WO2018078702A1 - セパレータ、およびセパレータを含む二次電池 - Google Patents
セパレータ、およびセパレータを含む二次電池 Download PDFInfo
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- WO2018078702A1 WO2018078702A1 PCT/JP2016/081479 JP2016081479W WO2018078702A1 WO 2018078702 A1 WO2018078702 A1 WO 2018078702A1 JP 2016081479 W JP2016081479 W JP 2016081479W WO 2018078702 A1 WO2018078702 A1 WO 2018078702A1
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
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Definitions
- One embodiment of the present invention relates to a separator and a secondary battery including the separator.
- one embodiment of the present invention relates to a separator that can be used in a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery including the separator.
- a typical example of a non-aqueous electrolyte secondary battery is a lithium ion secondary battery.
- Lithium ion secondary batteries have a high energy density, and are therefore widely used in electronic devices such as personal computers, mobile phones, and portable information terminals.
- the lithium ion secondary battery has a positive electrode, a negative electrode, an electrolytic solution filled between the positive electrode and the negative electrode, and a separator.
- the separator functions as a membrane that separates the positive electrode and the negative electrode and allows the electrolyte and carrier ions to pass therethrough.
- Patent Documents 1 to 5 disclose separators containing polyolefin.
- One of the objects of the present invention is to provide a separator that can be used in a secondary battery such as a non-aqueous electrolyte secondary battery, and a secondary battery including the separator.
- a separator capable of suppressing a decrease in rate characteristics when the secondary battery is repeatedly discharged and charged, and a secondary battery including the separator.
- One embodiment of the present invention is a separator having a first layer made of porous polyolefin. After impregnating the first layer with N-methylpyrrolidone containing 3% by weight of water, when the first layer is irradiated with microwaves having a frequency of 2455 MHz at an output of 1800 W, the temperature rise convergence time of the first layer is 2.9 s ⁇ m 2 / g or more and 5.7 s ⁇ m 2 / g or less, and the white index of the first layer is 86 or more and 98 or less.
- a separator that provides a secondary battery that can exhibit excellent rate characteristics even after repeated charge and discharge, and a secondary battery such as a non-aqueous electrolyte secondary battery including the separator.
- the expression “substantially containing only A” includes a substance other than A, a state containing A and impurities, and a substance other than A due to measurement error. This includes situations that are mistaken for When this expression indicates a state containing A and impurities, there is no limitation on the type and concentration of impurities.
- the secondary battery 100 includes a positive electrode 110, a negative electrode 120, and a separator 130 that separates the positive electrode 110 and the negative electrode 120.
- the secondary battery 100 has an electrolytic solution 140.
- the electrolyte solution 140 is present mainly in the gaps between the positive electrode 110, the negative electrode 120, and the separator 130 and in the gaps between the members.
- the positive electrode 110 may include a positive electrode current collector 112 and a positive electrode active material layer 114.
- the negative electrode 120 can include a negative electrode current collector 122 and a negative electrode active material layer 124.
- the secondary battery 100 further includes a housing, and the positive electrode 110, the negative electrode 120, the separator 130, and the electrolytic solution 140 are held by the housing.
- the separator 130 is a film that is provided between the positive electrode 110 and the negative electrode 120, separates the positive electrode 110 and the negative electrode 120, and carries the movement of the electrolyte solution 140 within the secondary battery 100.
- FIG. 1B is a schematic cross-sectional view of the separator 130.
- the separator 130 has the 1st layer 132 containing porous polyolefin, and can further have the porous layer 134 as arbitrary structures. As shown in FIG. 1B, the separator 130 may have a structure in which two porous layers 134 sandwich the first layer 132. However, the separator 130 is porous only on one surface of the first layer 132.
- the layer 134 may be provided, or the porous layer 134 may not be provided.
- the first layer 132 may have a single-layer structure or may include a plurality of layers.
- the first layer 132 has pores connected to the inside. Due to this structure, the electrolyte solution 140 can pass through the first layer 132, and carrier ions such as lithium ions can move through the electrolyte solution 140. At the same time, physical contact between the positive electrode 110 and the negative electrode 120 is prohibited. On the other hand, when the secondary battery 100 reaches a high temperature, the first layer 132 melts and becomes nonporous, thereby stopping the movement of carrier ions. This operation is called shutdown. By this operation, heat generation and ignition due to a short circuit between the positive electrode 110 and the negative electrode 120 are prevented, and high safety can be ensured.
- the first layer 132 may be made of porous polyolefin. That is, the first layer 132 may be configured to include only porous polyolefin or substantially only porous polyolefin. Alternatively, the first layer 132 can include a porous polyolefin and an additive. In this case, the first layer 132 may be composed of only the porous polyolefin and the additive, or substantially only the porous polyolefin and the additive. When the porous polyolefin and the organic additive are included, the polyolefin can be contained in the porous polyolefin with a composition of 95% by weight or more, or 97% by weight or more, or 99% by weight or more.
- the polyolefin can be included in the first layer 132 with a composition of 95 wt% or more, or 97 wt% or more, or 99 wt% or more.
- the polyolefin content in the porous film may be 100% by weight or 100% by weight or less.
- the additive include an organic compound (organic additive), and the organic compound may be an antioxidant (organic antioxidant) or a lubricant.
- Examples of the polyolefin constituting the porous polyolefin include homopolymers obtained by polymerizing ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, and copolymers thereof. be able to.
- the first layer 132 may contain a mixture of these homopolymers and copolymers.
- the organic additive can have a function of preventing oxidation of the polyolefin.
- phenols and phosphates can be used as the organic additive.
- Phenols having a bulky substituent at the ⁇ -position and / or ⁇ -position of the phenolic hydroxyl group may be used.
- Typical examples of the polyolefin include a polyethylene polymer.
- a polyethylene polymer either low density polyethylene or high density polyethylene may be used.
- a copolymer of ethylene and ⁇ -olefin may be used.
- These polymers or copolymers may be a high molecular weight body having a weight average molecular weight of 100,000 or more, or an ultrahigh molecular weight body having a weight average molecular weight of 1,000,000 or more.
- the shutdown function can be expressed at a lower temperature, and high safety can be imparted to the secondary battery 100.
- the mechanical strength of a separator can be improved by using the ultra high molecular weight body whose weight average molecular weight is 1 million or more.
