WO2021010605A1 - Batterie secondaire au lithium - Google Patents

Batterie secondaire au lithium Download PDF

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Publication number
WO2021010605A1
WO2021010605A1 PCT/KR2020/008043 KR2020008043W WO2021010605A1 WO 2021010605 A1 WO2021010605 A1 WO 2021010605A1 KR 2020008043 W KR2020008043 W KR 2020008043W WO 2021010605 A1 WO2021010605 A1 WO 2021010605A1
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Prior art keywords
positive electrode
secondary battery
solvent
lithium
sulfur
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PCT/KR2020/008043
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English (en)
Korean (ko)
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송명준
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주식회사 엘지화학
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Priority claimed from KR1020200073784A external-priority patent/KR20210009272A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080028671.2A priority Critical patent/CN113692665A/zh
Priority to US17/605,761 priority patent/US20220231342A1/en
Priority to BR112021020560A priority patent/BR112021020560A2/pt
Priority to JP2021563684A priority patent/JP7427025B2/ja
Priority to EP20840658.7A priority patent/EP3951931A4/fr
Publication of WO2021010605A1 publication Critical patent/WO2021010605A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium secondary battery.
  • lithium-ion As the application area of secondary batteries expands to electric vehicles (EV) or energy storage systems (ESS), lithium-ion has a relatively low energy storage density ( ⁇ 250 Wh/kg) compared to its weight. Ion secondary batteries have limitations in their application to these products. In contrast, lithium-sulfur secondary batteries are in the spotlight as a next-generation secondary battery technology because they can theoretically realize a high energy storage density ( ⁇ 2,600 Wh/kg) to weight.
  • the lithium-sulfur secondary battery is a battery system using a sulfur-based material having a sulfur-sulfur bond as a positive electrode active material and lithium metal as a negative electrode active material.
  • This lithium-sulfur secondary battery has the advantage that sulfur, which is the main material of the positive electrode active material, has an abundance of resources worldwide, is non-toxic, and has a low weight per atom.
  • lithium which is a negative electrode active material
  • a sulfur-based material which is a positive electrode active material
  • the oxidation reaction of lithium is a process in which lithium metal releases electrons and is converted into lithium cation form.
  • the sulfur reduction reaction is a process in which a sulfur-sulfur bond accepts two electrons and is converted into a sulfur anion form. The lithium cation generated by the oxidation reaction of lithium is transferred to the positive electrode through the electrolyte, and forms a salt by combining with the sulfur anion generated by the reduction reaction of sulfur.
  • Sulfur which is a positive active material, has low electrical conductivity, so it is difficult to secure reactivity with electrons and lithium ions in a solid-state form.
  • Existing lithium-sulfur secondary batteries induce a liquid-state reaction and improve reactivity by generating an intermediate polysulfide in the form of Li 2 S x to improve the reactivity of sulfur.
  • an ether solvent such as dioxolane and dimethoxyethane having high solubility in lithium polysulfide is used as a solvent for the electrolyte solution.
  • the existing lithium-sulfur secondary battery builds a catholyte-type lithium-sulfur secondary battery system to improve reactivity.
  • Korean Patent Laid-Open No. 2016-0037084 uses a carbon nanotube aggregate of a three-dimensional structure coated with graphene with a carbon material to block the melting of lithium polysulfide and improve the conductivity of the sulfur-carbon nanotube composite. It discloses that it can be improved.
  • Korean Patent Registration No.1379716 uses a graphene composite containing sulfur prepared by treating graphene with hydrofluoric acid to form pores on the surface of graphene and growing sulfur particles in the pores as a positive electrode active material. It is disclosed that lithium polysulfide elution can be suppressed to minimize a decrease in capacity of the battery.
  • a lithium-sulfur secondary battery including a graphene composite positive electrode containing sulfur and a manufacturing method thereof
  • the present inventors manufactured a lithium secondary battery using an electrolyte solution including a positive electrode slurry with a particle size adjusted and a solvent having a dipole moment less than a certain value, and that the lithium secondary battery thus manufactured exhibits improved life characteristics. Confirmed.
  • an object of the present invention is to provide a lithium secondary battery with improved life characteristics.
