 2020226329A1 KR 2020005615 W KR2020005615 W KR 2020005615W WO 2020226329 A1 WO2020226329 A1 WO 2020226329A1
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Prior art keywords
catalyst point
catalyst
separation membrane
point
lithium
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PCT/KR2020/005615
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English (en)
Korean (ko)
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김기현
김민수
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주식회사 엘지화학
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Priority claimed from KR1020200049799A external-priority patent/KR20200127869A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080005806.3A priority Critical patent/CN112913075B/zh
Priority to EP20801822.6A priority patent/EP3859823A4/fr
Priority to US17/289,090 priority patent/US20220006131A1/en
Priority to JP2021547028A priority patent/JP7162147B2/ja
Publication of WO2020226329A1 publication Critical patent/WO2020226329A1/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 functional separator in which a catalyst point is introduced, a method of manufacturing the same, and a lithium secondary battery including the same, and more particularly, in order to solve the problem caused by lithium polysulfide eluted from the anode, lithium on the surface of the separator
  • the present invention relates to a functional separator in which a catalyst point is introduced, a method of manufacturing the same, and a lithium secondary battery including the same, which can improve the capacity and life of a battery by coating a material capable of serving as a reduction catalyst of polysulfide.
  • Electrochemical devices are the field that is receiving the most attention in this respect, and among them, the development of secondary batteries such as lithium-sulfur batteries capable of charging and discharging has become the focus of interest, and in recent years, capacity density and In order to improve the specific energy, research and development on the design of new electrodes and batteries are being conducted.
  • Such an electrochemical device among which a Li-S battery, has a high energy density (theoretical capacity), and is in the spotlight as a next-generation secondary battery that can replace a lithium ion battery.
  • a reduction reaction of sulfur and an oxidation reaction of lithium metal occur during discharge, and at this time, sulfur forms lithium polysulfide (LiPS) of a linear structure from S 8 having a ring structure.
  • the lithium-sulfur battery is characterized by a stepwise discharge voltage until the polysulfide is completely reduced to Li 2 S.
  • Korean Patent Laid-Open No. 10-2017-0108496 (hereinafter referred to as 0108496, Applicant: Ulsan Institute of Science and Technology, Publication Date: 2017.09.27) has a problem in that the performance of a lithium-sulfur battery is deteriorated due to the elution of polysulfide. It discloses a lithium-sulfur battery for improving the. That is, the lithium-sulfur battery of No.
  • 0108496 has a structure in which a positive electrode, an intermediate layer (or porous and conductive film), a separator and a negative electrode are sequentially located, and a porous matrix including metal phthalocyanine in the intermediate layer (i.e., NiPc-PBBA Including COF or ZnPc-Py COF), the purpose of which is to block the migration of polysulfide to the outside of the positive electrode while lithium ions move smoothly.
  • NiPc-PBBA Including COF or ZnPc-Py COF
  • the COF of No. 0108496 is unable to act as a reduction catalyst, contains pores inside, so it only adsorbs lithium polysulfide eluted from the anode, and does not have electron conductivity, so in the area where there is no conductive network (carbon structure) Problems that remain without reduction may occur.
  • the first matrix which is a conductive carbon layer
  • it is disadvantageous to have a thickness of several tens of ⁇ m (actual experimental example: 45 ⁇ m). (It is obvious that the energy density per weight and volume will decrease with the use of such a thick matrix, resulting in a very disadvantageous in terms of battery performance).
  • Patent Document 1 Korean Patent Publication No. 10-2017-0108496
  • an object of the present invention is to provide a metal phthalocyanine catalyst point capable of serving as a catalyst for reduction of lithium polysulfide on the surface of a separator, or a coating layer including conductive carbon, in order to solve the problem caused by lithium polysulfide eluted from the anode. It is to provide a functional separator in which a catalyst point is introduced, a method of manufacturing the same, and a lithium secondary battery including the same, which can improve the capacity and life of a battery by forming.
  • the base separation membrane In order to achieve the above object, the present invention, the base separation membrane; And a coating layer containing a catalyst point located on the surface of the base separation membrane.
  • the present invention (a) dispersing the catalyst point in a solvent to prepare a dispersion containing the catalyst point; (b) filtering the prepared dispersion containing catalyst points; (c) obtaining and drying the catalyst point-containing powder from the upper layer of the filtrate obtained through the filtration; And (d) coating the obtained and dried catalyst point-containing powder on the surface of the base separation membrane; provides a method for producing a functional separation membrane containing a catalyst point is introduced.
  • the present invention provides a lithium secondary battery comprising; and an electrolyte.