- the thickness of the first layer 132 may be determined as appropriate in consideration of the thickness of other members in the secondary battery 100 and the like, and may be 4 ⁇ m to 40 ⁇ m, 5 ⁇ m to 30 ⁇ m, or 6 ⁇ m to 15 ⁇ m. be able to.
- the basis weight of the first layer 132 may be appropriately determined in consideration of strength, film thickness, weight, and handleability. For example, 4 g / m 2 or more and 20 g / m 2 or less, 4 g / m 2 or more and 12 g / m 2 or less, or 5 g / m 2 or more so that the weight energy density and volume energy density of the secondary battery 100 can be increased. It can be 10 g / m 2 or less.
- the basis weight is the weight per unit area.
- the air permeability of the first layer 132 can be selected from the range of 30 s / 100 mL to 500 s / 100 mL, or 50 s / 100 mL to 300 s / 100 mL in terms of Gurley value. Thereby, sufficient ion permeability can be obtained.
- the porosity of the first layer 132 is in the range of 20% by volume to 80% by volume, or 30% by volume to 75% by volume so that the retention amount of the electrolytic solution 140 can be increased and the shutdown function can be expressed more reliably. You can choose from. Further, the pore diameter (average pore diameter) of the first layer 132 is 0.01 ⁇ m or more and 0.3 ⁇ m or less, or 0.01 ⁇ m or more and 0 or more so that sufficient ion permeability and a high shutdown function can be obtained. It can be selected from the range of 14 ⁇ m or less.
- the first layer 132 is impregnated with N-methylpyrrolidone containing 3% by weight of water, and then the time per unit area until the temperature rises when the microwave with a frequency of 2455 MHz is irradiated at an output of 1800 W (hereinafter referred to as the basis weight).
- the temperature rise convergence time is 2.9 s ⁇ m 2 / g or more and 5.7 s ⁇ m 2 / g or less, or 2.9 s ⁇ m 2 / g or more and 5.3 s ⁇ m 2 / g or less.
- the first layer 132 has a white index (hereinafter referred to as WI) of 86 to 98, or 90 to 97.
- WI white index
- WI is WI defined in E313 of AMERICA Standards TEST Methods. WI can be measured using an optical measuring device such as an integrating sphere spectrocolorimeter.
- the structure of the pores of the first layer 132 (capillary force in the pores and the area of the walls of the pores), and the ability to supply the electrolytic solution 140 from the first layer 132 to the electrodes (the positive electrode 110 and the negative electrode 120) Is related to a decrease in rate characteristics when the battery is repeatedly charged and discharged or operated with a large current.
- the electrode expands.
- the negative electrode 120 expands during charging
- the positive electrode 110 expands during discharging. Therefore, the electrolytic solution 140 contained in the first layer 132 is pushed out from the expanding electrode side to the opposing electrode side. With such a mechanism, the electrolytic solution 140 moves in the pores of the first layer 132 during the charge / discharge cycle.
- the wall surfaces of the pores are subjected to pressure by the electrolytic solution 140.
- the strength of the pressure is related to the pore structure. Specifically, it is considered that the pressure applied to the wall surface of the pore increases as the capillary force increases, and increases as the area of the wall surface of the pore increases. Further, the strength of the pressure is also related to the amount of the electrolytic solution 140 that moves in the pores, and is considered to increase when the amount of the moving electrolytic solution 140 is large, that is, when the secondary battery 100 is operated with a large current. .
- the pressure increases, the wall surface is deformed so as to close the pores by the pressure, and as a result, the battery output characteristics are deteriorated. For this reason, rate characteristics are gradually deteriorated by repeatedly charging / discharging the secondary battery 100 or operating it with a large current.
- N-methylpyrrolidone containing water when N-methylpyrrolidone containing water is irradiated with microwaves, heat is generated by vibration energy of water. The generated heat is transferred to the first layer 132 in contact with N-methylpyrrolidone.
- the temperature rise of N-methylpyrrolidone converges when the heat release rate and the heat release rate due to heat transfer to the first layer 132 reach equilibrium. Therefore, the time until the temperature rise converges (temperature rise convergence time) is related to the degree of contact between the solvent contained in the first layer 132 (here, N-methylpyrrolidone containing water) and the first layer 132. To do.
- the degree of this contact is closely related to the capillary force in the pores of the first layer 132 and the area of the pore walls
- the structure of the pores of the first layer 132 depends on the temperature rise convergence time. Can be evaluated. Specifically, as the temperature rise convergence time is shorter, the capillary force in the pore is larger and the area of the pore wall is larger.
- the degree of this contact increases as the electrolyte easily moves in the pores of the first layer 132. Therefore, the ability to supply the electrolytic solution 140 from the first layer 132 to the positive electrode 110 or the negative electrode 120 can be evaluated based on the temperature rise convergence time. Specifically, the supply capability of the electrolytic solution 140 is higher as the temperature rise convergence time is shorter.
- the capillary force in the pores of the first layer 132 and the area of the pore walls are too large.
- the pressure applied to the walls of the pores by the electrolytic solution 140 that moves in the pores increases and the pores are blocked.
- the temperature rise convergence time exceeds 5.7 s ⁇ m 2 / g
- the solvent becomes difficult to move in the pores of the first layer 132 and the moving speed of the electrolytic solution 140 is reduced in the vicinity of the electrode.
- the rate characteristics of the battery deteriorate.
- the internal resistance of the secondary battery 100 increases, the rate characteristics after repeated charge / discharge are reduced, and the output characteristics are reduced.
- WI is an index representing color (whiteness), and the higher the WI, the higher the whiteness. It is considered that the lower the WI (that is, the lower the whiteness), the greater the amount of functional groups such as carboxy groups on the surface and inside of the first layer 132. Since the polar functional group such as a carboxy group inhibits the transmission of carrier ions (that is, the permeability becomes low), it is considered that the rate characteristic of the secondary battery 100 decreases as the WI decreases.
- the WI of the first layer 132 is not less than 86 and not more than 98, the amount of the functional group on the surface and inside of the first layer 132 is suitable for maintaining carrier ion permeability.
- the carrier ion permeability of the layer 132 can be in a suitable range. As a result, by using the first layer 132 in which the WI satisfies the above-described range, it is possible to suppress a decrease in the rate characteristics of the secondary battery, and to exhibit excellent rate characteristics even after repeated charge and discharge. be able to.