  • the present invention is a positive electrode; cathode; A separator interposed therebetween; And as a lithium secondary battery comprising an electrolyte,
  • the positive electrode includes a positive electrode slurry including a sulfur-carbon composite, a binder, and a conductive material,
  • the particle size (based on D 50 ) of the positive electrode slurry is 15 to 50 ⁇ m
  • the electrolyte solution contains a solvent and a lithium salt
  • the solvent is,
  • a first solvent having a DV 2 factor value of 1.75 or less represented by Equation 1 below;
  • lithium secondary battery comprising a second solvent that is a fluorinated ether-based solvent:
  • DV is the dipole moment per unit volume (D ⁇ mol/L)
  • ⁇ is the viscosity of the solvent (cP, 25°C)
  • ⁇ is 100 (constant).
  • the lithium secondary battery of the present invention includes a positive electrode including a positive electrode slurry having a particle size (based on D 50 ) of 15 to 50 ⁇ m; And an electrolytic solution including a first solvent having a DV 2 factor of 1.75 or less and a second solvent that is a fluorinated ether-based solvent; when it contains, there is an effect of improving high energy density and lifespan characteristics.
  • lithium-sulfur secondary batteries have a high discharge capacity and energy density among many secondary batteries, and sulfur used as a positive electrode active material has abundant reserves and is inexpensive, so the manufacturing cost of the battery can be lowered, and it is environmentally friendly. As a result, it is in the spotlight as a next-generation secondary battery.
  • the loss of sulfur occurs due to the inability to suppress the elution of lithium polysulfide as described above, and the amount of sulfur participating in the electrochemical reaction rapidly decreases. And not all of the theoretical energy density.
  • the eluted lithium polysulfide in addition to being suspended or precipitated in the electrolyte, reacts directly with lithium metal, which is the negative electrode, and is fixed in the form of Li 2 S on the surface of the negative electrode, thereby corroding the lithium metal negative electrode, and initial capacity and cycle after a certain cycle. It causes a problem of rapidly deteriorating properties.
  • the porosity (or porosity) of the positive electrode active material layer is low, the loading amount of sulfur as the positive electrode active material is high, and the particle size (based on D 50 ) is 15.
  • the conditions related to the electrolyte are specified to have a high energy density compared to the existing lithium-sulfur secondary battery when actually implemented, A lithium-sulfur secondary battery having excellent properties can be provided.
  • the present invention is an anode; cathode; A separator interposed therebetween; And as a lithium secondary battery comprising an electrolyte,
  • the positive electrode includes a positive electrode slurry including a sulfur-carbon composite, a binder, and a conductive material,
  • the particle size (based on D 50 ) of the positive electrode slurry is 15 to 50 ⁇ m
  • the electrolyte solution contains a solvent and a lithium salt
  • the solvent is,
  • a first solvent having a DV 2 factor value of 1.75 or less represented by Equation 1 below;
  • It relates to a lithium secondary battery comprising a second solvent which is a fluorinated ether solvent.
  • DV is the dipole moment per unit volume (D ⁇ mol/L)
  • ⁇ is the viscosity of the solvent (cP, 25°C)
  • ⁇ is 100 (constant).
  • the lithium secondary battery may preferably be a lithium-sulfur secondary battery.
  • the positive electrode for a lithium secondary battery of the present invention includes a positive electrode slurry containing a sulfur-carbon composite, a binder, and a conductive material, and the particle size (based on D 50 ) of the positive electrode slurry is 15 to 50 ⁇ m.
  • the positive electrode for a lithium secondary battery of the present invention includes a positive electrode current collector; And a positive electrode active material layer formed on at least one surface of the positive electrode current collector, wherein the positive electrode active material layer may be formed of a positive electrode slurry having a particle size of 15 to 50 ⁇ m (based on D 50 ).
  • the particle size of the positive electrode slurry refers to the particle size of the positive electrode slurry itself finally obtained by mixing a sulfur-carbon composite, a binder, and a conductive material in a solvent.
  • the particle size of the positive electrode slurry may depend on the particle size of the sulfur-carbon composite contained therein, but the particle size of the sulfur-carbon composite decreases due to the process of mixing for dispersion during the manufacturing process of the positive electrode slurry.
  • the particle size of the slurry and the particle size of the sulfur-carbon composite are distinct.
  • the particle size (based on D 50 ) of the positive electrode slurry including the sulfur-carbon composite, the binder, and the conductive material may be 15 to 50 ⁇ m, preferably more than 15 ⁇ m and 30 ⁇ m or less, and more preferably 17 to 30 ⁇ m.
  • the particle size (based on D 50 ) of the positive electrode slurry is 15 to 50 ⁇ m, life characteristics of a lithium-sulfur secondary battery including the same may be improved.