  • the functional separator in which a catalyst point is introduced according to the present invention, a method of manufacturing the same, and a lithium secondary battery including the same, serve as a reduction catalyst of lithium polysulfide on the surface of the separator in order to solve the problem caused by lithium polysulfide eluting from the positive electrode. It has the advantage of improving the capacity and life of a battery by forming a coating layer including a metal phthalocyanine catalyst point or conductive carbon thereon.
  • FIG. 1 is a graph showing life characteristics of a lithium secondary battery according to an embodiment and a comparative example of the present invention.
  • FIG. 2 is a real image of a functional separation membrane for introducing a catalyst point according to the present invention.
  • FIG 3 is an electron microscope observation image of the functional separation membrane for introducing a catalyst point according to the present invention.
  • FIGS. 4 and 5 are graphs showing initial discharge capacity (a), secondary discharge capacity (b), and life characteristics (c) of lithium secondary batteries according to an exemplary embodiment and a comparative example of the present invention.
  • the functional separation membrane into which the catalyst point according to the present invention is introduced includes a base separation membrane and a catalyst point-containing coating layer located on the surface of the base separation membrane.
  • the separator is interposed between the positive electrode and the negative electrode (i.e., a physical separator having a function of physically separating the electrode), allowing the transport of lithium ions between the positive electrode and the negative electrode while separating or insulating the positive electrode and the negative electrode from each other. do.
  • a physical separator having a function of physically separating the electrode
  • the resistance to ion migration of the electrolyte is low and the electrolyte-moisture ability is excellent, and may be made of a porous, non-conductive or insulating material.
  • the base separation membrane in which the catalyst point-containing coating layer is not formed may be an independent member such as a film, or a coating layer added (adhesion, etc.) to any one or more of the anode and the cathode, and specifically, a porous polymer film ,
  • a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer is used alone or by laminating them.
  • it may be a conventional porous nonwoven fabric, for example, a nonwoven fabric made of high melting point glass fibers or polyethylene terephthalate fibers, but is not limited thereto.
  • a metal phthalocyanine catalyst point (specifically, a metal phthalocyanine catalyst that can serve as a reduction catalyst of lithium polysulfide on the surface of the base separation membrane) Transition metal-nitrogen-carbon catalyst point) or by forming a catalyst point-containing coating layer on the surface of the base separator by introducing a metal phthalocyanine catalyst point on the inside and outside of the conductive carbon having a high specific surface area and high porosity. It has features that improve and life. Accordingly, the functional separator for introducing a catalyst point of the present invention can be applied to various energy storage devices including lithium secondary batteries such as lithium-sulfur batteries that require high catalytic effect.
  • the catalyst point is a complex formed by bonding a nitrogen atom to a transition metal and a carbon atom to the nitrogen atom, and acts as a catalyst on the surface of the base separation membrane (at least one of the outer surface and the inner surface of the pores) to various energy storage devices It can improve the kinetic of the. That is, the catalyst point 20 is adsorbed and bonded to at least one of the outer surface and the inner surface of the pores of the base separation membrane, and thus, the catalyst point is a lithium secondary battery, especially a separator of a lithium-sulfur battery, among energy storage devices. It may be suitable as a solvent catalyst.
  • the catalyst point is a type of macrocyclic compound having a structure in which rings of nitrogen atoms and carbon atoms cross, and has a chemical structure in which metal ions are coordinated in the center. That is, in other words, the catalyst point may include a transition metal-nitrogen-carbon continuous bond (or sequential bond).
  • the number of nitrogen atoms bonded to the transition metal is preferably four. If the number of nitrogen atoms bonded to the transition metal is less than 4, the activity as a catalyst may be deteriorated. When it exceeds 4, structural stability may be deteriorated and thus catalytic activity may be lowered.
  • nitrogen is bonded to a transition metal, its structure is stable and exhibits excellent catalytic properties. Therefore, it has very high stability and catalyst compared to the catalyst point formed by bonding of atoms other than nitrogen to the transition metal. It can have an effect.
  • the molar ratio of the transition metal and nitrogen may be 1: 2 to 10, preferably 1: 2 to 8, more preferably 1: 3 to 5. If the molar ratio of the transition metal and nitrogen is out of the range, the surface of the base separation membrane may not be sufficiently doped as required or the amount of nitrogen per unit weight may increase, resulting in a decrease in catalytic activity.
  • the catalyst point is a nano-level composite having a size of 0.1 to 10 nm, preferably 0.5 to 8 nm, more preferably 0.5 to 5 nm, and the volume of the pores even if bonded to the inner surface of the pores of the base separation membrane There is almost no reduction in size and, so pore clogging does not occur when passing through pores such as lithium ions.
  • the transition metal may be at least one selected from the group consisting of iron (Fe), nickel (Ni), manganese (Mn), copper (Cu), and zinc (Zn), but a transition metal capable of exhibiting catalytic activity If so, it is not limited thereto.