- the WI of the first layer 132 is preferably 90 or more and 97 or less.
- the WI of the first layer 132 is 86 or more, the amount of functional groups on the surface and inside of the first layer 132 is small, so that the carrier ion permeability of the first layer 132 is high. As a result, it is possible to suppress a decrease in rate sustainability.
- the WI of the first layer 132 exceeds 98, the affinity of the first layer 132 with respect to the electrolytic solution 140 is reduced because the amount of surface functional groups on the surface and inside of the first layer 132 becomes too small. Therefore, the movement of carrier ions is inhibited.
- the separator 130 including the first layer 132 that satisfies the above parameters it is possible to provide the secondary battery 100 that can exhibit excellent rate characteristics even after repeated charge and discharge.
- the positive electrode 110 may include the positive electrode current collector 112 and the positive electrode active material layer 114.
- the negative electrode 120 can include a negative electrode current collector 122 and a negative electrode active material layer 124 (see FIG. 1A).
- the positive electrode current collector 112 and the negative electrode current collector 122 have a function of holding the positive electrode active material layer 114 and the negative electrode active material layer 124 and supplying current to the positive electrode active material layer 114 and the negative electrode active material layer 124, respectively.
- the positive electrode current collector 112 and the negative electrode current collector 122 for example, a metal such as nickel, stainless steel, copper, titanium, tantalum, zinc, iron, cobalt, or an alloy containing these metals such as stainless steel can be used. .
- the positive electrode current collector 112 and the negative electrode current collector 122 may have a structure in which a plurality of films containing these metals are stacked.
- the positive electrode active material layer 114 and the negative electrode active material layer 124 each include a positive electrode active material and a negative electrode active material.
- the positive electrode active material and the negative electrode active material are materials responsible for the release and absorption of carrier ions such as lithium ions.
- the positive electrode active material examples include materials that can be doped / undoped with carrier ions.
- a lithium composite oxide containing at least one transition metal such as vanadium, manganese, iron, cobalt, or nickel can be given.
- such composite oxides include lithium composite oxides having an ⁇ -NaFeO 2 type structure such as lithium nickelate and lithium cobaltate, and lithium composite oxides having a spinel type structure such as lithium manganese spinel. These composite oxides have a high average discharge potential.
- the lithium composite oxide may contain other metal elements, for example, titanium, zirconium, cerium, yttrium, vanadium, chromium, manganese, iron, cobalt, copper, silver, magnesium, aluminum, gallium, indium, tin, etc.
- composite lithium nickelate containing aluminum or manganese and having nickel of 85 mol% or more, or 90 mol% or more can be used as the positive electrode active material.
- a material that can be doped / undoped with carrier ions can be used as the negative electrode active material.
- lithium metal or a lithium alloy can be used.
- carbonaceous materials such as graphite such as natural graphite and artificial graphite, coke, carbon black, and burned polymer compound such as carbon fiber; oxide that performs doping and dedoping of lithium ions at a lower potential than the positive electrode, Chalcogen compounds such as sulfides; elements such as aluminum, lead, tin, bismuth and silicon that are alloyed or combined with alkali metals; cubic intermetallic compounds (AlSb, Mg that can insert alkali metals between lattices) 2 Si, NiSi 2); lithium nitrogen compounds (Li 3-x M x N (M: transition metal)) and the like can be used.
- carbonaceous materials mainly composed of graphite such as natural graphite and artificial graphite have high potential flatness and low average discharge potential, and therefore give a large energy density when combined with the positive electrode 110.
- carbonaceous materials mainly composed of graphite such as natural graphite and artificial graphite have high potential flatness and low average discharge potential, and therefore give a large energy density when combined with the positive electrode 110.
- a mixture of graphite and silicon having a silicon to carbon ratio of 5 mol% or more or 10 mol% or more can be used as the negative electrode active material.
- the positive electrode active material layer 114 and the negative electrode active material layer 124 may each include a conductive additive, a binder, and the like in addition to the positive electrode active material and the negative electrode active material.
- Examples of conductive aids include carbonaceous materials. Specific examples include graphite such as natural graphite and artificial graphite, coke, carbon black, pyrolytic carbon, and fired organic polymer compound such as carbon fiber. A plurality of the above materials may be mixed and used as a conductive aid.
- PVDF polyvinylidene fluoride
- vinylidene fluoride-hexafluoropropylene copolymer tetrafluoroethylene-hexafluoropropylene copolymer
- tetrafluoroethylene-perfluoroalkyl vinyl ether Copolymer ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, etc.
- copolymers using vinylidene fluoride as one of the monomers thermoplastic polyimide
- thermoplastic resins such as polyethylene and polypropylene, acrylic resins, and styrene-butadiene rubber. Note that the binder also has a function as a thickener.
- the positive electrode 110 can be formed, for example, by applying a mixture of a positive electrode active material, a conductive additive, and a binder onto the positive electrode current collector 112. In this case, a solvent may be used to create or apply the mixture. Alternatively, the positive electrode 110 may be formed by pressurizing and molding a mixture of the positive electrode active material, the conductive additive, and the binder, and placing the mixture on the positive electrode 110.
- the negative electrode 120 can also be formed by a similar method.
- the electrolytic solution 140 includes a solvent and an electrolyte, and at least a part of the electrolyte is dissolved in the solvent and ionized.
- the solvent water or an organic solvent can be used.
- an organic solvent is used.
- Organic solvents include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane Ethers such as tetrahydrofuran, 2-methyltetrahydrofuran; esters such as methyl formate, methyl acetate and ⁇ -butyrolactone; nitriles such as acetonitrile and butyronitrile; amides such as N, N-dimethylformamide and N, N-dimethylacetamide Carbamates such as 3-methyl-2-oxazolidone; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 1,3-propane sultone; and fluorine is introduced into the organic solvent. Such as fluorine-containing organic solvent and the like. A mixed solvent of these organic solvents may be used
- a typical electrolyte includes a lithium salt.
- a lithium salt For example, LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , Li 2 B 10 Cl 10 , carbon number 2 To 6 carboxylic acid lithium salts, LiAlCl 4 and the like. Only one type of lithium salt may be used, or two or more types may be combined.
