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WO2019059440A1 - Séparateur d'accumulateur au lithium employant un électrolyte liquide inorganique - Google Patents

Séparateur d'accumulateur au lithium employant un électrolyte liquide inorganique Download PDF

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Publication number
WO2019059440A1
WO2019059440A1 PCT/KR2017/010687 KR2017010687W WO2019059440A1 WO 2019059440 A1 WO2019059440 A1 WO 2019059440A1 KR 2017010687 W KR2017010687 W KR 2017010687W WO 2019059440 A1 WO2019059440 A1 WO 2019059440A1
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Prior art keywords
secondary battery
lithium secondary
separator
lithium
liquid electrolyte
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English (en)
Korean (ko)
Inventor
김한수
김아영
송주혜
정호재
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Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a separator for a lithium secondary battery employing an inorganic liquid electrolyte and a method for producing the same, and more particularly, to a separator for a lithium secondary battery employing an inorganic liquid electrolyte based on sulfur dioxide, To a separation membrane for a lithium secondary battery.
  • the separator which is one of the key components of the lithium secondary battery according to the necessity of a high output and a large capacity battery in an electric vehicle or a medium and large-sized energy storage system including a light weight and miniaturization of a portable electronic device, A material that can be improved is required.
  • the lithium secondary battery includes an electrode assembly composed of an anode, a cathode, and a separator disposed between the anode and the cathode, and an electrolyte containing a lithium salt.
  • charging and discharging proceed while repeating the process of inserting and separating lithium ions from each other between the positive electrode and the negative electrode.
  • the separation membrane includes micro pores, it provides a path through which lithium ions move through the pores, and physically separates the positive and negative electrodes to perform a function of being electrically insulated.
  • the thickness of the separator is reduced, the distance between the anode and the cathode is reduced, which is advantageous in terms of high output and high energy density of the battery.
  • the pore size must be very small in order to maintain the insulating property, .
  • the volume of the electrode assembly itself may become large and the volume-capacity may be deteriorated.
  • the electrochemical characteristics may be deteriorated. If the electrode is partially depleted due to the local depletion of the electrolyte or if the reaction is locally concentrated, lithium metal may precipitate and there is a risk of resin dendrite growth of lithium. Therefore, the electrolyte must be rapidly permeated into the separation membrane, and the state must be maintained uniformly even after wet. In addition, the interface between the electrode and the separation membrane and the electrolyte must be maintained firmly to achieve excellent charge / discharge characteristics and cycle life.
  • the polyolefin separator commercialized for lithium secondary batteries is excellent in chemical stability and mechanical strength, but has a disadvantage in that it has poor affinity with electrolytic solution, especially inorganic liquid electrolyte, and has poor thermal stability. Therefore, a system requiring high output and safety It is necessary to improve it.
  • an example using a composite membrane in which a polyolefin separator is coated with a polymer material or ceramic has been known.
  • lithium secondary battery employing a non-aqueous electrolyte in which a lithium salt is added to a mixed solvent of ethylene carbonate or propylene carbonate which is a high-dielectric solvent and dimethyl carbonate or diethyl carbonate which is a low-viscosity solvent, And a cycle life is limited, and a lithium secondary battery employing an inorganic liquid electrolyte having excellent wettability of a separator has not been reported.
  • the present inventors have found that when the surface of the separator is coated with a polymer material, the wettability of the separator to the electrolyte is greatly improved, and the sulfur dioxide-based The charging / discharging characteristics and the cycle life of the lithium secondary battery including the inorganic liquid electrolyte and the separator can be remarkably improved.
  • the present invention has been accomplished based on this finding.
  • Patent Document 1 Korean Patent Publication No. 10-2016-0109227
  • Patent Document 2 Korean Patent No. 10-1470696
  • Patent Document 3 JP-A-2016-081606
  • the present invention has been made in view of the above problems, and it is an object of the present invention to provide a lithium secondary battery, which is capable of significantly improving the wettability of a separator for an inorganic liquid electrolyte and significantly improving charge / discharge characteristics and cycle life,
  • the present invention provides a separator for a lithium secondary battery employing a sulfur dioxide-based inorganic liquid electrolyte capable of being stably driven even when the separator is used.