  • the catalyst point is a metal-phthalocyanine (MePc), iron phthalocyanine (FePc), nickel phthalocyanine (NiPc), manganese phthalocyanine (MnPc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc) and these Mixtures and the like can be illustrated.
  • the catalyst point-containing coating layer may be formed on a part of the surface of the base separation membrane, but in order to maximize the effect of the use of the catalyst point (up to conductive carbon, if necessary), it is preferable to form it on the entire surface of the base separation membrane. desirable.
  • the catalyst point-containing coating layer has a thickness of 0.1 to 20 ⁇ m, preferably 0.5 to 10 ⁇ m, more preferably 1 to 8 ⁇ m (even when conductive carbon to be described later is included in the coating layer), the catalyst point-containing coating layer If the thickness of is less than 0.1 ⁇ m, the conductive network is not sufficiently formed, resulting in a problem of lowering the electronic conductivity. If it exceeds 20 ⁇ m, the cell resistance increases by interfering with the passage of lithium ions, and the energy density per volume There is also a concern that adverse problems may arise.
  • the content of the coating layer containing the catalyst point is 1 to 200 ⁇ g/cm 2 , preferably 10 to 150 ⁇ g/cm 2 , more preferably 20 to 120 ⁇ g/cm 2 with respect to the surface area of the base separation membrane to be coated. It may be (even when conductive carbon to be described later is included in the coating layer). If the coating content of the coating layer containing the catalyst point is less than 1 ⁇ g/cm 2 with respect to the surface area of the base separation membrane, the effect of the use of the catalyst point may be insignificant, and if it exceeds 200 ⁇ g/cm 2 , the catalyst point is There may be no further effects that can be obtained with use.
  • the functional separation membrane into which the catalyst point according to the present invention is introduced may further contain conductive carbon in the catalyst point-containing coating layer.
  • the conductive carbon is also coated on the surface of the base separator, serves to support an inorganic material, and the conductive carbon itself has a pore structure, so that the electrolyte can be freely accessed.
  • the conductive carbon has conductivity as the name suggests, and by this property, lithium polysulfide can be reduced by transferring electrons to a supported inorganic material such as the catalyst point.
  • the catalyst point When conductive carbon is further included in the coating layer containing the catalyst point as described above, the catalyst point may be bonded to any one or more of the outer surface of the conductive carbon and the inner surface of the hole, and specifically, the outer surface of the conductive carbon. And adsorbed to the inner surface of the hole through van der Waals attraction. That is, the Van der Waals action has a bond form between faces and faces, not between specific elements, and may exhibit a stronger adsorption power than other types of bonds. Therefore, even if a catalyst point is bonded to the surface of the conductive carbon, conductivity Can maintain the natural characteristics of carbon.
  • the mixing ratio of the catalyst point and the conductive carbon may be 0.1 to 99.9: 10 to 90 as a weight ratio.
  • any conductive carbon material capable of exhibiting the above effects may be applied without particular limitation.
  • carbon nanotubes (CNT), graphene, and reduced graphene oxide (rGO) may be exemplified, and the use of the reduced graphene oxide is preferable, and peeling is advantageous due to thermal expansion, and accordingly, it is thinner. It may be more preferable to use a thermally exfoliated reduced graphene oxide (TErGO), which can exhibit excellent performance due to area coating.
  • TErGO thermally exfoliated reduced graphene oxide
  • the thermally exfoliated reduced graphene oxide may be obtained by heat-treating the graphene oxide to prepare thermally expanded graphene oxide (or thermally exfoliated graphene oxide), followed by reduction treatment.
  • the heat treatment for preparing the thermally expanded graphene oxide may be performed by a known method or various methods of modifying it, and is not particularly limited in the present invention.
  • the heat treatment may be performed for 10 minutes to 3 hours at a temperature range of 300 to 900 °C.
  • the thermal exfoliation-reduced graphene oxide (TErGO) is exfoliated, and may have a thickness of 0.5 to 40 nm, preferably 5 to 30 nm, more preferably 10 to 20 nm, and may have a plate shape or a flake shape.
  • the degree of thermal expansion of the thermally exfoliated reduced graphene oxide (TErGO) may vary from less than 100 m 2 /g to 900 m 2 /g in the range of BET, and the degree of reduction can be measured through XPS or EA. Do.
  • the reduced graphene oxide may be about 9:1.
  • the reduced graphene oxide before peeling has a thickness of about 50 to 500 nm, and because it is easily desorbed when coated in the form of particles, it not only requires the use of a binder (even if it is not a separator), but also has a low coating density to achieve the desired effect. I could't get enough.