- the electrolyte sometimes refers to a solution in which the electrolyte is dissolved in a broad sense, but the narrow meaning is adopted in the present specification and claims. That is, the electrolyte is a solid, is ionized by being dissolved in a solvent, and is treated as giving ion conductivity to the resulting solution.
- a negative electrode 120, a separator 130, and a positive electrode 110 are arranged to form a stacked body.
- the laminate is installed in a housing (not shown), and the housing is filled with the electrolyte, and the housing is sealed while reducing the pressure, or the housing is sealed and then the housing is filled with the electrolyte and then sealed.
- the secondary battery 100 can be manufactured.
- the shape of the secondary battery 100 is not particularly limited, and may be a thin plate (paper) type, a disk type, a cylindrical type, a rectangular column type such as a rectangular parallelepiped, or the like.
- the separator 130 of the present embodiment has a first layer 132 containing porous polyolefin, and the first layer 132 satisfies the above-described temperature rise convergence time and WI ranges.
- the secondary battery 100 includes a separator 130 including a first layer 132 that satisfies such characteristics. Therefore, the secondary battery 100 can exhibit a small decrease in rate characteristics, that is, excellent rate characteristic maintainability.
- One of the methods for producing the first layer 132 is (1) a step of kneading an ultrahigh molecular weight polyethylene, a low molecular weight polyolefin having a weight average molecular weight of 10,000 or less, and a pore-forming agent to obtain a polyolefin composition, (2 ) A step of rolling a polyolefin composition with a rolling roll to form a sheet (rolling step), (3) a step of removing a hole forming agent from the sheet obtained in step (2), (4) step (3) The process of extending
- the pore-forming agent used in step (1) may contain an organic substance or an inorganic substance.
- the organic substance include a plasticizer.
- the plasticizer include low molecular weight hydrocarbons such as liquid paraffin.
- inorganic substances include inorganic materials that are soluble in neutral, acidic, or alkaline solvents, and examples include calcium carbonate, magnesium carbonate, and barium carbonate.
- inorganic compounds such as calcium chloride, sodium chloride, and magnesium sulfate can be used.
- BET Brunauer-Emmett-Teller
- water or a solution obtained by adding an acid or a base to an organic solvent can be used as the cleaning liquid.
- a surfactant may be added to the cleaning liquid.
- the addition amount of the surfactant can be arbitrarily selected in the range of 0.1 wt% to 15 wt%, or 0.1 wt% to 10 wt%. By selecting the addition amount from this range, it is possible to ensure high cleaning efficiency and prevent the surfactant from remaining.
- the washing temperature may be selected from a temperature range of 25 ° C. to 60 ° C., 30 ° C. to 55 ° C., or 35 ° C. to 50 ° C. Thereby, high cleaning efficiency can be obtained and evaporation of the cleaning liquid can be suppressed.
- the pore-forming agent may be removed using a cleaning solution, and then further washing with water may be performed.
- the temperature at the time of washing with water can be selected from a temperature range of 25 ° C. to 60 ° C., 30 ° C. to 55 ° C., or 35 ° C. to 50 ° C.
- the pore structure of the first layer 132 further includes the strain rate during stretching in the step (4) and the temperature of the heat setting treatment (annealing treatment) after stretching per unit thickness of the stretched film (after stretching). This is also affected by the heat setting temperature per unit thickness of the film (hereinafter referred to as heat setting temperature). Therefore, by adjusting the strain rate and the heat setting temperature, the pore structure of the first layer 132 can be controlled to satisfy the range of the temperature rise convergence time described in the first embodiment.
- the first layer 132 can be obtained by adjusting the strain rate and the heat setting temperature in the range inside the triangle with the three points as vertices.
- the porous layer 134 can be provided on one side or both sides of the first layer 132 (see FIG. 1B). When the porous layer 134 is stacked on one surface of the first layer 132, the porous layer 134 may be provided on the positive electrode 110 side or the negative electrode 120 side of the first layer 132.
- the porous layer 134 is preferably insoluble in the electrolytic solution 140 and contains an electrochemically stable material in the usage range of the secondary battery 100.
- materials include polyolefins such as polyethylene, polypropylene, polybutene, and ethylene-propylene copolymer; polyvinylidene fluoride (PVDF), polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene, and the like.
- -Fluoropolymer such as hexafluoropropylene copolymer; aromatic polyamide (aramid); styrene-butadiene copolymer and its hydride, methacrylate ester copolymer, acrylonitrile-acrylate copolymer, styrene- Rubbers such as acrylate copolymer, ethylene propylene rubber, and polyvinyl acetate; polyphenylene ether, polysulfone, polyethersulfone, polyphenylene sulfide, polyether Polymers having a melting point or glass transition temperature of 180 ° C. or higher, such as polyvinylids, polyamideimides, polyether amides, and polyesters; A functional polymer.
- aromatic polyamide aromatic polyamide (aramid); styrene-butadiene copolymer and its hydride, methacrylate ester copolymer, acrylonitrile-acrylate copolymer, st
- Aromatic polyamides include, for example, poly (paraphenylene terephthalamide), poly (metaphenylene isophthalamide), poly (parabenzamide), poly (metabenzamide), poly (4,4′-benzanilide terephthalamide), poly (Paraphenylene-4,4′-biphenylenedicarboxylic acid amide), poly (metaphenylene-4,4′-biphenylenedicarboxylic acid amide), poly (paraphenylene-2,6-naphthalenedicarboxylic acid amide), poly (metaphenylene) -2,6-naphthalenedicarboxylic acid amide), poly (2-chloroparaphenylene terephthalamide), paraphenylene terephthalamide / 2,6-dichloroparaphenylene terephthalamide copolymer, metaphenylene terephthalamide / 2,6-dichloroparaphth Such as two-terephthalamide copolymer.
- the porous layer 134 may contain a filler.
- the filler include fillers made of organic or inorganic substances, but fillers made of inorganic substances called fillers are suitable, and silica, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, zeolite, hydroxylated More preferred are fillers made of inorganic oxides such as aluminum and boehmite, at least one filler selected from the group consisting of silica, magnesium oxide, titanium oxide, aluminum hydroxide, boehmite and alumina is more preferred, and alumina is particularly preferred. .