  • a separation membrane for a lithium secondary battery comprising: (a) the lithium secondary battery includes a lithium salt-containing inorganic liquid electrolyte into which sulfur dioxide is injected; (b) a separation layer for a lithium secondary battery, wherein a coating layer of a polymer material is formed on both sides of the separation layer.
  • the lithium salt is characterized by at least one selected from the group consisting of LiAlCl 4 , LiGaCl 4 , Li 2 CoCl 4 , Li 2 NiCl 4 , Li 2 CuCl 4 , Li 2 MnCl 4 , Li 2 ZnCl 4 and LiAlBr 4 .
  • the sulfuric acid-impregnated lithium salt-containing inorganic liquid electrolyte is characterized by being LiAlCl 4 -3 SO 2 .
  • the separator is a separator selected from the group consisting of polyethylene, polypropylene, polyester, polyamide, polyimide, polycarbonate, polyacetal, polyether sulfone, polyetheretherketone, polyphenylene oxide, polyphenylene sulfide Or more porous substrate.
  • the polymer material may be selected from the group consisting of polyethylene oxide, polyvinyl pyrrolidone, polyacrylonitrile, polyvinylidene fluoride, polymethylmethacrylate, polyvinyl acetate, ethylene vinyl acetate copolymer, cellulose acetate, carboxymethylcellulose and polyimide And at least one selected from the group consisting of
  • the coating layer has a thickness of 1 to 10 mu m.
  • the present invention also provides a lithium secondary battery including an anode, an anode, an electrode assembly composed of a porous separator disposed between the anode and the cathode, and an electrolyte, wherein the porous separator has a coating layer of a polymer material on both sides, wherein the electrolyte is a lithium salt-containing inorganic liquid electrolyte into which sulfur dioxide is injected.
  • the present invention also provides an energy storage element comprising the lithium secondary battery.
  • the polymer material is coated on the porous separator for a lithium secondary battery, and the wettability of the separator to the electrolyte is greatly improved by employing an inorganic liquid electrolyte based on sulfur dioxide, and ultimately the charge / Life can be remarkably improved.
  • it can be stably driven at a low temperature, so that it can be applied to energy storage devices such as portable electronic devices or electric vehicles.
  • Example 1 is a scanning electron microscope (SEM) image of a membrane according to Example 1 (PEO coated PE separator), PE separator and glass fiber filter of the present invention.
  • Example 2 is a photograph of the wettability of the separator according to Example 1 (PEO coated PE), Comparative Example 1 (PE) and Comparative Example 2 (Glass fiber filter) of the present invention.
  • Example 3 is a graph showing characteristics of an initial cell of a lithium secondary battery manufactured from Example 1 and Comparative Examples 1 to 3 of the present invention.
  • Example 4 is a graph showing the charge-discharge cycle capacity and lifetime characteristics of a lithium secondary battery manufactured from Example 1 and Comparative Examples 1 to 3 of the present invention.
  • Example 5 is a graph showing the coulomb efficiency in the charge and discharge cycles of the lithium secondary battery manufactured from Example 1 and Comparative Examples 1 to 3 of the present invention.
  • Example 6 is a graph showing the relationship between the initial discharge capacity of the lithium secondary battery fabricated in Example 1 of the present invention and the initial discharge capacity of the lithium secondary battery according to Example 1 (75 wt%, 50 wt%, 25 wt%, 10 Weight%) A graph comparing initial discharge capacities of the produced lithium secondary batteries.
  • FIG. 7 is a graph comparing the initial discharge capacities of the lithium secondary batteries manufactured in Example 2 and Comparative Examples 4 to 7, according to Examples and Comparative Examples 1 and 2 of the present invention.
  • Example 8 is a graph showing characteristics of an initial cell by driving the lithium secondary battery fabricated from Example 1 and Comparative Example 3 of the present invention at a low temperature.