  • the particle size of the positive electrode slurry (based on D 50 ) is less than 15 ⁇ m, adhesion to the positive electrode current collector decreases, and there is a problem of being separated from the positive electrode current collector, and an overvoltage occurs when the lithium-sulfur secondary battery is driven, resulting in a decrease in lifespan characteristics. I can.
  • the particle size (based on D 50 ) of the positive electrode slurry exceeds 50 ⁇ m, the particle size distribution of the particles present in the positive electrode active material layer increases, thereby increasing the non-uniformity of the positive electrode active material layer, which may cause battery performance degradation.
  • the particles of the sulfur-carbon composite may be too large to cause scratches, which may cause difficulties in manufacturing the positive electrode.
  • the sulfur-carbon composite is a cathode active material for a lithium secondary battery, and includes sulfur and carbon nanotubes, and more specifically, is a sulfur-carbon composite in which sulfur is uniformly supported inside and outside the carbon nanotubes.
  • the carbon nanotubes may be entangled type carbon nanotubes having a particle size (based on D 50 ) of 15 to 50 ⁇ m.
  • the entangled type refers to a form made of one particle by lumping together entangled carbon nanotubes, and is also referred to as a non-bundle type.
  • the particle shape means a particle whose specific shape is not determined.
  • the particle size of the entangled carbon nanotubes in the form of particles is controlled through a milling process, the particle size of the sulfur-carbon composite including the same and the particle size of the positive electrode slurry can be controlled.
  • the sulfur may be one or more selected from the group consisting of inorganic sulfur (S 8 ), Li 2 S n (n ⁇ 1) and organic sulfur compounds, preferably inorganic sulfur (S 8 ).
  • the sulfur-carbon composite may include the sulfur and carbon nanotubes in a weight ratio of 55:45 to 90:10. When the weight ratio of the sulfur and the carbon material contained in the sulfur-carbon composite is satisfied, the capacity of the battery can be improved and the conductivity can be maintained.
  • the sulfur-carbon composite may be prepared by mixing the carbon nanotubes and sulfur, and then impregnating the sulfur into the carbon nanotubes through a melt diffusion method.
  • the sulfur-carbon composite may be included in an amount of 60 to 95% by weight, preferably 65 to 95% by weight, more preferably 70 to 90% by weight, based on the total weight of the positive electrode slurry. If the sulfur-carbon composite is less than 60% by weight, battery performance may deteriorate, and if it exceeds 95% by weight, the content of conductive materials or binders other than the positive electrode active material is relatively reduced, resulting in a decrease in properties such as conductivity or durability. .
  • the conductive material is not particularly limited, but may include graphite such as natural graphite or artificial graphite; Carbon blacks such as carbon black (super-p), acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and denka 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; It may be a conductive material such as a polyphenylene derivative.
  • the conductive material may be in an amount of 0.05% to 5% by weight based on the total weight of the positive electrode slurry.
  • the binder is SBR (Styrene-Butadiene Rubber)/CMC (Carboxymethyl Cellulose), poly(vinyl acetate), polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated Polyethylene oxide, cross-linked polyethylene oxide, polyvinyl ether, poly(methyl methacrylate), polyvinylidene fluoride, a copolymer of polyhexafluoropropylene and polyvinylidene fluoride (trade name: Kynar), poly(ethyl) Acrylate), polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinylpyridine, polystyrene, polyacrylic acid, derivatives, blends, copolymers and the like thereof may be used.
  • SBR Styrene-Butadiene Rubber
  • CMC Carboxymethyl Cellulose
  • polyvinyl alcohol polyethylene oxide
  • the content of the binder may be 1 to 20% by weight, preferably 3 to 18% by weight, more preferably 5 to 15% by weight based on the total weight of the positive electrode slurry. If it is less than the above range, the bonding force between the positive electrode active material or between the positive electrode active material and the current collector may be reduced, thereby deteriorating electrode stability. In addition, suppression of polysulfide elution due to the interaction between polysulfide and specific functional groups of the polymer chain used as a binder can be expected. If it exceeds the above range, the battery capacity may decrease.
  • the positive electrode slurry is prepared as a slurry having a particle size of 15 to 50 ⁇ m (based on D 50 ) by mixing a sulfur-carbon composite, a conductive material, and a binder in a solvent, and after applying the slurry having the particle size on a current collector Drying and selectively rolling may be performed to prepare a positive electrode having a positive electrode active material layer formed thereon.
  • a solvent for preparing the sulfur-carbon composite, the conductive material, and the binder in a slurry state may include acetonitrile, methanol, ethanol, tetrahydrofuran, water, isopropyl alcohol, etc., but is not limited thereto.
