WO2015152478A1 - 수명 성능이 향상된 이차전지 - Google Patents
수명 성능이 향상된 이차전지 Download PDFInfo
- Publication number
- WO2015152478A1 WO2015152478A1 PCT/KR2014/009354 KR2014009354W WO2015152478A1 WO 2015152478 A1 WO2015152478 A1 WO 2015152478A1 KR 2014009354 W KR2014009354 W KR 2014009354W WO 2015152478 A1 WO2015152478 A1 WO 2015152478A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separator
- secondary battery
- porous substrate
- porous
- coating layer
- Prior art date
Links
Images
Classifications
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- 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
- H01M50/429—Natural polymers
-
- 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
- H01M50/44—Fibrous 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic 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
- H01M50/46—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a secondary battery having improved lifespan performance, and more particularly to a secondary battery having improved lifespan performance, including a high voltage positive electrode active material and a separator in which pores are not blocked even when used with the high voltage positive electrode active material.
- LiCoO 2 One commercially available cathode active material is LiCoO 2 .
- LiCoO 2 is expensive, the actual electric capacity is 140 ⁇ 150mAh / g is only about 50% of the theoretical capacity, active research into a positive electrode active material to replace it.
- a separator is used to prevent a short circuit between the positive electrode and the negative electrode, and a porous membrane formed from a polyolefin resin is widely used as the separator material.
- polyolefin-based resins generally have physical properties that melt at 200 ° C. or lower, and have a weakness of heat shrinking to their original size at a high temperature when a stretching process is performed to control pore size and porosity.
- the battery rises to a high temperature due to internal / external stimulation, it is more likely that the positive electrode and the negative electrode are shorted to each other due to shrinkage or melting of the separator, and thus the battery may be exploded due to the release of electrical energy. It has a risk.
- the present invention is to solve the above technical problem, to solve the problem of membrane pore occlusion caused by eluting the positive electrode active material when a high voltage positive electrode is used.
- the present invention is to provide a secondary battery having an excellent high temperature cycle capacity.
- the positive electrode in an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, the positive electrode includes a high voltage positive electrode active material, the separator is a porous substrate, and inorganic particles and An electrode assembly including an organic binder polymer and a porous coating layer formed on at least one surface of the porous substrate, wherein the pores formed in the separator have a longest diameter in the range of 10 nm to 5 ⁇ m.
- the lithium oxide may be one or a mixture of two or more selected from compounds represented by Formulas 1 to 4 below:
- LiMn 2-x M x O 4 (M Ni, Co, Fe and Al, at least one element selected from the group consisting of 0 ⁇ x ⁇ 2)
- the pores may have a longest diameter in the range from 50 to 500 nm.
- the separator may have a Gurley value in the range of 1 to 3000 sec / 100 cc.
- the separator may have a Gurley value in the range of 50 to 2000 sec / 100 cc.
- the porous coating layer may be formed on at least one side of the porous substrate to a thickness of 0.5 to 20 ⁇ m on the one side of the porous substrate.
- the porous coating layer may be formed on at least one side of the porous substrate to a thickness of 3 to 6 ⁇ m based on one side of the porous substrate.
- the porous coating layer is formed on one surface of the porous substrate, it may be interposed between the positive electrode and the negative electrode facing the negative electrode.
- the porous substrate may be a porous membrane formed from polyethylene resin.
- the porous substrate may be a nonwoven fabric.
- a secondary battery comprising the electrode assembly described above.
- the secondary battery may have an upper limit voltage of 4.3V or more and 5.0V or less.
- a porous coating layer is formed on a porous substrate having large pores such as a nonwoven fabric, and the separator is employed in a secondary battery, particularly a high voltage secondary battery, a cathode active material for high voltage as a cathode active material Even when used, the capacity drop does not occur at high temperature cycles and the life of the secondary battery is improved.
- Example 1 is a graph showing high temperature life performance of secondary batteries manufactured in Comparative Example 4-2 and Example 5-2.
- Figure 2 is a graph showing the high temperature life performance of the secondary battery produced in Comparative Example 1-2, Comparative Example 2-2 and Example 1-2.