  • the present invention relates to a separator for a lithium secondary battery, comprising: a) the lithium secondary battery comprises a lithium salt-containing inorganic liquid electrolyte into which sulfur dioxide is injected; (b) a separation layer for a lithium secondary battery, wherein a coating layer of a polymer material is formed on both sides of the separation layer.
  • the electrolyte for a lithium secondary battery is mainly composed of a non-aqueous electrolyte containing lithium salt and lithium, and non-aqueous electrolyte, organic solid electrolyte and inorganic solid electrolyte are used as the non-aqueous electrolyte.
  • the nonaqueous electrolytic solution include nonaqueous electrolytes such as N-methyl-2-pyrrolidinone, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide or tetrahydrofuran A non-magnetic organic solvent is used.
  • a polymer including an ionic dissociation group such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphoric acid ester polymer, and a polyvinyl alcohol is used.
  • the inorganic solid electrolyte a nitride, a halide or a sulfate of lithium is used.
  • a lithium salt such as LiCl or LiPF 6 is added to a mixed solvent of ethylene carbonate or propylene carbonate which is a high-dielectric solvent and dimethyl carbonate or diethyl carbonate which is a low-viscosity solvent as a non-aqueous electrolyte,
  • ethylene carbonate or propylene carbonate which is a high-dielectric solvent
  • dimethyl carbonate or diethyl carbonate which is a low-viscosity solvent as a non-aqueous electrolyte
  • the wettability of the separator which is a core component of the lithium secondary battery, is further improved by employing the inorganic salt electrolyte containing lithium salt into which sulfur dioxide is injected as a novel type of electrolyte.
  • LiAlCl 4 , LiGaCl 4 , Li 2 CoCl 4 , Li 2 NiCl 4 , Li 2 CuCl 4 , Li 2 MnCl 4 , Li 2 ZnCl 4 and LiAlBr 4 is used as the lithium salt
  • LiAlCl 4 -3 SO 2 in the form of sulfur dioxide is more preferably used as an inorganic liquid electrolyte.
  • the separation membrane may be formed of a polyolefin (polyethylene or polypropylene), a polyester, a polyamide, a polyimide, a polycarbonate, a polyacetal, a polyether sulfone, a polyether ether ketone, a polyphenylene oxide, May be used as the porous substrate.
  • the separation membrane (porous substrate) has a disadvantage in that the wettability of the inorganic salt liquid electrolyte containing lithium salt injected with sulfur dioxide is somewhat low
  • the present invention is not limited thereto.
  • both sides of the separation membrane are coated with a polymer material, Thereby greatly improving the wettability of the lithium salt-containing inorganic liquid electrolyte.
  • polymer material examples include polyethylene oxide, polyvinyl pyrrolidone, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polyvinyl acetate, ethylene vinyl acetate copolymer, cellulose acetate, carboxymethyl cellulose and polyimide At least one selected from the group consisting of polyethylene oxide is preferably used, and polyethylene oxide is more preferably used.
  • the coating layer of the polymer material preferably has a thickness of 1 to 10 mu m. If the thickness of the coating layer is less than 1 mu m, the affinity with the inorganic liquid electrolyte is poor and the wettability may deteriorate. If the thickness of the coating layer is less than 10 mu m , The initial discharge capacity may be lowered.
  • the conventional lithium secondary battery includes an anode, a cathode, an electrode assembly composed of a porous separator disposed between the anode and the cathode, and an electrolyte.
  • an anode, a cathode, And the electrolyte is a lithium salt-containing inorganic liquid electrolyte into which sulfur dioxide is injected.
  • porous separator base material
  • polymer material coated on both sides of the porous separator and the lithium salt-containing inorganic liquid electrolyte into which the sulfur dioxide is injected are as described above, and thus the further explanation is omitted.
  • the lithium secondary battery according to the present invention ultimately significantly improves the charge / discharge characteristics and cycle life of the lithium secondary battery, and can be stably driven even at a low temperature, Therefore, the present invention can provide an energy storage device including the lithium secondary battery.