  • the present invention can be uniformly and densely coated on a substrate by using a thermally exfoliated reduced graphene oxide in a plate or flake shape having a thickness in a certain range through peeling.
  • pores are formed in the conductive carbon, and the porosity of the pores is 40 to 90%, preferably 60 to 80%, and if the porosity of the pores is less than 40%, lithium ions cannot be transferred normally, and thus the resistance component It may act as a problem, and if it exceeds 90%, a problem of lowering the mechanical strength may occur.
  • the pore size of the conductive carbon is 10 nm to 5 ⁇ m, preferably 50 nm to 5 ⁇ m, and if the pore size is less than 10 nm, there may be a problem in which lithium ion transmission is impossible, and the pore size exceeding 5 ⁇ m In this case, a battery short circuit and safety problems may occur due to contact between electrodes.
  • a binder may be interposed so that the coating layer containing the catalyst point can be more easily coated on the surface of the base separation membrane.
  • TErGO thermally exfoliated reduced graphene oxide
  • rGO reduced graphene oxide
  • the catalyst point-containing coating layer It can be easily coated on the surface of the base separator by being free-standing without a silver binder.
  • the functional separation membrane into which the catalyst point as described above is introduced can be widely used in energy storage devices. Specifically, it can be used as a separator for a lithium secondary battery, and in particular, it can be applied as a separator for a lithium-sulfur battery accompanied by a reduction reaction of sulfur, so that high performance of the battery can be realized, and the manufacturing cost is also inexpensive, so it can be advantageous for commercialization. .
  • the catalyst point of the present invention can serve as a reduction catalyst, whereas the non-conductive COF (Covalent -Organic Framework) is impossible, and because COF contains pores inside, it only plays a role of adsorbing lithium polysulfide eluted from the anode.
  • the catalyst point of the present invention is to increase the reaction rate by reducing sulfur (S8) or long chain polysulfide to reduce it to short chain polysulfide. ) Is advantageous.
  • COF may remain unreduced at a portion where there is no conduction network (carbon structure) because there is no electronic conductivity
  • the energy density per weight and volume will decrease if such a thick matrix is used, and as a result, it is very disadvantageous in terms of battery performance.
  • the present invention it is possible to manufacture the separator as thin as 20 ⁇ m or less by using the membrane as a support, and is advantageous in terms of cell energy density.
  • the catalyst point of the present invention is used as a reduction catalyst, it is possible to improve performance even with a minimum amount.
  • the COF of No. 0108496 since lithium polysulfide must be adsorbed in the internal pores, the effect can be exhibited only when the amount of the amount is increased. For this reason, coupling COF to the catalyst point is very disadvantageous in terms of efficiency and energy density, and if lithium polysulfide accumulates inside the COF due to the loss of the conductive network, active material is lost and the amount of discharge decreases, and these materials act as resistance. As a result, there is a fear of deteriorating the performance of the battery.
  • the method of manufacturing the functional separation membrane into which the catalyst points are introduced includes the steps of: (a) dispersing the catalyst points in a solvent to prepare a dispersion containing the catalyst points, (b) filtering the prepared dispersion containing the catalyst points, (c) the Obtaining and drying the catalyst point-containing powder from the upper layer of the filtrate obtained through filtration, and (d) coating the obtained and dried catalyst point-containing powder on the surface of the base separation membrane, and if necessary, the ( After step a), a step (a-1) of preparing a dispersion containing catalyst points including conductive carbon by supplying conductive carbon to the prepared dispersion containing catalyst points may be further included.
  • a catalyst point dispersion may be prepared by dispersing (or dissolving) the catalyst point in a solvent, and if necessary, after dispersing the catalyst point in a solvent, bath sonication is performed.
  • the concentration of the catalyst point dispersion may be 5 to 15%, preferably 5 to 12%, more preferably 5 to 10% based on the weight of the solid content. If the concentration of the catalyst point dispersion is less than 5% based on the weight of the solid content, the weight of the catalyst point is reduced and there is a fear of poor catalytic activity. If it exceeds 15%, the content of the catalyst point is excessive and coating The pores of the target base separation membrane may be clogged.
  • the catalyst point is metal-phthalocyanine (MePc) as described above, for example, iron phthalocyanine (FePc), nickel phthalocyanine (NiPc), manganese phthalocyanine (MnPc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), and And mixtures thereof.
  • the metal-phthalocyanine is a kind of macrocyclic compound having a structure in which rings of nitrogen atom-carbon atom cross, and has a chemical structure in which metal ions are coordinated in the center. As described above, since metal-phthalocyanine is used as a catalyst point, it is possible to prepare a catalyst material including a catalyst point having a stable structure in which four nitrogens are bonded to a transition metal.