  • the positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery, for example, stainless steel, aluminum, nickel, titanium, and calcined carbon. , Or a surface-treated aluminum or stainless steel surface with carbon, nickel, titanium, silver, or the like may be used.
  • the positive electrode current collector may be in various forms such as a film, sheet, foil, net, porous material, foam, non-woven fabric having fine irregularities formed on the surface so as to increase adhesion to the positive electrode active material.
  • the anode is classified by an SC factor value represented by Equation 2 below.
  • P is the porosity (%) of the positive electrode active material layer in the positive electrode
  • L is the mass of sulfur per unit area of the positive electrode active material layer in the positive electrode (mg/cm 3 )
  • ⁇ is 10 (constant).
  • the lithium secondary battery according to the present invention preferably a lithium-sulfur secondary battery, implements a high energy density by organic bonding of the above-described positive electrode as well as a negative electrode, a separator, and an electrolyte, and according to a specific embodiment of the present invention, lithium
  • the SC factor value may be greater than 0.45, preferably greater than 0.5.
  • the upper limit of the SC factor value is not particularly limited, but considering an embodiment of an actual lithium-sulfur secondary battery, the SC factor value may be 4.5 or less.
  • the SC factor value is more than 0.45, in the case of a conventional lithium-sulfur secondary battery, performance such as energy density of the battery is deteriorated in actual implementation, but in the case of the lithium-sulfur secondary battery according to the present invention, The performance of the battery is maintained without deterioration.
  • the electrolyte is a non-aqueous electrolyte containing a lithium salt, and includes a lithium salt and a solvent.
  • the electrolyte solution has a density of less than 1.5 g/cm 3 .
  • the electrolyte has a density of 1.5 g/cm 3 or more, it is difficult to achieve a high energy density of a lithium secondary battery, preferably a lithium-sulfur secondary battery, due to an increase in weight of the electrolyte.
  • the lithium salt is a material that can be easily dissolved in a non-aqueous organic solvent, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiB(Ph) 4 , LiC 4 BO 8 , LiPF 6 , LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, LiSO 3 CH 3, LiSO 3 CF 3, LiSCN, LiC (CF 3 SO 2) 3, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2 ) 2 , LiN(SO 2 F) 2 , lithium chloroborane, lithium lower aliphatic carboxylic acid, lithium tetraphenylborate, and lithium imide.
  • the lithium salt may be a lithium imide such as LiTFSI.
  • the concentration of the lithium salt is 0.1 to 8.0 M, depending on various factors such as the exact composition of the electrolyte mixture, the solubility of the salt, the conductivity of the dissolved salt, the charging and discharging conditions of the battery, working temperature and other factors known in the lithium secondary battery field. , Preferably 0.5 to 5.0 M, more preferably 1.0 to 3.0 M may be. If the concentration of the lithium salt is less than the above range, the conductivity of the electrolyte may be lowered and battery performance may be deteriorated. If the concentration of the lithium salt is less than the above range, the viscosity of the electrolyte may increase and the mobility of lithium ions (Li + ) may decrease. It is desirable to select an appropriate concentration.
  • the solvent includes a first solvent and a second solvent.
  • the first solvent is characterized by having the highest dipole moment per unit volume among the constituents contained in the solvent at least 1% by weight, and thus has a high dipole moment and a low viscosity.
  • a solvent having a high dipole moment is used, it has an effect of improving the solid state reactivity of sulfur, and this effect can be excellently expressed when the solvent itself has a low viscosity.
  • the first solvent is classified by a DV 2 factor represented by Equation 1 below.
  • DV is the dipole moment per unit volume (debye(D) ⁇ mol/L)
  • ⁇ is the viscosity of the solvent (cP, 25°C)
  • ⁇ is 100 (constant).
  • the DV 2 factor value may be 1.75 or less, preferably 1.5 or less.
  • the lower limit of the DV 2 factor value is not particularly limited, but considering an embodiment of an actual lithium secondary battery, preferably a lithium-sulfur secondary battery, the DV 2 factor value may be 0.1 or more. .
  • a solvent having a DV 2 factor of 1.5 or less, such as the first solvent when applied to a lithium-sulfur secondary battery including a surface-modified sulfur-carbon composite as described above, it is possible to improve battery performance, such as improving life characteristics. It can be advantageous.
  • the type is not particularly limited, but propionitrile, dimethylacetamide, dimethylformamide, gamma- It may be one or more selected from the group consisting of butyrolactone (Gamma-Butyrolactone), triethylamine (Triethylamine) and 1-iodopropane (1-iodopropane).
  • the first solvent may contain 1 to 50% by weight, preferably 5 to 40% by weight, and more preferably 10 to 30% by weight, based on the solvent constituting the electrolyte.
  • the solvent according to the present invention contains the first solvent within the above-described weight% range, as described above, a positive electrode slurry having a low porosity, a high loading amount of sulfur, and a particle size (based on D 50 ) of 15 to 50 ⁇ m
  • it may be advantageous in improving battery performance, such as improving life characteristics.
  • the lithium secondary battery of the present invention may be further classified by an NS factor obtained by combining the SC factor and the DV 2 factor.
  • the NS factor is represented by Equation 3 below.
  • the SC factor is the same as the value defined by Equation 2
  • the DV 2 factor is the same as the value defined by Equation 1 above.
  • the value of the NS factor may be 3.5 or less, preferably 3.0 or less, and more preferably 2.7 or less.
  • the lower limit of the value of the NS factor is not particularly limited, but considering an embodiment of an actual lithium secondary battery, preferably a lithium-sulfur secondary battery, the NS factor value may be 0.1 or more. When the NS factor value is adjusted within the above range, the effect of improving the performance of the lithium-sulfur secondary battery may be more excellent.
  • the second solvent is a fluorinated ether solvent.
  • a solvent such as dimethoxyethane and dimethylcarbonate has been used as a diluent to adjust the viscosity of the electrolyte.
  • high loading as in the present invention , It is not possible to drive a battery including a positive electrode having a low porosity and a particle size of the positive electrode slurry within a certain range.
  • the second solvent is added together with the first solvent to drive the anode according to the present invention.
  • the second solvent is a fluorinated ether solvent generally used in the relevant technical field, the type is not particularly limited, but 1H,1H,2'H,3H-decafluorodipropyl ether (1H,1H,2' H,3H-Decafluorodipropyl ether), difluoromethyl 2,2,2-trifluoroethyl ether, 1,2,2,2-tetrafluoroethyl trifluoro Methyl ether (1,2,2,2-Tetrafluoroethyl trifluoromethyl ether), 1,1,2,3,3,3-hexafluoropropyl difluoromethyl ether (1,1,2,3,3,3- Hexafluoropropyl difluoromethyl ether), pentafluoroethyl 2,2,2-trifluoroethyl ether and 1H,1H,2′H
  • the second solvent may contain 50 to 99% by weight, preferably 60 to 95% by weight, and more preferably 70 to 90% by weight, based on the solvent constituting the electrolyte.
  • the solvent according to the present invention contains a second solvent within the range of 50 to 99% by weight described above, like the first solvent, the positive electrode slurry having a particle size (based on D 50 ) of 15 to 50 ⁇ m as described above is included.
  • it may be advantageous in improving battery performance, such as improving life characteristics.
  • the second solvent When mixing the first solvent and the second solvent, the second solvent may be included in the electrolyte in an amount equal to or greater than the first solvent in consideration of an effect of improving the performance of the battery.
  • the solvent may contain a first solvent and a second solvent in a weight ratio of 1:1 to 1:9, preferably 3:7 to 1:9 (first solvent: second solvent). I can.
  • the non-aqueous electrolyte solution for a lithium-sulfur battery of the present invention may further include nitric acid or nitrous acid-based compounds as an additive.
  • the nitric acid or nitrous acid-based compound has an effect of forming a stable film on the lithium electrode and improving charging/discharging efficiency.
  • the nitric acid or nitrous acid-based compound is not particularly limited in the present invention, but lithium nitrate (LiNO 3 ), potassium nitrate (KNO 3 ), cesium nitrate (CsNO 3 ), barium nitrate (Ba(NO 3 ) 2 ), ammonium nitrate Inorganic nitric acid or nitrite compounds such as (NH 4 NO 3 ), lithium nitrite (LiNO 2 ), potassium nitrite (KNO 2 ), cesium nitrite (CsNO 2 ), and ammonium nitrite (NH 4 NO 2 ); Organic nitric acids such as methyl nitrate, dialkyl imidazolium nitrate, guanidine nitrate, imidazolium nitrate, pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, and oc
  • the non-aqueous electrolyte may further include other additives for the purpose of improving charging/discharging properties and flame retardancy.
  • the additives include pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazoli Dione, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride, fluoroethylene carbonate (FEC), propene sultone (PRS), vinylene carbonate ( VC) and the like.
  • FEC fluoroethylene carbonate
  • PRS propene sultone
  • VC vinylene carbonate
  • the negative electrode for a lithium secondary battery of the present invention includes a negative electrode current collector; And a negative active material layer formed on at least one surface of the current collector.
  • the negative active material layer includes a negative active material, a binder, and a conductive material.
  • a material capable of reversibly intercalating or deintercalating lithium ions (Li + ) a material capable of reversibly forming a lithium-containing compound by reacting with lithium ions, lithium metal or lithium alloy
  • the material capable of reversibly occluding or releasing lithium ions (Li + ) 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 binder, the conductive material, and the negative electrode current collector may be the same as the material used in the positive electrode.
  • the separator is a physical separator having a function of physically separating an electrode, and if it is used as a conventional separator, it can be used without special limitation. In particular, it is preferable that the separator has low resistance against ion migration of the electrolyte and has excellent electrolyte moisture-repelling ability. Do.
  • the separator separates or insulates the positive electrode and the negative electrode from each other and enables transport of lithium ions between the positive electrode and the negative electrode.
  • a separator has a porosity of 30 to 50%, and may be made of a non-conductive or insulating material.
  • a porous polymer film for example, an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, etc.
  • a porous polymer film for example, an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, etc.
  • nonwoven fabrics made of high melting point glass fibers or the like can be used.
  • a porous polymer film is preferably used.
  • an ethylene homopolymer (polyethylene) polymer film is used as a separator, and a polyimide nonwoven fabric is used as a buffer layer.
  • the polyethylene polymer film preferably has a thickness of 10 to 25 ⁇ m and a porosity of 40 to 50%.
  • the lithium secondary battery of the present invention preferably a lithium-sulfur secondary battery, is prepared by placing a separator between a positive electrode and a negative electrode to form an electrode assembly, and the electrode assembly is placed in a cylindrical battery case or a prismatic battery case, and then an electrolyte is injected. can do.
  • an electrolyte is injected. can do.
  • it may be impregnated with an electrolyte, and the resulting product may be sealed by putting it in a battery case.
  • the lithium secondary battery preferably lithium-sulfur secondary battery according to the present invention is classified by the ED factor value represented by Equation 4 below.
  • V is the nominal discharge voltage (V) for Li/Li +
  • D is the density of the electrolyte (g/cm 3 )
  • C is the discharge capacity (mAh/g) when discharging at a 0.1C rate
  • SC factor I is the same as the value defined by Equation 2 above. The higher the value of the ED factor, the higher the energy density can be realized in the actual lithium-sulfur secondary battery.
  • the ED factor value may be 850 or more, preferably 870 or more, and more preferably 891 or more.
  • the upper limit of the ED factor value is not particularly limited, but considering an embodiment of an actual lithium-sulfur secondary battery, the ED factor value may be 10,000 or less.
  • the range of the ED factor value means that the lithium-sulfur secondary battery according to the present invention can realize an improved energy density than the conventional lithium-sulfur secondary battery.
  • 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 supply for medium and large 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 powered by an omniscient motor and moves; 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.
  • An entangled type carbon nanotube having a particle size (based on D 50 ) of 100 to 150 ⁇ m was manufactured using a ball mill to prepare an entangled type carbon nanotube having a reduced particle size (based on D 50 ).
  • the weight ratio of sulfur and entangled carbon nanotubes in the sulfur-carbon composite was 70:30.
  • a positive electrode slurry having a concentration of 20% based on the solid content was prepared.
  • the particle size of the positive electrode slurry was measured using a particle size analyzer (PSA), and the particle size (based on D 50 ) of the positive electrode slurry was 27 ⁇ m.
  • the positive electrode slurry was coated on an aluminum current collector to form a positive electrode active material layer, followed by drying and rolling to prepare a positive electrode.
  • the porosity of the positive electrode active material layer calculated by measuring the electrode weight and the electrode thickness (using TESA- ⁇ HITE equipment) in the manufactured positive electrode was 60%, and the mass of sulfur per unit area of the positive electrode active material layer was 4.54 mg/cm 3 Was.
  • the SC factor value calculated based on this was 0.757.
  • a polyethylene separator having a thickness of 20 ⁇ m and a porosity of 45% was interposed between the positive electrode and the negative electrode.
  • a lithium foil having a thickness of 60 ⁇ m was used as the negative electrode.
  • the electrolyte is prepared by dissolving lithium bis (trifluoromethyl sulfonyl) imide (LiTFSI) having a concentration of 3 M in an organic solvent, and the organic solvent is propionitrile (first solvent) and 1H,1H,
  • first solvent propionitrile
  • second solvent solvent obtained by mixing 2'H,3H-decafluorodipropyl ether (second solvent) in a 3:7 weight ratio (w/w) was used.
  • the dipole moment per unit volume in the first solvent was 97.1 D ⁇ mol/L
  • the viscosity of the solvent measured by using a BROOKFIELD AMETEK LVDV2T-CP viscometer was 0.38 cP (25° C.).
  • the DV 2 factor value calculated based on this was 0.39. Charging and discharging of the manufactured battery was performed at 45°C.
  • An entangled-type carbon nanotube having a particle size (based on D 50 ) of 100 to 150 ⁇ m was used with a ball mill to increase the ball mill time compared to Example 1, so that the particle size (based on D 50 ) was reduced compared to Example 1.
  • a type of carbon nanotube was prepared.
  • Example 2 The particle size of the positive electrode slurry of Example 2 was measured using a particle size analyzer (PSA), and the particle size (based on D 50 ) of the positive electrode slurry was 24 ⁇ m.
  • PSD particle size analyzer
  • the porosity of the positive electrode active material layer calculated by measuring the electrode weight and the electrode thickness (using TESA- ⁇ HITE equipment) in the manufactured positive electrode was 60%, and the mass of sulfur per unit area of the positive electrode active material layer was 4.54 mg/cm 3 Was.
  • the SC factor value calculated based on this was 0.757.
  • An entangled type carbon nanotube having a particle size (based on D 50 ) of 100 to 150 ⁇ m was used in a ball mill to increase the ball mill time compared to Example 2, so that the particle size (based on D 50 ) was reduced compared to Example 2.
  • a type of carbon nanotube was prepared.
  • Example 3 The particle size of the positive electrode slurry of Example 3 was measured using a particle size analyzer (PSA), and the particle size (based on D 50 ) of the positive electrode slurry was 18 ⁇ m.
  • PSD particle size analyzer
  • the porosity of the positive electrode active material layer calculated by measuring the electrode weight and the electrode thickness (using TESA- ⁇ HITE equipment) in the prepared positive electrode was 60%, and the mass of sulfur per unit area of the positive electrode active material layer was 4.35 mg/cm 3 .
  • the SC factor value calculated based on this was 0.725.
  • An entangled-type carbon nanotube having a particle size (based on D 50 ) of 100 to 150 ⁇ m was used in a ball mill to increase the ball mill time compared to Example 3, so that the particle size (based on D 50 ) was reduced compared to Example 3
  • a type of carbon nanotube was prepared.
  • Example 4 The particle size of the positive electrode slurry of Example 4 was measured using a particle size analyzer (PSA), and the particle size (based on D 50 ) of the positive electrode slurry was 15 ⁇ m.
  • PSD particle size analyzer
  • the porosity of the positive electrode active material layer calculated by measuring the electrode weight and the electrode thickness (using TESA- ⁇ HITE equipment) in the prepared positive electrode was 60%, and the mass of sulfur per unit area of the positive electrode active material layer was 4.6 mg/cm 3 Was.
  • the SC factor value calculated based on this was 0.767.
  • An entangled type carbon nanotube having a particle size (based on D 50 ) of 100 to 150 ⁇ m was used in a ball mill to increase the ball mill time compared to Example 4, so that the particle size (based on D 50 ) was reduced compared to Example 4.
  • a type of carbon nanotube was prepared.
  • Example 2 Subsequent processes were carried out in the same manner as in Example 1 to prepare a lithium-sulfur secondary battery.
  • the particle size of the positive electrode slurry of Comparative Example 1 was measured using a particle size analyzer (PSA), and the particle size (based on D 50 ) of the positive electrode slurry was 11 ⁇ m.
  • PSD particle size analyzer
  • the porosity of the positive electrode active material layer calculated by measuring the electrode weight and electrode thickness (using TESA- ⁇ HITE equipment) in the prepared positive electrode was 60%, and the mass of sulfur per unit area of the positive electrode active material layer was 4.73 mg/cm 3 . Based on this, the calculated SC factor value was 0.788.
  • An entangled type carbon nanotube having a particle size (based on D 50 ) of 100 to 150 ⁇ m was used in a ball mill to increase the ball mill time compared to Example 4, resulting in a reduced particle size (based on D 50 ) than in Example 4.
  • An entangle-type carbon nanotube was prepared.
  • Example 2 Subsequent processes were carried out in the same manner as in Example 1 to prepare a lithium-sulfur secondary battery.
  • the particle size of the positive electrode slurry of Comparative Example 2 was measured using a particle size analyzer (PSA), and the particle size (based on D 50 ) of the positive electrode slurry was 8 ⁇ m.
  • PSD particle size analyzer
  • the porosity of the positive electrode active material layer calculated by measuring the electrode weight and electrode thickness (using TESA- ⁇ HITE equipment) in the prepared positive electrode was 60%, and the mass of sulfur per unit area of the positive electrode active material layer was 4.37 mg/cm 3 . Based on this, the calculated SC factor value was 0.728.
  • An entangled type carbon nanotube having a particle size (based on D 50 ) of 100 to 150 ⁇ m was ball milled at the same time as in Example 4, and the entangled type carbon nanotube having the same particle size (based on D 50 ) as in Example 4 The tube was prepared.
  • Example 3 Subsequent processes were carried out in the same manner as in Example 1 to prepare a lithium-sulfur secondary battery.
  • the particle size of the positive electrode slurry of Comparative Example 3 was measured using a particle size analyzer (PSA), and the particle size (based on D 50 ) of the positive electrode slurry was 15 ⁇ m.
  • PSD particle size analyzer
  • the porosity of the positive electrode active material layer calculated by measuring the electrode weight and electrode thickness (using TESA- ⁇ HITE equipment) in the prepared positive electrode was 60%, and the mass of sulfur per unit area of the positive electrode active material layer was 2.7 mg/cm 3 .
  • the SC factor value calculated based on this was 0.45.
  • Example 1 Particle size of positive electrode slurry (D 50 , ⁇ m) SC factor DV 2 factor NS factor ED factor
  • Example 1 27 0.757 0.39 0.515 1433.185
  • Example 2 24 0.757 0.39 0.515 1422.955
  • Example 3 18 0.725 0.39 0.538 1434.375
  • Example 4 15 0.767 0.39 0.508 1392.043 Comparative Example 1 11 0.788 0.39 0.495 1359.417 Comparative Example 2 8 0.728 0.39 0.535 992.8758 Comparative Example 3 15 0.45 0.39 0.866 822.1622
  • the lithium-sulfur secondary batteries of Examples 1 to 4 having a particle size (based on D 50 ) of 15 to 50 ⁇ m of the positive electrode slurry exhibited excellent results in life characteristics.
  • the positive electrode slurry had a particle size (based on D 50 ) of 15 ⁇ m, and the lifespan characteristics were not superior to those of Examples 1 to 3, but the results were superior to that of Comparative Example 1. Therefore, it can be seen that the particle size (based on D 50 ) of the positive electrode slurry has a critical significance at 15 ⁇ m.
  • Comparative Examples 1 and 2 the particle size (based on D 50 ) of the positive electrode slurry was less than 15 ⁇ m, and it can be seen that the ED factor rapidly decreased as the cycle was repeated.
  • the SC factor value is 0.45 or less, and it can be seen that the ED factor shows a low energy density of 800 levels during the charge/discharge cycle.
  • the particle size (based on D 50 ) of the positive electrode slurry is 15 to 50 ⁇ m, the battery life characteristics are excellent.

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Abstract

La présente invention concerne une batterie secondaire au lithium et, plus particulièrement, une batterie secondaire au lithium comprenant une suspension épaisse d'électrode positive ayant une taille particulaire (sur la base de D50) située dans la plage allant de 15 à 50 µm, une condition pour un électrolyte étant spécifiée, et une densité d'énergie élevée et une longue durée de vie pouvant ainsi être mises en œuvre par rapport aux batteries secondaires au lithium classiques.
PCT/KR2020/008043 2019-07-16 2020-06-22 Batterie secondaire au lithium WO2021010605A1 (fr)

Priority Applications (5)

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CN202080028671.2A CN113692665A (zh) 2019-07-16 2020-06-22 锂二次电池
US17/605,761 US20220231342A1 (en) 2019-07-16 2020-06-22 Lithium secondary battery
BR112021020560A BR112021020560A2 (pt) 2019-07-16 2020-06-22 Bateria secundária de lítio
JP2021563684A JP7427025B2 (ja) 2019-07-16 2020-06-22 リチウム二次電池
EP20840658.7A EP3951931A4 (fr) 2019-07-16 2020-06-22 Batterie secondaire au lithium

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