  • a lithium salt-containing inorganic liquid electrolyte in which sulfur dioxide was injected a battery (2032 coin type) was produced by using LiAlCl 4 -3 SO 2. Graphite was used as a working electrode and lithium metal was used as a counter electrode.
  • a battery (2032 coin type) was fabricated in the same manner as in Example 1 except that the thickness of the coating layer was adjusted to 2 ⁇ .
  • a cell (2032 coin type) was fabricated in the same manner as in Example 1, except that a PE separator without a PEO coating was used.
  • a cell (2032 coin type) was fabricated in the same manner as in Example 1 except that a glass fiber filter not coated with PEO was used as a separator.
  • Example 1 was repeated except that 1 M LiPF 6 was added to a mixed organic solvent (1: 1, volume ratio) of ethylene carbonate (EC) / dimethyl carbonate (DMC) instead of the inorganic liquid electrolyte of the above- A battery (2032 coin type) was produced in the same manner.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • Example 1 shows a scanning electron microscope (SEM) image of a separation membrane according to Example 1 (PEO coated PE separator), Comparative Example 1 (PE separator) and Comparative Example 2 (Glass fiber filter) It can be confirmed that polyethylene oxide (PEO) was uniformly coated on the porous PE separator according to Example 1 of the present invention.
  • SEM scanning electron microscope
  • FIG. 2 is a photograph showing the wettability of the membrane according to Example 1 (PEO coated PE), Comparative Example 1 (PE) and Comparative Example 2 (Glass fiber filter) of the present invention.
  • Example 1 PET coated PE
  • Comparative Example 1 PE
  • Comparative Example 2 Glass fiber filter
  • Example 1 and Comparative Example 2 did not melt or shrink without reacting with the electrolytic solution, while in the case of Comparative Example 1, It can be seen that it is floating without being impregnated.
  • Figure 3 in Example 1 and Comparative Examples 1 to 3 was it exhibited an initial battery characteristics of the lithium secondary battery manufactured in a graph bar, amperage 20 mA g from the present invention result of driving the each cell to 1, the arms the initial capacity of the lithium secondary battery employing the liquid electrolyte is not as big a Comparative example 1, Comparative example 2 and carrying respective capacitance differences in 356.7 mAh g -1, 354.2 mAh g -1, 356.9 mAh g -1 in example 1 . As the graphite inserts and removes lithium, the flat voltage appears, and the deviation between the three cells is not so large.
  • the initial capacity is 340.9 mAh g -1 , which is much smaller than that of the inorganic liquid electrolyte.
  • the flat voltage is not clearly distinguished, and when a conventional organic liquid electrolyte is employed, the coating layer of the polymer material acts as a resistance of lithium movement, and the resistance of the battery increases.
  • FIG. 4 is a graph showing the charge-discharge cycle capacity and lifetime characteristics of the lithium secondary battery manufactured from Example 1 and Comparative Examples 1 to 3 of the present invention.
  • Example 1 since the separation membrane having a thinner thickness and improved electrolyte wettability is used, an inorganic liquid electrolyte based on sulfur dioxide is employed, so the conductivity of lithium ion is increased and the internal resistance is lowered, thereby improving the life characteristic. It can be seen that after 20 cycles, the capacity retention rate rapidly decreases in the case of the comparative example 1, and the capacity retention rate is the lowest in comparison with the comparative example 2 and the example 1. [ The capacity was 221.1 mAh g- 1 on a 47-cycle basis with a 61.9% capacity reduction over the first cycle.
  • FIG. 5 is a graph showing the coulombic efficiency in the charge / discharge cycle of the lithium secondary battery manufactured in Example 1 of the present invention and Comparative Examples 1 to 3.
  • the efficiency was 97 to 98.8% While Comparative Example 1 is maintained at a low efficiency of 94.5 to 96%, while Comparative Example 2 shows a gradual decrease to 95%. Therefore, it can be seen that the lithium secondary battery manufactured from Example 1 has remarkably improved battery performance as compared with the lithium secondary battery manufactured from Comparative Example 1 and Comparative Example 2.