  • the solvent used in step (a) is dimethyl carbonate, dimethyl formamide, N-methyl formamide, sulfolane (tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, N-butyl sulfone, dimethyl Sulfoxide, pyrolidinone (HEP), dimethylpiperidone (DMPD), N-methylpyrrolidinone (NMP), N-methylacetamide, dimethylacetamide (DMAc), N,N-dimethylformamide (DMF) , Diethylacetamide (DEAc), dipropylacetamide (DPAc), ethanol, propanol, butanol, hexanol, isopropyl alcohol (IPA), ethylene glycol, tetrachloroethylene, propylene glycol, toluene, trpentine, methyl acetate , Ethyl acetate, petroleum ether, acetone, cresol, and may be one or more organic solvent
  • step (a-1) is a process of adsorbing (or introducing) the catalyst point to the surface of the conductive carbon, that is, transition metal-nitrogen-on the inner and outer surfaces of the conductive carbon having a high specific surface area and high porosity.
  • the carbon catalyst point is adsorbed and bonded through the van der Waals attraction.
  • the mixing ratio of the catalyst point and the conductive carbon applies mutatis mutandis to the above.
  • ultrasonic treatment may be performed if necessary.
  • the filtering in step (b) may be applied mutatis mutandis to a general filtration method such as a vacuum pump, and after the filtration process is performed, a washing process using alcohol such as ethanol may be additionally performed as necessary. have.
  • the step (c) is a process of obtaining and drying the catalyst point-containing powder from the upper layer of the filtrate obtained through filtration in the step (b), and when applying to the conductive carbon, the bonding force between the catalyst point and the conductive carbon
  • the drying process be performed under a specific temperature and time. At this time, the drying is 1 to 24 hours, preferably 5 to 20 hours, more preferably 10 to 14 hours at a temperature of 60 to 100 °C, preferably 65 to 95 °C, more preferably 70 to 90 °C Can be performed during.
  • the step (d) is a step in which the obtained and dried catalyst point-containing powder is coated on the surface of the base separation membrane to finally prepare a functional separation membrane into which the catalyst point according to the present invention is introduced.
  • the coating is a dropcast method, a dip-coating method, a blade coating method, a spray coating method, a meyer bar coating method, or a vacuum filtration method. It can be performed by the (vacuum filter) method.
  • the lithium secondary battery including the functional separator into which the catalyst point is introduced includes a positive electrode, a negative electrode, the catalyst point introduction functional separator and an electrolyte interposed between the positive electrode and the negative electrode, and a lithium-sulfur battery, a lithium air battery and a lithium All lithium secondary batteries known in the art, such as metal batteries, can be exemplified, and among them, lithium-sulfur batteries are preferred.
  • the description of the functional separator included in the lithium secondary battery is instead of the above, and other positive electrodes, negative electrodes, and electrolytes applied to the lithium secondary battery may be conventional ones used in the art, and a detailed description thereof will be described later. Do it.
  • the battery module or battery pack may include a power tool; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or a system for power storage; It can be used as a power supply for any one or more of medium and large devices.
  • EVs electric vehicles
  • PHEVs plug-in hybrid electric vehicles
  • a system for power storage It can be used as a power supply for any one or more of medium and large devices.
  • a positive electrode composition including a positive electrode active material, a conductive material, and a binder
  • a slurry prepared by diluting it in a predetermined solvent (dispersion medium) is directly coated on the positive electrode current collector, and By drying, an anode layer can be formed.
  • a film obtained by peeling from the support may be laminated on a positive electrode current collector to prepare a positive electrode layer.
  • a positive electrode may be manufactured in various ways using a method widely known to those skilled in the art.
  • the conducting material serves as a path through which electrons move from the positive electrode current collector to the positive electrode active material, thereby imparting electron conductivity, as well as electrically connecting the electrolyte and the positive electrode active material so that lithium ions (Li+) in the electrolyte At the same time, it acts as a pathway to move to and react to sulfur. Therefore, if the amount of the conductive material is insufficient or the role cannot be performed properly, the non-reactive portion of the sulfur in the electrode increases, resulting in a decrease in capacity. In addition, since it adversely affects the high rate discharge characteristics and charge/discharge cycle life, it is necessary to add an appropriate conductive material.
  • the content of the conductive material is preferably added appropriately within the range of 0.01 to 30% by weight based on the total weight of the positive electrode composition.
  • the conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery, for example, graphite; Carbon blacks such as denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride, aluminum and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives may be used.
  • Carbon blacks such as denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black
  • Conductive fibers such as carbon fibers and metal fibers
  • Metal powders such as carbon fluoride, aluminum and nickel powder
  • Conductive whiskers such as zinc oxide and potassium titanate
  • Conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives may be used.