- Example 3 is a graph showing the high temperature life performance of the secondary batteries produced in Comparative Example 2-2 and Examples 2-2 to 4-2.
- Figure 4 is a graph showing the high temperature life performance of the secondary battery produced in Comparative Example 1-2 and Example 6-2.
- the present invention provides a composite separator in which a porous coating layer is formed to ensure smooth movement of the cathode active material.
- a porous coating layer including inorganic particles having a lithium ion transfer capacity and a binder polymer as a component is formed on at least one surface of the porous substrate.
- the composite separator not only improves the electrolyte impregnation rate due to the micropores formed in the porous substrate, but also increases the lithium ion conductivity due to the lithium ion transfer ability of the inorganic particles.
- the porous substrate usable in the present invention may be in the form of a nonwoven fabric in which a porous web is formed by crossing nanofibers, or in the form of a porous membrane including a plurality of pores.
- Non-limiting examples of these include high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, polypropylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, polyester, Polyacetal, polyamide, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylene Sulfidero (polyphenylenesulfidro), polyethylenenaphthalene (polyethylenenaphthalene) or a mixture thereof.
- a nonwoven fabric having a large number of large pore structures therein to improve the electrolyte impregnation rate is preferable.
- the thickness of the porous substrate is not particularly limited, but is preferably in the range of 1 to 100 ⁇ m, more preferably in the range of 5 to 50 ⁇ m. If it is less than 1 ⁇ m, it is difficult to achieve a desired effect, and if it is more than 100 ⁇ m, it may act as a resistive layer.
- the porous coating layer formed by applying and drying the slurry for the porous coating layer including the inorganic particles, the organic polymer binder, and the solvent to the porous substrate may have a thickness of 0.5 to 20 ⁇ m based on one surface of the porous substrate, for example, 3 to 3. It may be 6 ⁇ m thick. When the thickness is less than 0.5 ⁇ m, it is difficult to obtain a desired effect such as pore securing, and when the thickness is more than 20 ⁇ m, it may act as a resistive layer.
- the inorganic particles used for forming the porous coating layer of the present invention are not particularly limited as long as they are electrochemically stable. That is, the inorganic particles that can be used in the present invention are not particularly limited as long as the oxidation and / or reduction reactions do not occur in the operating voltage range of the secondary battery (for example, 0 to 5V based on Li / Li + ). In particular, in the case of using the inorganic particles having the ion transport ability, it is possible to improve the performance by increasing the ion conductivity in the secondary battery.
- the ionic conductivity of the electrolyte may be improved by contributing to an increase in the dissociation degree of the electrolyte salt such as lithium salt in the liquid electrolyte.
- the inorganic particles it is preferable to use, as the inorganic particles, high dielectric constant inorganic particles having a dielectric constant of 5 or more, preferably 10 or more, inorganic particles having a lithium ion transfer ability, or a mixture thereof.
- Non-limiting examples of inorganic particles having a dielectric constant of 5 or more include BaTiO 3 , Pb (Zr, Ti) O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT), PB (Mg 3 Nb 2/3 ) O 3 -PbTiO 3 (PMN-PT), Hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2, SiC Or mixtures thereof.
- Inorganic particles such as 3 (PMN-PT) and hafnia (HfO 2 ) not only exhibit high dielectric constants with dielectric constants of more than 100, but also generate charges when tensioned or compressed under constant pressure, resulting in potential differences between both sides.
- PMN-PT Pb 1-x La x Zr 1-y Ti y O 3
- PB Mg 3 Nb 2/3
- O 3 -PbTiO Inorganic particles such as 3 (PMN-PT) and hafnia (HfO 2 ) not only exhibit high dielectric constants with dielectric constants of more than 100, but also generate charges when tensioned or compressed under constant pressure, resulting in potential differences between both sides.
- PMN-PT Pb 1-x La
- the inorganic particles having a lithium ion transfer capacity refers to an inorganic particle containing lithium element but having a function of transferring lithium ions without storing lithium, and the inorganic particles having a lithium ion transfer capacity are formed inside the particle structure. Since lithium ions can be transferred and transported due to a kind of defect present, lithium ion conductivity in the battery is improved, thereby improving battery performance.