- Alumina has many crystal forms such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina, and any of them can be suitably used. Among these, ⁇ -alumina is most preferred because of its particularly high thermal stability and chemical stability. Only one type of filler may be used for the porous layer 134, or two or more types of fillers may be used in combination.
- the shape of the filler is not limited, and the filler can take a spherical shape, a cylindrical shape, an elliptical shape, a bowl shape, or the like. Alternatively, a filler in which these shapes are mixed may be used.
- the content of the filler can be 1% to 99% by volume, or 5% to 95% by volume of the porous layer 134.
- the thickness of the porous layer 134 can be selected in the range of 0.5 ⁇ m to 15 ⁇ m, or 2 ⁇ m to 10 ⁇ m. Therefore, when the porous layer 134 is formed on both surfaces of the first layer 132, the total film thickness of the porous layer 134 can be selected from a range of 1.0 ⁇ m to 30 ⁇ m, or 4 ⁇ m to 20 ⁇ m.
- the total film thickness of the porous layer 134 By setting the total film thickness of the porous layer 134 to 1.0 ⁇ m or more, an internal short circuit due to damage of the secondary battery 100 can be more effectively suppressed.
- the total film thickness of the porous layer 134 30 ⁇ m or less, it is possible to prevent an increase in the transmission resistance of carrier ions, and the deterioration of the positive electrode 110 due to an increase in the transmission resistance of carrier ions, a decrease in rate characteristics, and cycle characteristics Can be suppressed. Furthermore, an increase in the distance between the positive electrode 110 and the negative electrode 120 can be avoided, and the secondary battery 100 can be reduced in size.
- the basis weight of the porous layer 134 can be selected from a range of 1 g / m 2 to 20 g / m 2 , or 2 g / m 2 to 10 g / m 2 . Thereby, the weight energy density and volume energy density of the secondary battery 100 can be made high.
- the porosity of the porous layer 134 can be 20% to 90% by volume, or 30% to 80% by volume. Thereby, the porous layer 134 can have sufficient ion permeability.
- the average pore diameter of the pores of the porous layer 134 can be selected from the range of 0.01 ⁇ m or more and 1 ⁇ m or less, or 0.01 ⁇ m or more and 0.5 ⁇ m or less, whereby sufficient ions for the secondary battery 100 can be obtained. Transparency can be imparted and the shutdown function can be improved.
- the air permeability of the separator 130 including the first layer 132 and the porous layer 134 described above can be a Gurley value of 30 s / 100 mL to 1000 s / 100 mL, or 50 s / 100 mL to 800 s / 100 mL.
- the separator 130 can ensure sufficient strength and shape stability at high temperature, and at the same time have sufficient ion permeability.
- a coating solution In the case of forming the porous layer 134 containing a filler, the above-described polymer or resin is dissolved or dispersed in a solvent, and then the filler is dispersed in the mixed solution (hereinafter referred to as a coating solution).
- Create Solvents include water; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and t-butyl alcohol; acetone, toluene, xylene, hexane, N-methylpyrrolidone, N, N-dimethylacetamide, N, And N-dimethylformamide. Only one type of solvent may be used, or two or more types of solvents may be used.
- a mechanical stirring method for example, a mechanical stirring method, an ultrasonic dispersion method, a high-pressure dispersion method, a media dispersion method, or the like may be applied.
- the filler after the filler is dispersed in the mixed solution, the filler may be wet pulverized using a wet pulverizer.
- additives such as a dispersing agent, a plasticizer, surfactant, and a pH adjuster
- the coating solution is applied onto the first layer 132.
- the coating liquid is directly applied to the first layer 132 by using a dip coating method, a spin coating method, a printing method, a spray method, or the like, and then the porous layer 134 is formed by removing the solvent. 132 can be formed.
- the coating liquid may not be directly formed on the first layer 132 but may be transferred onto the first layer 132 after being formed on another support.
- a resin film, a metal belt, a drum, or the like can be used as the support.
- any of natural drying, air drying, heat drying, and vacuum drying may be used.
- the solvent may be replaced with another solvent (for example, a low boiling point solvent) before drying.
- heating it can be carried out at 10 ° C. or higher and 120 ° C. or lower, or 20 ° C. or higher and 80 ° C. or lower. Thereby, it can avoid that the pore of the 1st layer 132 shrinks and air permeability falls.
- the thickness of the porous layer 134 can be controlled by the thickness of the coating film in a wet state after coating, the filler content, the concentration of polymer or resin, and the like.
- Ultra high molecular weight polyethylene powder (GUR4032, manufactured by Ticona) is 70% by weight, polyethylene wax having a weight average molecular weight of 1000 (FNP-0115, manufactured by Nippon Seiki Co., Ltd.), 30% by weight, and the total of the ultra high molecular weight polyethylene and polyethylene wax is As 100 parts by weight, antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals) 0.4% by weight, (P168, manufactured by Ciba Specialty Chemicals) 0.1% by weight, sodium stearate 1.3% by weight Furthermore, calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having an average pore diameter of 0.1 ⁇ m and a BET specific surface area of 11.6 m 2 / g is added as a pore-forming agent so as to be 36% by volume with respect to the total volume, and these powders Mix with a Henschel mixer, melt and knead with a twin screw kn
- the polyolefin resin composition was rolled using a pair of rolls having a surface temperature of 150 ° C. to prepare a sheet.
- This sheet was immersed in hydrochloric acid (4 mol / L) containing 0.5% by weight of a nonionic surfactant to remove calcium carbonate, followed by 6 to 100-105 ° C. at a strain rate of 1250% / min.
- the film was stretched 2 times to obtain a film having a thickness of 15.5 ⁇ m. Further, heat setting was performed at 120 ° C. to obtain the first layer 132. This first layer 132 was used as the separator 130.
- Example 2 Calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having 71 wt% ultra high molecular weight polyethylene powder, 29 wt% polyethylene wax, calcium carbonate having an average pore diameter of 0.1 ⁇ m and a BET specific surface area of 11.8 m 2 / g Except that it was used at 37% by volume, the polyolefin resin composition was stretched 7.0 times at a strain rate of 2100% / min, and the heat setting treatment was performed at 123 ° C.
- a separator 130 was obtained by the method described above. The film thickness of the separator 130 was 11.7 ⁇ m.