  • the capacity is gradually increased due to the initial low capacity expression, and the efficiency is maintained to be high.
  • Example 6 shows the initial discharge capacity of the lithium secondary battery fabricated in Example 1 of the present invention and the initial discharge capacity of the lithium secondary battery according to Example 1 (75 wt%, 50 wt%, 25 wt% , 10% by weight).
  • the graph of the initial discharge capacity of the produced lithium secondary battery is shown in FIG.
  • the lithium secondary battery (having a concentration of the polymer solution for coating of 90 wt%) manufactured from Example 1 of the present invention and the remaining lithium produced by varying the concentration of the polymer solution for coating It was found that the concentration of the polymer solution for the coating was not a large variable affecting the initial discharge capacity.
  • the lithium secondary battery manufactured in Example 1 It can be seen that the initial discharge capacity of the battery is relatively high.
  • Example 7 is a graph showing the initial discharge capacities of the lithium secondary batteries fabricated in Example 1 and Comparative Example 1 and in Example 2 and Comparative Examples 4 to 7 in different coating thicknesses. As can be seen, in the case of the discharge capacity to be developed, although the difference in the average capacity is not large, it is confirmed that the capacity gradually decreases from the case where the thickness of the coating layer exceeds 10 ⁇ , so that the thickness of the coating layer is preferably 1 ⁇ to 10 ⁇ Do.
  • Example 8 is a graph showing the characteristics of an initial cell by driving the lithium rechargeable battery fabricated from Example 1 and Comparative Example 3 at a low temperature. As the driving temperature is gradually lowered, a comparative example 3 shows that the capacity of the lithium secondary battery fabricated from Example 3 is lowered.
  • the lithium secondary battery employing the inorganic liquid electrolyte maintains a higher ionic conductivity than the lithium secondary battery employing the organic liquid electrolyte even at a low temperature, thereby maintaining the capacity for expressing the lithium secondary battery. It can be seen that the separation membrane having the polymer coating layer formed therein as in Example 1 is used and the lithium secondary battery employing the inorganic liquid electrolyte can be stably driven at a low temperature.
  • the polymer material is coated on the porous separator for a lithium secondary battery and the inorganic liquid electrolyte based on sulfur dioxide is employed, the wettability of the separator to the electrolyte is greatly improved, and ultimately, The cycle life is remarkably improved, and it can be stably driven even at a low temperature, so that it can be applied to an energy storage device such as a portable electronic device or an electric automobile.

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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)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

La présente invention concerne un séparateur d'accumulateur au lithium caractérisé en ce que : (a) l'accumulateur au lithium comprend un électrolyte liquide inorganique contenant un sel de lithium dans lequel est injecté du dioxyde de soufre ; et (b) des couches de revêtement constituées d'un matériau polymère sont formées sur les deux surfaces du séparateur. La présente invention a une mouillabilité grandement améliorée d'un séparateur dans un électrolyte, améliore finalement et remarquablement les caractéristiques de charge/décharge et la longévité de cycle d'un accumulateur au lithium, et en particulier, peut être exploitée de manière stable même à température ambiante, pouvant ainsi être applicable à un dispositif accumulateur d'énergie de type appareil électronique portatif ou véhicule électrique.
PCT/KR2017/010687 2017-09-25 2017-09-27 Séparateur d'accumulateur au lithium employant un électrolyte liquide inorganique Ceased WO2019059440A1 (fr)

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KR1020170123631A KR102465701B1 (ko) 2017-09-25 2017-09-25 무기 액체 전해질을 채용한 리튬이차전지용 분리막
KR10-2017-0123631 2017-09-25

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113994514A (zh) * 2019-07-11 2022-01-28 株式会社Lg新能源 锂二次电池用电解质以及包含其的锂二次电池
CN113994512A (zh) * 2019-08-26 2022-01-28 株式会社Lg新能源 锂二次电池及其制备方法
CN115136404A (zh) * 2020-02-28 2022-09-30 帝人株式会社 非水系二次电池用隔膜及非水系二次电池

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