- Non-limiting examples of the inorganic particles having a lithium ion transfer capacity is lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3) , Lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), 14Li 2 O-9Al 2 O 3 -38TiO 2 -39P (LiAlTiP) x O y series glass such as 2 O 5 (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 13), lithium lanthanum titanate (Li x La y TiO 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), Li germanium thiophosphate such as Li 3.25 Ge 0.25 P 0.75 S 4 (Li x Ge y P z S
- Li x P y S z such as (Li x Si y S z , 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 4), LiI-Li 2 SP 2 S 5, etc.) , 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 3, 0 ⁇ z ⁇ 7) or mixtures thereof.
- the size of the inorganic particles is not limited, but is preferably in the range of 0.01 to 10 ⁇ m. If it is less than 0.01 ⁇ m dispersibility is difficult to control the structure and physical properties of the porous coating layer, if it exceeds 10 ⁇ m, the thickness of the porous coating layer formed from the same solid content is increased, mechanical properties are lowered, too The large pore size increases the likelihood of internal short circuits during battery charging and discharging.
- any organic polymer binder that can be used to form the porous coating layer together with the inorganic particles may be used.
- the organic polymer binder having a solubility index of 15 to 45 Mpa 1/2 is used.
- the organic binder polymer performs a function of stably fixing by connecting the inorganic particles.
- Non-limiting examples of such organic binder polymer polyvinylidene fluoride-co-hexafluoropropylene (polyvinylidene fluoride-co-hexafluoropropylene), polyvinylidene fluoride-co-trichloroethylene (polyvinylidene fluoride-co-trichloroethylene) , Polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, ethylene vinyl acetate copolymer (polyethylene-co-vinyl acetate), polyethylene oxide (polyethylene oxide), cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol ), Cyanoethycellulose (cyanoethy lcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose, acrylon
- the content of the inorganic particles having the lithium ion transporting capacity is preferably in the range of 50 to 99% by weight, more preferably 60 to 95% by weight, per 100 parts by weight of the inorganic particles and the organic binder polymer constituting the porous coating layer. If the content is less than 50% by weight, the content of the organic binder polymer is too high, resulting in a decrease in pore size and porosity due to a decrease in the void space formed between the inorganic particles, resulting in deterioration of final battery performance. Since the polymer content is too low, the mechanical properties of the final composite separator are degraded due to the weakening of the adhesion between the inorganic materials.
- the solubility index is similar to that of the binder polymer to be used, and the boiling point is low. This is because mixing can be made uniform, and then the solvent can be easily removed.
- the solvent include acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, N-methyl-2-pyrrolidone (N -methyl-2-pyrrolidone (NMP), cyclohexane, water or a mixture thereof.
- the porous coating layer formed on the composite separator may form an interstitial volume in micro units by adjusting the size of inorganic particles, the content of inorganic particles, and the composition of the inorganic particles and the organic binder polymer, and also the pore size and pore. You can adjust the degree.
- the term 'interstitial volume' refers to an empty space defined by the inorganic particles substantially interviewed in a closed packed or densely packed, in which inorganic particles of the porous coating layer are bound to each other by a binder polymer. This is understood as a space for forming pores.
- the porous coating layer is formed only on one surface of the porous substrate and is interposed between the positive electrode and the negative electrode so as to face the negative electrode, and the secondary battery including the electrode assembly of this embodiment is a high temperature even if a high voltage positive electrode active material is used as the positive electrode active material. There is no drop in capacity during the cycle.
- the metal ions eluted from the high-voltage cathode active material is deposited on the cathode.
- the metal ions fill the pores of the porous coating layer first, thereby increasing the overall pore size and porosity of the separator. This is because the pore closure at the time of lithium dendrite generation can be delayed. As a result, lifespan performance can be greatly improved.
- high voltage positive electrode active material as used herein is understood to mean a compound that can be applied to high voltages in the range of 4.3 V to 5.0 V and capable of reversibly intercalating / deintercalating lithium. At this time, the 4.3 V to 5.0 V may be the upper limit voltage of the positive electrode active material.