  • conductive materials include acetylene black-based Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack, EC-based Armak Company (Armak Company) product, Vulcan (Vulcan) XC-72 Cabot Company (Cabot Company) product and Super-P (Timcal company product), and the like can be used.
  • the binder is for attaching the positive electrode active material to the current collector well, and must be well soluble in a solvent, and must not only form a conductive network between the positive electrode active material and the conductive material, but also have adequate impregnation of the electrolyte.
  • the binder may be any binder known in the art, and specifically, a fluororesin binder including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE); Rubber binders including styrene-butadiene rubber, acrylonitrile-butadiene rubber, and styrene-isoprene rubber; Cellulose-based binders including carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, and regenerated cellulose; Polyalcohol binder; Polyolefin-based binders including polyethylene and polypropylene; Polyimide-based binder, polyester-based binder, silane-based binder; may be a mixture or a copolymer selected from the group consisting of, but is not limited thereto.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • Rubber binders including styrene-butadiene rubber,
  • the content of the binder may be 0.5 to 30% by weight based on the total weight of the positive electrode composition, but is not limited thereto.
  • the content of the binder resin is less than 0.5% by weight, the physical properties of the positive electrode are deteriorated, so that the positive electrode active material and the conductive material may fall off, and if it exceeds 30% by weight, the ratio of the active material and the conductive material in the positive electrode is relatively reduced. Battery capacity may be reduced, and efficiency may be lowered by acting as a resistance element.
  • the positive electrode composition including the positive electrode active material, the conductive material, and the binder may be diluted in a predetermined solvent and coated on the positive electrode current collector using a conventional method known in the art.
  • a positive electrode current collector is prepared.
  • the positive electrode current collector has a thickness of 3 to 500 ⁇ m.
  • Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing a chemical change in the battery.
  • stainless steel, aluminum, nickel, titanium, sintered carbon, or aluminum or stainless steel Carbon, nickel, titanium, silver, or the like may be used on the surface of the steel.
  • the current collector may increase the adhesion of the positive electrode active material by forming fine irregularities on its surface, and various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics are possible.
  • a slurry obtained by diluting a positive electrode composition including a positive electrode active material, a conductive material, and a binder in a solvent is applied on the positive electrode current collector.
  • the positive electrode composition including the positive electrode active material, the conductive material, and the binder may be mixed with a predetermined solvent to prepare a slurry.
  • the solvent should be easy to dry and can dissolve the binder well, but it is most preferable that the positive electrode active material and the conductive material can be maintained in a dispersed state without dissolving.
  • the solvent may be water or an organic solvent, and the organic solvent may be at least one selected from the group of dimethylformamide, isopropyl alcohol or acetonitrile, methanol, ethanol, and tetrahydrofuran.
  • the method of applying the slurry-like positive electrode composition for example, Doctor blade coating, Dip coating, Gravure coating, Slit die coating. coating), spin coating, comma coating, bar coating, reverse roll coating, screen coating, cap coating, etc. It can be manufactured.
  • evaporation of the solvent (dispersion medium), the denseness of the coating film, and adhesion between the coating film and the current collector are achieved through a subsequent drying process. At this time, drying is carried out according to a conventional method, and this is not particularly limited.
  • any one capable of occluding and releasing lithium ions can be used, and examples thereof include metal materials such as lithium metal and lithium alloys, and carbon materials such as low crystalline carbon and high crystalline carbon.
  • Soft carbon and hard carbon are typical examples of low-crystalline carbon, and natural graphite, kish graphite, pyrolytic carbon, and liquid crystal pitch-based carbon fiber are high-crystalline carbon.
  • High-temperature calcined carbons such as (Mesophase pitch based carbon fiber), Meso-carbon microbeads, Mesophase pitches, and Petroleum or coal tar pitch derived cokes are typical.
  • alloys containing silicon or oxides such as Li 4 Ti 5 O 12 are also well-known cathodes.
  • the negative electrode may include a binder, and as the binder, polyvinylidenefluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), and polyacrylonitrile (Polyacrylonitrile), polymethylmethacrylate (Polymethylmethacrylate), styrene-butadiene rubber (SBR), and various kinds of binder polymers can be used.
  • PVDF polyvinylidenefluoride
  • PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • SBR styrene-butadiene rubber
  • the negative electrode may optionally further include a negative electrode current collector for supporting the negative electrode active layer including the negative electrode active material and the binder.
  • the negative electrode current collector may be specifically selected from the group consisting of copper, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof.
  • the stainless steel may be surface-treated with carbon, nickel, titanium, or silver, and an aluminum-cadmium alloy may be used as the alloy.
  • calcined carbon, a non-conductive polymer surface-treated with a conductive agent, or a conductive polymer may be used.