- Example 3 A point using calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having an average pore diameter of 0.1 ⁇ m and a BET specific surface area of 11.6 m 2 / g as calcium carbonate, a point of stretching the polyolefin resin composition at a strain rate of 750% / min, A separator 130 was obtained by the same method as in Example 1 except that the heat setting treatment was performed at 115 ° C. The film thickness of the separator 130 was 16.3 ⁇ m.
- Comparative Example 1 71% by weight of ultra high molecular weight polyethylene powder (GUR4032, manufactured by Ticona), 29% by weight of polyethylene wax having a weight average molecular weight of 1000 (FNP-0115, manufactured by Nippon Seiki Co., Ltd.), and the total of this ultra high molecular weight polyethylene and polyethylene wax.
- GUR4032 ultra high molecular weight polyethylene powder
- FNP-0115 polyethylene wax having a weight average molecular weight of 1000
- antioxidant As 100 parts by weight, antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals) 0.4% by weight, (P168, manufactured by Ciba Specialty Chemicals) 0.1% by weight, sodium stearate 1.3% by weight
- calcium carbonate manufactured by Maruo Calcium Co., Ltd.
- the polyolefin resin composition was rolled with a pair of rolls having a surface temperature of 150 ° C. to prepare a sheet.
- This sheet was immersed in hydrochloric acid (4 mol / L) containing 0.5% by weight of a nonionic surfactant to remove calcium carbonate, followed by 7 to 100-105 ° C. at a strain rate of 750% / min.
- the film was stretched 1 time to obtain a film having a thickness of 11.5 ⁇ m. Furthermore, heat setting was performed at 128 ° C. to obtain a separator.
- Comparative Example 2 As the separator of the comparative example, a commercially available polyolefin porous film (manufactured by Celgard, # 2400) was used.
- Positive electrode> A commercially available positive electrode manufactured by applying a laminate of LiNi 0.5 Mn 0.3 Co 0.2 O 2 / conductive material / PVDF (weight ratio 92/5/3) to an aluminum foil was processed.
- LiNi 0.5 Mn 0.3 Co 0.2 O 2 is an active material layer.
- the aluminum foil is cut out so that the size of the positive electrode active material layer is 45 mm ⁇ 30 mm and the outer periphery thereof has a width of 13 mm and no positive electrode active material layer is formed. Used as a positive electrode in the process.
- the thickness of the positive electrode active material layer was 58 ⁇ m, the density was 2.50 g / cm 3 , and the positive electrode capacity was 174 mAh / g.
- Negative electrode> A commercial negative electrode manufactured by applying graphite / styrene-1,3-butadiene copolymer / sodium carboxymethylcellulose (weight ratio 98/1/1) to a copper foil was processed.
- graphite functions as a negative electrode active material layer.
- the copper foil is cut out so that the size of the negative electrode active material layer is 50 mm ⁇ 35 mm, the width is 13 mm, and the negative electrode active material layer is not formed, and the assembly described below is performed. Used as a negative electrode in the process.
- the thickness of the negative electrode active material layer was 49 ⁇ m, the density was 1.40 g / cm 3 , and the negative electrode capacity was 372 mAh / g.
- the positive electrode, the separator, and the negative electrode were laminated in this order to obtain a laminate.
- the positive electrode and the negative electrode were arranged so that the entire upper surface of the positive electrode active material layer overlapped with the main surface of the negative electrode active material layer.
- the laminated body was arrange
- electrolytic solution a mixed solution in which LiPF 6 having a concentration of 1.0 mol / L was dissolved in a mixed solvent having a volume ratio of ethyl methyl carbonate, diethyl carbonate, and ethylene carbonate of 50:20:30 was used.
- the secondary battery was produced by heat-sealing a housing
- the design capacity of the secondary battery was 20.5 mAh.
- the film thickness was measured using a high-precision digital length measuring machine manufactured by Mitutoyo Corporation.
- microwave irradiation was performed at 1800 W for 2 minutes.
- the temperature change of the separator after the start of microwave irradiation was measured every 0.2 seconds with the optical fiber thermometer.
- the temperature when no temperature increase was observed for 1 second or more was defined as the temperature rising convergence temperature
- the time from the start of microwave irradiation until the temperature rising convergence temperature was reached was defined as the convergence time.
- the temperature rise convergence time was calculated by dividing the obtained convergence time by the separator basis weight.
- the secondary battery 100 manufactured by the above-described method was subjected to initial charge and discharge for 4 cycles at 25 ° C. with a voltage range of 4.1 V to 2.7 V and a current value of 0.2 C as one cycle.
- the secondary battery 100 that was initially charged / discharged was charged / discharged at 55 ° C. with a constant current of a charge current value of 1 C and discharge current values of 0.2 C and 20 C for 3 cycles each. Thereafter, the secondary battery 100 was charged and discharged for 100 cycles at 55 ° C., with a constant current having a voltage range of 4.2 V to 2.7 V, a charging current value of 1 C, and a discharging current value of 10 C as one cycle. Thereafter, charging and discharging were performed for 3 cycles each at a constant current of 55C and a charging current value of 1C and discharging current values of 0.2C and 20C.
- the ratio of the discharge capacity at the third cycle (20C discharge capacity / 0.2C discharge capacity) at discharge current values of 0.2C and 20C, respectively, is calculated as the rate characteristics after 100 cycles of charge / discharge (rate characteristics after 100 cycles). did.
- the separator WI is a spectrocolorimeter (CM-2002, manufactured by MINOLTA) with a separator installed on black paper (Hokuetsu Kishu Paper Co., Ltd., high quality paper, black, thickest mouth, 46th edition T-th).
- CM-2002 manufactured by MINOLTA
- black paper Hekuetsu Kishu Paper Co., Ltd., high quality paper, black, thickest mouth, 46th edition T-th.
- SCI Specific Component Include (including specular reflection light)
- Table 1 summarizes the separators of Examples 1 to 3 and Comparative Examples 1 and 2 and the characteristics of the secondary batteries produced using these separators.
- the secondary battery includes a separator 130 having a temperature rise convergence time of 2.9 s ⁇ m 2 / g to 5.7 s ⁇ m 2 / g and a WI of 85 to 98. It was found that even after repeated charge and discharge, excellent rate characteristics can be exhibited. On the other hand, it was found that the rate characteristics of the secondary batteries using the separators 130 of Comparative Examples 1 and 2 that do not satisfy the above characteristics are significantly lowered by repeated charge and discharge.
- 100 secondary battery, 110: positive electrode, 112: positive electrode current collector, 114: positive electrode active material layer, 120: negative electrode, 122: negative electrode current collector, 124: negative electrode active material layer, 130: separator, 132: first 134: Porous layer 140: Electrolytic solution
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Abstract
Description
本発明の実施形態の一つである二次電池100の断面模式図を図1(A)に示す。二次電池100は、正極110、負極120、正極110と負極120を分離するセパレータ130を有する。図示していないが、二次電池100は電解液140を有する。電解液140は主に正極110、負極120、セパレータ130の空隙や各部材間の隙間に存在する。正極110は正極集電体112と正極活物質層114を含むことができる。同様に、負極120は負極集電体122と負極活物質層124を含むことができる。図1(A)では図示していないが、二次電池100はさらに筐体を有し、筐体によって正極110、負極120、セパレータ130、および電解液140が保持される。
<1-1.構成>
セパレータ130は、正極110と負極120の間に設けられ、正極110と負極120を分離するとともに、二次電池100内で電解液140の移動を担うフィルムである。図1(B)にセパレータ130の断面模式図を示す。セパレータ130は多孔質ポリオレフィンを含む第1の層132を有し、さらに任意の構成として、多孔質層134を有することができる。セパレータ130は、図1(B)に示すように、2つの多孔質層134が第1の層132を挟持する構造を有することもできるが、第1の層132の一方の面のみに多孔質層134を設けてもよく、あるいは多孔質層134を設けない構成とすることもできる。第1の層132は単層の構造を有していてもよく、複数の層から構成されていてもよい。
第1の層132は、3重量%の水を含むN-メチルピロリドンに含浸させた後、周波数2455MHzのマイクロ波を出力1800Wで照射したときの昇温が収束するまでの目付当たりの時間(以下、温度上昇収束時間と記す)が、2.9s・m2/g以上5.7s・m2/g以下、あるいは2.9s・m2/g以上5.3s・m2/g以下である。また、第1の層132は、ホワイトインデックス(以下、WIと記す)が86以上98以下、あるいは90以上97以下である。
上述したように、正極110は正極集電体112と正極活物質層114を含むことができる。同様に、負極120は負極集電体122と負極活物質層124を含むことができる(図1(A)参照)。正極集電体112、負極集電体122はそれぞれ、正極活物質層114、負極活物質層124を保持し、電流を正極活物質層114、負極活物質層124へ供給する機能を有する。
電解液140は溶媒と電解質を含み、電解質のうち少なくとも一部は溶媒に溶解し、電離している。溶媒としては水や有機溶媒を用いることができる。二次電池100を非水電解液二次電池として用いる場合には、有機溶媒が用いられる。有機溶媒としては、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、1,2-ジ(メトキシカルボニルオキシ)エタンなどのカーボネート類;1,2-ジメトキシエタン、1,3-ジメトキシプロパン、テトラヒドロフラン、2-メチルテトラヒドロフランなどのエーテル類;ギ酸メチル、酢酸メチル、γ-ブチロラクトンなどのエステル類;アセトニトリル、ブチロニトリルなどのニトリル類;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミドなどのアミド類;3-メチル-2-オキサゾリドンなどのカルバメート類;スルホラン、ジメチルスルホキシド、1,3-プロパンサルトンなどの含硫黄化合物;および上記有機溶媒にフッ素が導入された含フッ素有機溶媒などが挙げられる。これらの有機溶媒の混合溶媒を用いてもよい。
図1(A)に示すように、負極120、セパレータ130、正極110を配置し、積層体を形成する。その後図示しない筐体へ積層体を設置し、筐体内を電解液で満たし、減圧しつつ筐体を密閉することにより、または筐体内を減圧しつつ共体内を電解液で満たしたのちに密閉することにより、二次電池100を作製することができる。二次電池100の形状は特に限定されず、薄板(ペーパー)型、円盤型、円筒型、直方体などの角柱型などであってもよい。
本実施形態では、第1実施形態で述べた第1の層132の作成方法について述べる。第1実施形態と同様の構成に関しては説明を割愛することがある。
本実施形態では、セパレータ130が第1の層132とともに多孔質層134を有する態様を説明する。
第1実施形態で述べたように、多孔質層134は、第1の層132の片面、または両面に設けることができる(図1(B)参照)。第1の層132の片面に多孔質層134が積層される場合には、多孔質層134は、第1の層132の正極110側に設けてもよく、負極120側に設けてもよい。
フィラーを含む多孔質層134を形成する場合、上述した高分子や樹脂を溶媒中に溶解、あるいは分散させたのち、この混合液にフィラーを分散させて分散液(以下、塗工液と記す)を作成する。溶媒としては、水;メチルアルコール、エチルアルコール、n-プロピルアルコール、イソプロピルアルコール、t-ブチルアルコールなどのアルコール;アセトン、トルエン、キシレン、ヘキサン、N-メチルピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミドなどが挙げられる。1種類の溶媒のみを用いてもよく、2種類以上の溶媒を用いてもよい。
セパレータ130の作成例を以下に述べる。
超高分子量ポリエチレン粉末(GUR4032、ティコナ社製)を70重量%、重量平均分子量1000のポリエチレンワックス(FNP-0115、日本精鑞社製)30重量%、この超高分子量ポリエチレンとポリエチレンワックスの合計を100重量部として、酸化防止剤(Irg1010、チバ・スペシャリティ・ケミカルズ社製)0.4重量%、(P168、チバ・スペシャリティ・ケミカルズ社製)0.1重量%、ステアリン酸ナトリウム1.3重量%を加え、さらに全体積に対して36体積%となるように平均孔径0.1μm、BET比表面積11.6m2/gの炭酸カルシウム(丸尾カルシウム社製)を孔形成剤として加え、これらを粉末のままヘンシェルミキサーで混合した後、二軸混練機で溶融混練してポリオレフィン樹脂組成物を得た。このポリオレフィン樹脂組成物を表面温度が150℃一対のロールを用いて圧延し、シートを作成した。このシートを非イオン系界面活性剤0.5重量%を含む塩酸(4mol/L)に浸漬させることで炭酸カルシウムを除去し、続いて100~105℃、歪速度1250%/分の速度で6.2倍に延伸し、膜厚15.5μmのフィルムを得た。さらに120℃で熱固定処理を行い、第1の層132を得た。この第1の層132をセパレータ130として用いた。