- the pores formed in the composite separator more specifically, the pores formed in the porous coating layer of the composite separator preferably has a longest diameter of 10 nm to 5 ⁇ m or 50 nm to 1 ⁇ m or 50 nm to 500 nm. If the pore size is smaller than 10 nm, the pore size is similar to that of conventional membrane substrates such as polyethylene and polypropylene, and the effect of the porous coating layer cannot be expected. If the pore size exceeds 5 ⁇ m, the mechanical strength of the membrane is significantly weakened. Problem occurs.
- the pore size described above assumes that the interstitial volumes are assumed to be ideal pores, assuming that alumina having a diameter of 400 nm is a sphere, but since the actual pores have an inverse opal structure, the pore size is the same as that of alumina. It is a pore size determined in consideration of the fact that it must be larger than the radius of the inorganic particles and smaller than the diameter, and in fact, the particles do not ideally accumulate and there is an influence due to the binder.
- the composite separator of the present invention as described above preferably has a Gurley value in the range of 1 to 3000 sec / 100cc on the porous substrate. More preferably, it has a Gurley value in the range of 50-2000 sec / 100 cc.
- the Gurley value or the Gurley value means a time taken for 100 cc of air to pass through a predetermined area, and can be understood as 'airflow'.
- the separator of the present invention prepared as described above is used in the secondary battery by interposing between the positive electrode and the negative electrode.
- a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery among the secondary batteries is preferable.
- the secondary battery may be manufactured according to conventional methods known in the art, and for example, may be manufactured by injecting an electrolyte after assembling the separator between the positive electrode and the negative electrode.
- the electrode to be applied together with the separator may be prepared in a form in which the electrode active material is bound to the electrode current collector according to a conventional method known in the art.
- the positive electrode active material usable in the present invention may be used without limitation as long as it can be applied to a high voltage in the range of 4.3 V to 5.0 V and a compound capable of reversibly intercalating / deintercalating lithium.
- a non-limiting example is manganese.
- Preferred examples may include a cathode active material which is any one selected from Chemical Formulas 1 to 4 or a mixture of two or more thereof:
- LiMn 2-x M x O 4 (M at least one element selected from the group consisting of Ni, Co, Fe and Al, where 0 ⁇ x ⁇ 2)
- the average particle diameter of the particles in the positive electrode active material is preferably 5 to 15 ⁇ m, when the average particle diameter is less than 5 ⁇ m has the disadvantage that the tap density of the active material falls, when the average particle diameter exceeds 15 ⁇ m, the active material particle distribution is uniform If the density of the tap is not reduced and the size of the particles is too large, the diffusion length of Li ions is increased, resulting in a decrease in electrochemical properties.
- Non-limiting examples of the negative electrode active material may be a conventional negative electrode active material that can be used for the negative electrode of a conventional secondary battery, in particular lithium metal or lithium alloy, carbon, petroleum coke, activated carbon, graphite Lithium adsorbents such as graphite or other carbons are preferred.
- Non-limiting examples of the positive electrode current collector is a foil made by aluminum, nickel or a combination thereof, and non-limiting examples of the negative electrode current collector by copper, gold, nickel or copper alloy or a combination thereof Foils produced.
- Electrolyte that may be used in one embodiment of the present invention is A + B - A salt of the structure, such as, A + comprises a Li +, Na +, an alkali metal cation or an ion composed of a combination thereof, such as K + B - it is PF 6 -, BF 4 -, Cl -, Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C Salts containing ions consisting of anions such as (CF 2 SO 2 ) 3 - or a combination thereof are propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl Carbonate (DPC), dimethylsulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (N
- the electrolyte injection may be performed at an appropriate stage of the battery manufacturing process, depending on the manufacturing process and the required physical properties of the final product. That is, it may be applied before the battery assembly or at the end of battery assembly.
- a lamination (stacking) and a folding process of the separator and the electrode may be performed in addition to the general winding process.
- PVdF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
- the slurry thus prepared was coated on one surface of a porous polyethylene resin (SK512GK, SKI, thickness 12 ⁇ m, porosity 40%) by dip coating, and the thickness of the coating layer was about 5 ⁇ m.
- the separator thus prepared had a pore size in the range of about 50 nm to 1 ⁇ m.