  • the binder serves as a paste of the negative active material, mutual adhesion between the active materials, adhesion between the active material and the current collector, and a buffering effect on expansion and contraction of the active material.
  • the binder is the same as described above for the binder of the positive electrode.
  • the negative electrode may be a lithium metal or a lithium alloy.
  • the negative electrode may be a thin film of lithium metal, and lithium and one selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, and Sn It may be an alloy with the above metals.
  • the electrolyte solution includes a solvent and a lithium salt, and may further include additives, if necessary.
  • a solvent a conventional non-aqueous solvent serving as a medium through which ions involved in the electrochemical reaction of a battery can move may be used without particular limitation.
  • the non-aqueous solvent include carbonate-based solvents, ester-based solvents, ether-based solvents, ketone-based solvents, alcohol-based solvents, and aprotic solvents.
  • the carbonate-based solvent dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC) ), ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC), and the ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethylethyl acetate, methyl Propionate, ethyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, mevalonolactone, and caprolactone, and the ether solvents include di Ethyl ether, dipropyl ether, dibutyl ether, dimethoxymethane, trimethoxymethane, dimethoxyethane, die
  • the ketone solvent includes cyclohexanone
  • the alcohol solvent includes ethyl alcohol and isopropyl alcohol
  • the aprotic solvent includes nitriles such as acetonitrile, and amino acids such as dimethylformamide.
  • Dioxolanes such as Drew, 1,3-dioxolane (DOL), and sulfolane.
  • Non-aqueous solvents as described above can be used alone or in combination of two or more, and the mixing ratio in the case of mixing two or more can be appropriately adjusted according to the performance of the intended battery, and 1,3-dioxolane and dimethoxyethane A solvent mixed in a volume ratio of 1: 1 can be illustrated.
  • NiPc nickel phthalocyanine
  • DMF N,N-dimethylformamide
  • NiPc nickel phthalocyanine
  • the dried powder was coated on the entire surface of a porous base separator made of polyethylene by vacuum filtration and then dried to prepare a functional separator in which a catalyst point was introduced. Meanwhile, during the coating, the thickness of the coating material was 0.5 ⁇ m, and the coating amount was 10 ⁇ g/cm 2.
  • NiPc nickel phthalocyanine
  • NiPc-PBBA COF containing metal phthalocyanine here, the raw material of COF is 1,4-benzenediboronic acid
  • CNT paper After preparing a composite by coating NiPc-PBBA COF containing metal phthalocyanine (here, the raw material of COF is 1,4-benzenediboronic acid) on CNT paper, it is placed so as to face the separator in the bare state, and in the bare state A conventional separator in which the separator and the composite are physically separated was prepared (corresponding to Korean Patent Publication No. 10-2017-0108496, which is a prior art document).
  • Example 1 The separator prepared in Example 1 and Comparative Examples 1 and 2, and an electrolyte solution (DOL:DME (1:1), 1.0 M LiTFSI, 1 wt% LiNO 3 ) 70 ⁇ l, a coin containing a sulfur anode and a lithium metal anode
  • DOL:DME (1:1), 1.0 M LiTFSI, 1 wt% LiNO 3 a coin containing a sulfur anode and a lithium metal anode
  • a cell-type lithium-sulfur battery was prepared (however, when the separator of Comparative Example 2 was interposed between the positive electrode and the negative electrode, the composite of the entire separator was opposed to the positive electrode side).
  • Example 1 is a graph showing the life characteristics of a lithium secondary battery according to an embodiment and a comparative example of the present invention. As shown in FIG. 1, the lithium-sulfur battery of Example 2 to which a functional separator having a catalyst point is applied is applied.
  • NiPc nickel phthalocyanine
  • DMF N,N-dimethylformamide
  • the mixture was filtered with a vacuum pump and washed with 1000 ml of ethanol, and the upper powder of the filtrate was dried at 80° C. for 12 hours.
  • the dried powder was coated on the entire surface of a porous base separator made of polyethylene by vacuum filtration and then dried to prepare a functional separator in which a catalyst point was introduced.
  • the thickness of the coating material was 1 ⁇ m, and the coating amount was 20 ⁇ g/cm 2.
  • a functional separator in which a catalyst point was introduced was prepared in the same manner as in Example 3 above.
  • a functional separation membrane in which a catalyst point was introduced was prepared in the same manner as in Example 3 above.
  • a conventional separator was prepared by surface coating only reduced graphene oxide (rGO, Sixth Element), which is conductive carbon, on the surface of the bare separator made of polyethylene (PE).
  • rGO reduced graphene oxide
  • PE polyethylene
  • FIGS. 2 and 3 it can be seen that the catalyst point-containing functional separator according to the present invention has a uniformly well formed catalyst point-containing coating layer.
  • the catalyst point-containing functional separator when the catalyst point-introducing functional separator was observed with an electron microscope, it can be seen that the catalyst point-containing coating layer is evenly spread in a plate shape without agglomeration.
  • the discharge current rate of the lithium-sulfur batteries prepared from Examples 6 to 8 and Comparative Example 6 was set to 0.1 C 3 times, 0.2 C 3 times, and then 0.5 C, and then the life characteristics were observed.
  • 4 is a graph showing discharge capacity (a) and life characteristics (b) of lithium secondary batteries according to an embodiment and a comparative example of the present invention. As shown in FIG. 4, Examples 6 to 8 in which the catalyst point introduction functional separator was applied to a lithium-sulfur battery were compared with the lithium-sulfur battery of Comparative Example 6 in which only conductive carbon was coated on the surface of the separator. It was confirmed that all appeared excellently.
  • FIG. 5 is a graph showing discharge capacity (a) and life characteristics (b) of a lithium secondary battery according to an embodiment and a comparative example of the present invention. As shown in FIG. 5, Examples 9 to 11 in which the functional separator introducing a catalyst point was applied to a lithium-sulfur battery. In addition, discharge capacity and lifespan characteristics compared to the lithium-sulfur battery of Comparative Example 7 in which only conductive carbon was coated on the surface of the separator. It was confirmed that all appeared excellently.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un séparateur fonctionnel comportant des sites catalytiques introduits en son sein, un procédé de fabrication associé, et une batterie secondaire au lithium le comprenant. Afin de résoudre des problèmes se produisant à cause du polysulfure de lithium élué à partir d'une cathode, un matériau pouvant jouer le rôle d'un catalyseur de réduction de polysulfure de lithium est enduit sur une surface du séparateur, ce qui permet d'améliorer la capacité et la durée de vie de la batterie. Le séparateur fonctionnel comportant des sites catalytiques introduits en son sein comprend : un séparateur de base ; et une couche de revêtement contenant des sites catalytiques positionnée sur une surface du séparateur de base.
PCT/KR2020/005615 2019-05-03 2020-04-28 Séparateur fonctionnel comportant des sites catalytiques introduits en son sein, procédé de fabrication associé, et batterie secondaire au lithium le comprenant WO2020226329A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202080005806.3A CN112913075B (zh) 2019-05-03 2020-04-28 引入了催化位点的功能性隔膜、其制造方法和包含其的锂二次电池
EP20801822.6A EP3859823A4 (fr) 2019-05-03 2020-04-28 Séparateur fonctionnel comportant des sites catalytiques introduits en son sein, procédé de fabrication associé, et batterie secondaire au lithium le comprenant
US17/289,090 US20220006131A1 (en) 2019-05-03 2020-04-28 Functional separator having catalytic sites introduced thereinto, manufacturing method therefor, and lithium secondary battery comprising same
JP2021547028A JP7162147B2 (ja) 2019-05-03 2020-04-28 触媒部位が導入された機能性分離膜、その製造方法及びこれを含むリチウム二次電池

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KR10-2019-0052321 2019-05-03
KR20190052321 2019-05-03
KR1020200049799A KR20200127869A (ko) 2019-05-03 2020-04-24 촉매점이 도입된 기능성 분리막, 그 제조 방법 및 이를 포함하는 리튬 이차전지
KR10-2020-0049799 2020-04-24

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CN113725558A (zh) * 2021-07-29 2021-11-30 长沙矿冶研究院有限责任公司 一种锂硫电池改性隔膜及其制备方法
CN114188669A (zh) * 2021-12-21 2022-03-15 云南大学 一种功能隔膜及其制备方法和应用

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KR20170108496A (ko) 2016-03-18 2017-09-27 울산과학기술원 리튬-황 전지용 다공성 및 전도성막, 이의 제조방법, 및 이를 포함하는 리튬-황 전지
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KR20190052321A (ko) 2017-11-08 2019-05-16 주식회사 케이티 무선 통신 방법 및 무선 통신 시스템
KR20200049799A (ko) 2017-09-29 2020-05-08 도쿄엘렉트론가부시키가이샤 유체로 기판을 코팅하기 위한 방법 및 시스템

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KR20100107012A (ko) * 2008-01-03 2010-10-04 유티씨 파워 코포레이션 Ｐｅｍ 연료 전지를 위한 보호 및 침전 층
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CN114188669A (zh) * 2021-12-21 2022-03-15 云南大学 一种功能隔膜及其制备方法和应用
CN114188669B (zh) * 2021-12-21 2022-08-02 云南大学 一种功能隔膜及其制备方法和应用

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