超高分子量ポリエチレン粉末を71重量%用いた点、ポリエチレンワックスを29重量%用いた点、炭酸カルシウムとして平均孔径0.1μm、BET比表面積11.8m2/gの炭酸カルシウム(丸尾カルシウム社製)を37体積%で用いた点、歪速度2100%/分の速度でポリオレフィン樹脂組成物を7.0倍に延伸した点、熱固定処理を123℃で行った点を除き、実施例1と同様の手法によりセパレータ130を得た。セパレータ130の膜厚は11.7μmであった。
炭酸カルシウムとして平均孔径0.1μm、BET比表面積11.6m2/gの炭酸カルシウム(丸尾カルシウム社製)を用いた点、歪速度750%/分の速度でポリオレフィン樹脂組成物を延伸した点、熱固定処理を115℃で行った点を除き、実施例1と同様の手法によりセパレータ130を得た。セパレータ130の膜厚は16.3μmであった。
超高分子量ポリエチレン粉末(GUR4032、ティコナ社製)を71重量%、重量平均分子量1000のポリエチレンワックス(FNP-0115、日本精鑞社製)29重量%、この超高分子量ポリエチレンとポリエチレンワックスの合計を100重量部として、酸化防止剤(Irg1010、チバ・スペシャリティ・ケミカルズ社製)0.4重量%、(P168、チバ・スペシャリティ・ケミカルズ社製)0.1重量%、ステアリン酸ナトリウム1.3重量%を加え、さらに全体積に対して36体積%となるように平均孔径0.1μm、BET比表面積11.6m2/gの炭酸カルシウム(丸尾カルシウム社製)を孔形成剤として加え、これらを粉末のままヘンシェルミキサーで混合した後、二軸混練機で溶融混練してポリオレフィン樹脂組成物を得た。このポリオレフィン樹脂組成物を表面温度が150℃一対のロールにて圧延し、シートを作成した。このシートを非イオン系界面活性剤0.5重量%を含む塩酸(4mol/L)に浸漬させることで炭酸カルシウムを除去し、続いて100~105℃、歪速度750%/分の速度で7.1倍に延伸し、膜厚11.5μmのフィルムを得た。さらに128℃で熱固定を行ってセパレータを得た。
比較例のセパレータとして、市販品のポリオレフィン多孔質フィルム(セルガード社製、#2400)を用いた。
実施例1から3、および比較例1、2のセパレータを含む二次電池の作製方法を以下に記す。
LiNi0.5Mn0.3Co0.2O2/導電材/PVDF(重量比92/5/3)の積層をアルミニウム箔に塗布することにより製造された市販の正極を加工した。ここで、LiNi0.5Mn0.3Co0.2O2は活物質層である。具体的には、正極活物質層の大きさが45mm×30mmであり、かつその外周に幅13mmで正極活物質層が形成されていない部分が残るように、アルミニウム箔を切り取り、以下に述べる組立工程において正極として用いた。正極活物質層の厚さは58μm、密度は2.50g/cm3、正極容量は174mAh/gであった。
黒鉛/スチレン-1,3-ブタジエン共重合体/カルボキシメチルセルロースナトリウム(重量比98/1/1)を銅箔に塗布することにより製造された市販の負極を加工した。ここで、黒鉛が負極活物質層として機能する。具体的には、負極活物質層の大きさが50mm×35mmであり、かつその外周に幅13mmで負極活物質層が形成されていない部分が残るように、銅箔を切り取り、以下に述べる組立工程において負極として用いた。負極活物質層の厚さは49μm、の密度は1.40g/cm3、負極容量は372mAh/gであった。
ラミネートパウチ内で、正極、セパレータ、および負極をこの順で積層し、積層体を得た。この時、正極活物質層の上面の全てが負極活物質層の主面と重なるように、正極および負極を配置した。
実施例1から3、および比較例1、2のセパレータの各種物性、およびこれらのセパレータを含む二次電池の特性の評価結果を以下に述べる。
膜厚は、株式会社ミツトヨ製の高精度デジタル測長機を用いて測定した。
8cm×8cmの大きさのセパレータを3wt%の水を添加したN-メチルピロリドンに含浸させた後、テフロン(登録商標)シート(サイズ:12cm×10cm)の上に広げ、ポリテトラフルオロエチレンで被覆された光ファイバー式温度計(アステック株式会社製、Neoptix Reflex 温度計)を挟むように半分に折り曲げた。
上述した方法で作製された二次電池100を、25℃で電圧範囲4.1Vから2.7V、電流値0.2Cを1サイクルとして、4サイクルの初期充放電を行った。
セパレータのWIは、黒紙(北越紀州製紙株式会社、色上質紙、黒、最厚口、四六版T目)上にセパレータを設置し、分光測色計(CM-2002、MINOLTA社製)を用いてSCI(Specular Component Include(正反射光を含む))法で測定した。3か所以上で測定した平均値を結果とした。
Claims (6)
- 多孔質ポリオレフィンからなる第1の層を有し、
3重量%の水を含むN-メチルピロリドンに前記第1の層を含浸させた後、周波数2455MHzのマイクロ波を出力1800Wで前記第1の層に照射したときの前記第1の層の温度上昇収束時間が2.9s・m2/g以上5.7s・m2/g以下であり、
前記第1の層のホワイトインデックスが86以上98以下であるセパレータ。 - 前記温度上昇収束時間が2.9s・m2/g以上5.3s・m2/g以下である、請求項1に記載のセパレータ。
- 前記ホワイトインデックスが90以上97以下である、請求項1に記載のセパレータ。
- 前記第1の層上に多孔質層をさらに含む、請求項1に記載のセパレータ。
- 前記第1の層を挟持する一対の多孔質層をさらに含む、請求項1に記載のセパレータ。
- 請求項1に記載の前記セパレータを有する二次電池。
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US16/344,094 US20190245181A1 (en) | 2016-10-24 | 2016-10-24 | Separator and secondary battery including the separator |
KR1020197013292A KR20190062537A (ko) | 2016-10-24 | 2016-10-24 | 세퍼레이터 및 세퍼레이터를 포함하는 이차 전지 |
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