- Li [Li 0.29 Ni 0.14 Co 0.11 Mn 0.46 ] O 2 94% by weight of Li [Li 0.29 Ni 0.14 Co 0.11 Mn 0.46 ] O 2 as the positive electrode active material, 3% by weight carbon black as the conductive material, 3% by weight PVdF as the binder N-methyl-2 pyrrolidone as a solvent (NMP) was added to prepare a positive electrode mixture slurry.
- the positive electrode mixture slurry was coated and dried on a thin film of aluminum (Al) which is a positive electrode current collector having a thickness of about 20 ⁇ m to prepare a positive electrode.
- Al aluminum
- a negative electrode mixture slurry was prepared by adding carbon powder as a negative electrode active material, PVdF as a binder, and carbon black as a conductive material at 96 wt%, 3 wt%, and 1 wt%, respectively, to NMP as a solvent.
- the negative electrode mixture slurry was coated and dried on a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 ⁇ m, to prepare a negative electrode.
- Cu copper
- the separator prepared in Example 1-1 was assembled between the positive electrode and the negative electrode so that the porous coating layer of the separator faced the negative electrode, and then assembled by using a stacking method.
- the assembled battery was 1M lithium hexafluorophosphate (LiPF). 6
- a secondary battery was manufactured according to the method described in Example 1-2 except for using the separator prepared in Example 2-1.
- a separator was prepared in the same manner as in Example 2-1 except that the separator was prepared such that the porous coating layer had a thickness of 5 ⁇ m (total 10 ⁇ m) on each side of the porous substrate.
- a secondary battery was manufactured according to the method described in Example 1-2 except for using the separator prepared in Example 3-1.
- a separator was prepared in the same manner as in Example 2-1 except that the separator was prepared such that the porous coating layer was formed to have a thickness of 6 ⁇ m (12 ⁇ m in total) on both sides of the porous substrate.
- a secondary battery was manufactured according to the method described in Example 1-2 except for using the separator prepared in Example 4-1.
- Example 2- except that polypropylene resin (PP1615, Celgard, 16 ⁇ m thick) is used as the porous substrate and that the porous coating layer is formed on both sides of the porous substrate to have a thickness of 5 ⁇ m (total 10 ⁇ m), respectively.
- a separator was prepared in the same manner as in Example 1.
- a secondary battery was manufactured according to the method described in Example 1-2 except for using the separator prepared in Example 5-1.
- Example 2- except that polyethylene terephthalate nonwoven fabric (PET) (15 ⁇ m in thickness) was used as the porous substrate and the porous coating layer was formed on both sides of the porous substrate to have a thickness of 5 ⁇ m (total 10 ⁇ m) respectively.
- a separator was prepared in the same manner as in Example 1.
- a secondary battery was manufactured according to the method described in Example 1-2 except for using the separator prepared in Example 6-1.
- Polyethylene resin (SK512GK, SKI, thickness 12 ⁇ m, Gurley value 160 sec), which is a porous substrate, was used as a separator.
- a secondary battery was manufactured according to the method described in Example 1-2 except for using the separator of Comparative Example 1-1.
- Example 1-1 The separator obtained in Example 1-1 was used.
- a secondary battery was manufactured according to the method of Example 2-2, except that the separator prepared in Comparative Example 2-1 was interposed between the cathode and the anode such that the porous coating layer was directed to the anode.
- Polypropylene / polyethylene / polypropylene resin (C210, Celgard, 16 ⁇ m thick), which is a porous substrate, was used as a separator.
- a secondary battery was manufactured according to the method described in Example 1-2 except for using the separator of Comparative Example 3-1.
- Polypropylene resin (PP1615, manufacturer name, thickness 16 ⁇ m) that is a porous substrate was used as a separator.
- a secondary battery was manufactured according to the method described in Example 1-2 except for using the separator of Comparative Example 4-1.
- Example 1-1 244 Example 2-1 1000
- Example 3-1 1350 Example 4-1 1450
- Example 5-1 857 Example 6-1 70 Comparative Example 1-1 160 Comparative Example 2-1 244 Comparative Example 3-1 464 Comparative Example 4-1 400
- Example 6-1 separator in which the porous coating layers were formed on both sides of the polyethylene terephthalate nonwoven fabric showed the best air permeability
- the separator of Comparative Example 1-1 in which the porous coating layer was not formed on the porous substrate was Excellent air permeability was shown
- the cells prepared in Examples and Comparative Examples were subjected to 40 cycles or 80 cycles of 1C charge / 1C discharge at a voltage range of 4.35 to 2.5V at 45 ° C, and the results are shown in FIGS. 1 to 4.
- the separators of Example 1-1 and Comparative Example 2-1 having the same thickness applied to only one surface of the porous substrate have the same result in terms of Gurley value, whereas these membranes are different only in the application direction of the porous coating layer.
- the secondary battery of Example 1-2 applied with the porous coating layer toward the anode the secondary battery of Comparative Example 2-2 applied with the porous coating layer toward the positive electrode It has been shown to have good hot cycle life compared to (see FIG. 2).
- the secondary battery of Example 6-2 having the porous coating layers formed on both surfaces of the nonwoven fabric has an excellent high temperature life compared to the secondary battery of Comparative Example 1-2 in which the porous coating layer is not formed.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
Description
분리막 | 걸리값 (sec/100mL ) |
실시예 1-1 | 244 |
실시예 2-1 | 1000 |
실시예 3-1 | 1350 |
실시예 4-1 | 1450 |
실시예 5-1 | 857 |
실시예 6-1 | 70 |
비교예 1-1 | 160 |
비교예 2-1 | 244 |
비교예 3-1 | 464 |
비교예 4-1 | 400 |
Claims (12)
- 양극, 음극, 및 양극과 음극 사이에 개재된 분리막을 포함하는 전극 조립체에 있어서,상기 양극이 고전압용 양극 활물질을 포함하고,상기 분리막이 다공성 기재, 및 무기물 입자와 유기 바인더 고분자를 포함하고 상기 다공성 기재의 적어도 일면에 형성된 다공성 코팅층을 포함하며,상기 분리막에 형성된 기공이 10 nm 내지 5 ㎛ 범위의 최장 직경을 갖는 것인 전극 조립체.
- 제1항에 있어서,상기 리튬산화물은 하기 화학식 1 내지 4로 표시되는 화합물로부터 선택되는 1종 또는 2종 이상의 혼합물인 전극 조립체:[화학식 1]Lix[NiaCobMnc]O2 (0.95≤x≤1.05, 0≤ a, b, c ≤1, a+b+c = 1이고, 단, a와 c는 동시에 0이 될 수 없다)[화학식 2]Li[LixNiaCobMnc]O2 (0.05≤x≤0.6, x+a+b+c = 1이다)[화학식 3]Lix[NiaCobMnc]O2 (0.95≤x≤1.05, 0 < a, b, c ≤1, a+b+c =1, 0.4<c<1)[화학식 4]LiMn2-xMxO4 (M=Ni, Co, Fe 및 Al로 이루어진 군에서 선택되는 하나 이상의 원소이고, 0 ≤x≤2이다)
- 제1항에 있어서,상기 기공이 50 내지 500 nm 범위의 최장 직경을 가지는 것을 특징으로 하는 전극 조립체.
- 제1항에 있어서,상기 분리막이 1 내지 3000 sec/100 cc 범위의 걸리(Gurley)값을 가지는 것인 전극 조립체.
- 제1항에 있어서,상기 분리막이 50 내지 2000 sec/100 cc 범위의 걸리값을 가지는 것인 전극 조립체.
- 제1항에 있어서,상기 다공성 코팅층이 다공성 기재의 일면 기준으로 0.5 내지 20 ㎛ 두께로 다공성 기재의 적어도 일면에 형성되는 것을 특징으로 하는 전극 조립체.
- 제1항에 있어서,상기 다공성 코팅층이 다공성 기재의 일면 기준으로 3 내지 6 ㎛ 두께로 다공성 기재의 적어도 일면에 형성되는 것을 특징으로 하는 전극 조립체.
- 제1항에 있어서,상기 다공성 코팅층이 상기 다공성 기재의 일면에 형성되어 있되, 음극을 향하도록 양극과 음극 사이에 개재되어 있는 전극 조립체.
- 제1항에 있어서,상기 다공성 기재가 폴리에틸렌 수지로부터 형성된 다공성 막(membrane)인 전극 조립체.
- 제1항에 있어서,상기 다공성 기재가 부직포인 전극 조립체.
- 제1항 내지 제10항중 어느 한 항에 기재된 전극 조립체를 포함하는 이차전지.
- 제11항에 있어서,4.3V 이상 5.0V 이하의 상한 전압을 가지는 것을 특징으로 하는 이차전지.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/646,598 US9887407B2 (en) | 2014-04-04 | 2014-10-02 | Secondary battery with improved life characteristics |
EP14888476.0A EP3048660A4 (en) | 2014-04-04 | 2014-10-02 | Secondary battery having improved life span performance |
CN201480063770.9A CN105794032B (zh) | 2014-04-04 | 2014-10-02 | 具有改善的寿命特性的二次电池 |
JP2016518752A JP6416237B2 (ja) | 2014-04-04 | 2014-10-02 | 寿命性能が向上した二次電池 |
US15/851,068 US10673045B2 (en) | 2014-04-04 | 2017-12-21 | Secondary battery with improved life characteristics |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20130037547 | 2013-04-05 | ||
KR10-2014-0040650 | 2014-04-04 | ||
KR1020140040650A KR101715696B1 (ko) | 2013-04-05 | 2014-04-04 | 수명 성능이 향상된 이차전지 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/646,598 A-371-Of-International US9887407B2 (en) | 2014-04-04 | 2014-10-02 | Secondary battery with improved life characteristics |
US15/851,068 Continuation US10673045B2 (en) | 2014-04-04 | 2017-12-21 | Secondary battery with improved life characteristics |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015152478A1 true WO2015152478A1 (ko) | 2015-10-08 |
Family
ID=51992945
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2014/009354 WO2015152478A1 (ko) | 2013-04-05 | 2014-10-02 | 수명 성능이 향상된 이차전지 |
Country Status (2)
Country | Link |
---|---|
KR (1) | KR101715696B1 (ko) |
WO (1) | WO2015152478A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112670673A (zh) * | 2020-12-24 | 2021-04-16 | 肇庆市华师大光电产业研究院 | 一种离子传导有机-无机复合修饰隔膜及其制备方法和应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20100135369A (ko) * | 2009-06-17 | 2010-12-27 | 에스케이에너지 주식회사 | 고내열성 유/무기 피복층을 갖는 폴리에틸렌계 복합 미세다공막 |
KR20110075631A (ko) * | 2009-12-28 | 2011-07-06 | 롯데알미늄 주식회사 | 나노기공을 갖는 세퍼레이터 및 이를 이용한 에너지 저장 장치 |
KR20120114143A (ko) * | 2011-04-04 | 2012-10-16 | 주식회사 톱텍 | 세퍼레이터, 세퍼레이터 제조 장치 및 세퍼레이터 제조 방법 |
KR20130043485A (ko) * | 2011-10-20 | 2013-04-30 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
KR20130117347A (ko) * | 2012-04-18 | 2013-10-25 | 주식회사 엘지화학 | 기계적 특성이 향상된 부직포 분리막의 제조방법 및 이를 사용하여 제조되는 부직포 분리막 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101491805B1 (ko) * | 2008-02-15 | 2015-02-11 | 삼성에스디아이 주식회사 | 전극조립체 및 이를 구비하는 리튬 이차 전지 |
-
2014
- 2014-04-04 KR KR1020140040650A patent/KR101715696B1/ko active IP Right Grant
- 2014-10-02 WO PCT/KR2014/009354 patent/WO2015152478A1/ko active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20100135369A (ko) * | 2009-06-17 | 2010-12-27 | 에스케이에너지 주식회사 | 고내열성 유/무기 피복층을 갖는 폴리에틸렌계 복합 미세다공막 |
KR20110075631A (ko) * | 2009-12-28 | 2011-07-06 | 롯데알미늄 주식회사 | 나노기공을 갖는 세퍼레이터 및 이를 이용한 에너지 저장 장치 |
KR20120114143A (ko) * | 2011-04-04 | 2012-10-16 | 주식회사 톱텍 | 세퍼레이터, 세퍼레이터 제조 장치 및 세퍼레이터 제조 방법 |
KR20130043485A (ko) * | 2011-10-20 | 2013-04-30 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
KR20130117347A (ko) * | 2012-04-18 | 2013-10-25 | 주식회사 엘지화학 | 기계적 특성이 향상된 부직포 분리막의 제조방법 및 이를 사용하여 제조되는 부직포 분리막 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112670673A (zh) * | 2020-12-24 | 2021-04-16 | 肇庆市华师大光电产业研究院 | 一种离子传导有机-无机复合修饰隔膜及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
KR20140121362A (ko) | 2014-10-15 |
KR101715696B1 (ko) | 2017-03-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2806483B1 (en) | Separator for secondary battery comprising dual porous coating layer of inorganic particles with different surface characteristics, secondary battery comprising the same, and method of manufacturing the separator | |
KR100918751B1 (ko) | 분리막과의 계면 접착이 향상된 전극 및 이를 포함하는전기 화학 소자 | |
KR101040482B1 (ko) | 다공성 코팅층이 코팅된 세퍼레이터 및 이를 구비한 전기화학소자 | |
WO2016093589A1 (ko) | 안전성이 향상된 전극조립체, 그의 제조방법 및 상기 전극조립체를 포함하는 전기화학소자 | |
WO2015065118A1 (ko) | 전극조립체 및 그를 포함하는 리튬 이차전지 | |
WO2016064256A1 (ko) | 유/무기 복합 다공층을 포함하는 이차 전지용 세퍼레이터 및 이의 제조 방법 | |
WO2013012292A2 (ko) | 세퍼레이터, 그 제조방법 및 이를 구비한 전기화학소자 | |
WO2012046966A2 (ko) | 사이클 특성이 개선된 전기화학소자 | |
WO2011019187A2 (ko) | 리튬 이차전지 | |
WO2013100653A1 (ko) | 리튬 이차전지 및 그 제조방법 | |
WO2014182095A1 (ko) | 절연층을 포함한 전극 구조체, 그 제조방법 및 상기 전극을 포함하는 전기화학소자 | |
WO2013070031A1 (ko) | 세퍼레이터 및 이를 구비한 전기화학소자 | |
WO2011105866A2 (ko) | 세퍼레이터의 제조방법, 이로부터 형성된 세퍼레이터 및 이를 포함하는 전기화학소자의 제조방법 | |
WO2013157902A1 (ko) | 세퍼레이터의 제조방법, 이로부터 형성된 세퍼레이터 및 이를 포함하는 전기화학소자 | |
WO2015047034A1 (ko) | 리튬 이차전지용 세퍼레이터의 제조방법, 그 방법에 의해 제조된 세퍼레이터, 및 이를 포함하는 리튬 이차전지 | |
WO2018038584A1 (ko) | 전기화학소자용 분리막 및 상기 분리막을 포함하는 전기화학소자 | |
KR20130066746A (ko) | 리튬 이차전지용 고내열성 복합체 세퍼레이터 및 이를 포함하는 리튬 이차전지 | |
WO2013066052A1 (ko) | 세퍼레이터 및 이를 구비한 전기화학소자 | |
WO2017213443A1 (ko) | 세퍼레이터 및 이를 포함하는 전기화학소자 | |
WO2012111956A2 (ko) | 세퍼레이터, 그 제조방법 및 이를 구비한 전기화학소자 | |
WO2017213444A1 (ko) | 세퍼레이터 및 이를 포함하는 전기화학소자 | |
WO2022075823A1 (ko) | 접착층을 포함하는 이차 전지용 분리막 및 상기 분리막의 제조방법 | |
WO2015065116A1 (ko) | 유기-무기 복합 다공성 막, 이를 포함하는 세퍼레이터 및 전극 구조체 | |
WO2019078650A1 (ko) | 세퍼레이터 및 이를 포함하는 전기화학소자 | |
TWI568062B (zh) | 具有經改善之壽命特性之二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 14646598 Country of ref document: US |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14888476 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016518752 Country of ref document: JP Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2014888476 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014888476 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |