WO2017014245A1 - リチウムイオン二次電池 - Google Patents
リチウムイオン二次電池 Download PDFInfo
- Publication number
- WO2017014245A1 WO2017014245A1 PCT/JP2016/071309 JP2016071309W WO2017014245A1 WO 2017014245 A1 WO2017014245 A1 WO 2017014245A1 JP 2016071309 W JP2016071309 W JP 2016071309W WO 2017014245 A1 WO2017014245 A1 WO 2017014245A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- ion secondary
- secondary battery
- lithium ion
- positive electrode
- Prior art date
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 85
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- 239000000463 material Substances 0.000 claims description 14
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Definitions
- the present invention relates to a lithium ion secondary battery.
- Lithium ion secondary batteries which are energy devices having a high energy density, are widely used as power sources for portable information terminals such as notebook computers, mobile phones, and PDAs.
- an electrode group is configured by alternately stacking positive and negative electrodes through separators.
- the negative electrode active material a carbon material having a multilayer structure capable of inserting and releasing lithium ions between layers is mainly used.
- lithium-containing composite metal oxides are mainly used as the positive electrode active material.
- a polyolefin porous membrane is mainly used for the separator.
- a lithium ion secondary battery made of such a material has high battery capacity and output, and good charge / discharge cycle characteristics.
- Lithium ion secondary batteries are at a high level in terms of safety.
- the lithium ion secondary battery has a high capacity and a high output, further improvement is demanded in terms of safety.
- the method of Patent Document 1 has been proposed as a method of interrupting current and suppressing heat generation.
- a temperature of a lithium ion secondary battery is increased by providing a PTC layer containing conductive particles, polymer particles, and a water-soluble polymer on a positive electrode current collector, a lithium ion secondary battery is used. It is disclosed that the effect of suppressing the overheating of the lithium ion secondary battery is exhibited by increasing the internal resistance of the battery to make it difficult for current to flow.
- Patent Document 1 it has been found that the lithium ion secondary battery described in Patent Document 1 is not sufficient in terms of higher safety when a temperature rise due to overcharging or the like occurs.
- the present invention has been made in view of the above-described problems, and an object of the present invention is to provide a lithium ion secondary battery that has excellent current interruption when overcharge occurs and has a high volumetric energy density.
- a lithium ion secondary battery including a positive electrode, a negative electrode, and a separator,
- the positive electrode has a current collector, a conductive layer formed on the current collector, and a positive electrode active material layer formed on the conductive layer;
- the conductive layer includes conductive particles, polymer particles, and a water-soluble polymer,
- the separator is a lithium ion secondary battery having a heat shrinkage rate at 160 ° C. of 30% or less.
- the separator includes a porous substrate and inorganic particles, and the porous substrate includes two or more different resins, and the resin includes polypropylene, polyethylene, polyvinyl alcohol, polyethylene terephthalate, polyacrylonitrile, and aramid.
- the lithium ion secondary battery according to ⁇ 1> selected from the group consisting of: ⁇ 3>
- ⁇ 4> The lithium ion secondary battery according to ⁇ 1>, wherein the separator has a Gurley value of 1000 seconds / 100 cc or less.
- ⁇ 5> The lithium ion secondary battery according to ⁇ 1> or ⁇ 4>, wherein the separator includes a porous substrate and inorganic particles, and the porous substrate includes polyester.
- the polyester includes polyethylene terephthalate.
- the polymer particles include polyethylene particles.
- the content ratio of the conductive particles and the mixed particles of the polymer particles to the water-soluble polymer is 99.9: 0.1 to 95: 5 in terms of mass ratio (mixed particles: water-soluble polymer).
- a lithium ion secondary battery including a positive electrode, a negative electrode, and a separator,
- the positive electrode has a current collector, a conductive layer formed on the current collector, and a positive electrode active material layer formed on the conductive layer;
- the conductive layer includes conductive particles, polymer particles, and a water-soluble polymer,
- the separator includes a porous base material and inorganic particles, and the porous base material is a lithium ion secondary battery that is a laminate in which polypropylene and polyethylene are alternately laminated.
- a lithium ion secondary battery including a positive electrode, a negative electrode, and a separator,
- the positive electrode has a current collector, a conductive layer formed on the current collector, and a positive electrode active material layer formed on the conductive layer;
- the conductive layer includes conductive particles, polymer particles, and a water-soluble polymer,
- the separator is a lithium ion secondary battery including a polyethylene terephthalate woven or nonwoven fabric and inorganic particles as a porous substrate.
- the inorganic particles are at least one of aluminum oxide (Al 2 O 3 ) and silicon oxide (SiO 2 ).
- the lithium ion secondary battery according to any one of the above. ⁇ 13> The separator includes a layer containing the inorganic particles on one surface of the porous substrate, and the layer containing the inorganic particles faces the positive electrode ⁇ 2>, ⁇ 3>, ⁇ 5>, ⁇ 6.
- ⁇ 14> The lithium ion secondary battery according to any one of ⁇ 1> to ⁇ 13>, wherein the separator has a thickness of 5 ⁇ m to 100 ⁇ m.
- ⁇ 15> The lithium ion secondary battery according to any one of ⁇ 1> to ⁇ 14>, wherein the conductive layer has a thickness of 0.1 ⁇ m to 10 ⁇ m.
- the present invention it is possible to provide a lithium ion secondary battery that is excellent in current interruption when overcharge occurs and has a high volumetric energy density.
- the numerical value range indicated by using “to” includes the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range.
- the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. It means the content rate of.
- the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
- the technology of the present invention can be widely applied to various non-aqueous electrolyte secondary batteries including an electrode in a form in which an electrode active material is held on a current collector.
- the conductive layer according to the technique of the present invention is interposed between the current collector and the electrode active material layer, so that the current collector and the electrode active material layer are interposed when the temperature of the battery rises. The effect of suppressing the overheating of the battery can be exhibited by increasing the electrical resistance of the battery.
- the present invention is not intended to be limited to such electrodes or batteries.
- a first lithium ion secondary battery of the present disclosure is a lithium ion secondary battery including a positive electrode, a negative electrode, and a separator, and the positive electrode includes a current collector, a conductive layer formed on the current collector, and the A positive electrode active material layer formed on the conductive layer, wherein the conductive layer includes conductive particles, polymer particles, and a water-soluble polymer, and the separator has a heat shrinkage rate of 160% or less at 160 ° C. belongs to.
- the second lithium ion secondary battery of the present disclosure is a lithium ion secondary battery including a positive electrode, a negative electrode, and a separator, and the positive electrode is a current collector and a conductive layer formed on the current collector.
- the third lithium ion secondary battery of the present disclosure is a lithium ion secondary battery including a positive electrode, a negative electrode, and a separator, and the positive electrode is a current collector and a conductive layer formed on the current collector. And a positive electrode active material layer formed on the conductive layer.
- the conductive layer includes conductive particles, polymer particles, and a water-soluble polymer.
- the separator is a woven polyethylene terephthalate as a porous substrate. It contains cloth or nonwoven fabric and inorganic particles.
- the first lithium ion secondary battery, the second lithium ion secondary battery, and the third lithium ion secondary battery may be collectively referred to as a lithium ion secondary battery of the present disclosure.
- the positive electrode includes a current collector, a conductive layer formed on the current collector, and a positive electrode active material layer formed on the conductive layer.
- the positive electrode may be a laminate in which a positive electrode active material layer, a conductive layer, and a current collector (positive electrode current collector) are superposed in this order.
- the conductive layer includes conductive particles, polymer particles, and a water-soluble polymer, and is configured as an aggregate of conductive particles, polymer particles, and a water-soluble polymer.
- the conductive particles are easily distributed uniformly in the conductive layer, so that a conductive network as an electron transfer path is formed almost uniformly on the entire conductive layer.
- adhesion between the positive electrode current collector and the conductive layer and between the positive electrode active material layer and the conductive layer is improved.
- the conductive layer is an aggregate of conductive particles, polymer particles, and a water-soluble polymer, the conductive particles are conductive inorganic particles, and the polymer particles are non-conductive thermoplastic resin particles.
- the output characteristics of the lithium ion secondary battery using the positive electrode having this conductive layer are further improved.
- the thickness of the conductive layer is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and further preferably 6 ⁇ m or less.
- the lower limit of the thickness of the conductive layer is not particularly limited, and is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 2 ⁇ m or more, from the viewpoint of film formability. The above is particularly preferable.
- the thickness of the conductive layer is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m, and more preferably 2 ⁇ m to 8 ⁇ m from the viewpoint of achieving both battery characteristics and PTC function. Is more preferably 3 ⁇ m to 6 ⁇ m.
- the conductive layer of the present disclosure not only improves the output characteristics but also functions to suppress further heat generation because the current flow in the conductive layer is interrupted when the conductive layer reaches a predetermined temperature due to heat generation ( Hereinafter, it may also be referred to as a PTC function).
- the positive electrode is composed of a positive electrode current collector, a conductive layer, and a positive electrode active material layer, and is disposed so as to face the negative electrode with a separator interposed therebetween.
- the positive electrode current collector those commonly used in the field of lithium ion secondary batteries can be used, and examples thereof include sheets and foils containing stainless steel, aluminum, titanium and the like. Among these, a sheet or foil containing aluminum is preferable.
- the thickness of the sheet and foil is not particularly limited, and is preferably 1 ⁇ m to 500 ⁇ m, more preferably 2 ⁇ m to 80 ⁇ m, and more preferably 5 ⁇ m, from the viewpoint of ensuring the strength and workability required for the current collector. More preferably, it is ⁇ 50 ⁇ m.
- the conductive layer is an aggregate of a mixture of conductive particles, polymer particles, and a water-soluble polymer.
- this aggregate is deformed at a preset temperature (hereinafter also referred to as “current cutoff temperature”), the current is interrupted and further heat generation is suppressed.
- the current interruption temperature can be appropriately set by selecting the type of polymer particles, the content of polymer particles, and the like.
- the conductive layer is formed on one or both surfaces in the thickness direction of the positive electrode current collector.
- the conductive particles include carbon particles such as graphite, acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black, metal particles such as nickel particles, WC, B 4 C, ZrC, NbC, Examples thereof include metal carbides such as MoC, TiC and TaC, metal nitrides such as TiN, ZrN and TaN, and metal silicides such as WSi 2 and MoSi 2 . Among these, carbon particles and metal particles are preferable, and carbon particles are more preferable.
- the conductive particles one kind may be used alone, or two or more kinds may be used in combination as necessary.
- conductive particles having a PTC function may be used.
- alkaline earth metal titanates such as barium titanate, barium strontium titanate, and barium lead titanate
- alkaline earth titanate examples thereof include a solid solution in which a different metal is dissolved in a metal salt.
- the average particle diameter of the primary particles constituting the carbon particles is preferably 10 nm to 500 nm, more preferably 15 nm to 200 nm, from the viewpoint of further improving battery characteristics.
- the thickness is preferably 20 nm to 100 nm.
- acetylene black having a structure in which primary particles are connected to some extent is particularly preferable.
- the degree of continuous primary particles is, for example, an acetylene having a shape factor of about 5 to 50 calculated by dividing the average length of the chain of primary particles divided by the average particle diameter of the primary particles. Black is preferred.
- polymer particles include non-conductive and thermoplastic resin particles.
- polymer particles include polyethylene, polypropylene, ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polyamide, polystyrene, polyacrylonitrile, thermoplasticity.
- EVA ethylene-vinyl acetate copolymer
- polyvinyl chloride polyvinylidene chloride
- polyvinyl fluoride polyvinylidene fluoride
- polyamide polystyrene
- thermoplasticity examples thereof include particles of elastomer, polyethylene oxide, polyacetal, thermoplastic modified cellulose, polysulfones, polymethyl (meth) acrylate and the like.
- polyolefin particles such as polyethylene and polypropylene are preferable.
- a polymer particle may be used individually by 1 type, or may be used in combination of 2 or more type as needed.
- “(meth) acrylate” means at least one of acrylate and methacrylate.
- the average particle diameter of the polymer particles is not particularly limited, and is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.2 ⁇ m to 4 ⁇ m from the viewpoint of further improving battery characteristics.
- the smaller the average particle size of the polyolefin particles the more the positive electrode active material layer tends to be uniformly formed on the positive electrode current collector.
- the larger the average particle size of the polyolefin particles the better the battery characteristics.
- the content ratio of the conductive particles and the polymer particles is not particularly limited, and is preferably 2:98 to 20:80 by mass ratio (conductive particles: polymer particles), more preferably 3: 97 to 15:85, and more preferably 5:95 to 10:90 by mass ratio. If the content ratio of the conductive particles is 2 or more, the electron transfer path in the conductive layer is sufficiently secured, and the output characteristics of the battery tend to be improved. When the content ratio of the conductive particles is 20 or less, the PTC function is sufficiently exerted, and the current blocking response to heat generation tends to be improved.
- the average particle diameter of the conductive particles and the polymer particles is, for example, a collection in which a conductive layer of about 5 ⁇ m is formed by applying an aqueous dispersion slurry of conductive particles, polymer particles, and a water-soluble polymer to a current collector and removing the water.
- the value of the long side length of all the particles in the image of the transmission electron micrograph in the range of 10 ⁇ m length ⁇ 10 ⁇ m width at the center can be a numerical value obtained by arithmetic averaging.
- water-soluble polymers include carboxymethylcellulose derivatives such as carboxymethylcellulose and sodium carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble alginic acid derivatives, gelatin, carrageenan, glucomannan, pectin, curdlan, gellan gum, polyacrylic acid, and polyacrylic. And acid derivatives.
- carboxymethyl cellulose derivatives, polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acid are particularly preferable, and carboxymethyl cellulose derivatives are more preferable.
- the content ratio of the mixed particles of conductive particles and polymer particles and the water-soluble polymer is not particularly limited, and is 99.9: 0.1 to 95: 5 in terms of mass ratio (mixed particle: water-soluble polymer). It is preferably 99.5: 0.5 to 98: 3, more preferably 99.5: 0.5 to 98: 2.
- the content ratio of the water-soluble polymer is 0.1 or more, the conductive particles are sufficiently dispersed, the electron transfer route in the conductive layer is sufficiently secured, and the battery characteristics tend to be improved.
- the content ratio of the water-soluble polymer is 5 or less, the viscosity of the obtained dispersion liquid is hardly increased, and the coatability to the current collector tends to be improved.
- the water-soluble polymer preferably has a weight average molecular weight of 1000 or more.
- the weight average molecular weight of the water-soluble polymer is more preferably 5,000 or more, further preferably 10,000 or more, and particularly preferably 50,000 or more.
- the weight average molecular weight of the carboxymethylcellulose derivative which is a water-soluble polymer
- the weight average molecular weight of the carboxymethylcellulose derivative can be determined, for example, by a GPC column (manufactured by Hitachi High-Technologies Corporation) on an HPLC system equipped with a differential refractometer (manufactured by Shimadzu Corporation, RID-10A) as a detector.
- GL-W560 a 0.2 M NaCl aqueous solution is used as the mobile phase, the molecular weight is measured at a flow rate of 1.0 mL / min, and the calculation can be made from a calibration curve using pullulan as the standard substance.
- the weight average molecular weights of water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acid are, for example, an HPLC pump (Hitachi Corporation) equipped with a differential refractometer (manufactured by Hitachi High-Technologies Corporation, model number L-3300). It can be measured by connecting a GPC column (model number W550 manufactured by Hitachi Chemical Co., Ltd.) to a high technology (model number L-7100) and using 0.3M NaCl as a mobile phase.
- the viscosity (60 rotations) at 25 ° C. when the water-soluble polymer is made into a 1% aqueous solution is preferably 100 mPa ⁇ s to 8000 mPa ⁇ s, and more preferably 500 mPa ⁇ s to 6000 mPa ⁇ s. More preferably, it is 1000 mPa ⁇ s to 4000 mPa ⁇ s.
- the current cutoff temperature of the conductive layer is preferably set to 70 ° C. to 140 ° C., more preferably 90 ° C. to 120 ° C. If the current cut-off temperature of the conductive layer is set to 70 ° C to 140 ° C, the current is cut off when an abnormality occurs in the battery itself or various devices equipped with the battery to suppress heat generation. Since the supply of power to the equipment can be stopped, very high safety can be obtained. In addition, when the temperature is set to 90 ° C. to 120 ° C., there is an advantage that there is no malfunction during normal use, and the current can be surely interrupted when an abnormality such as overcharge occurs.
- the current interruption temperature depends on the melting point of the polymer particles. When the current interruption temperature is set to 90 ° C. to 120 ° C., it is preferable to use polyethylene particles as the polymer particles.
- the positive electrode active material layer is formed on one or both surfaces in the thickness direction of the positive electrode current collector, contains the positive electrode active material, and may further contain a conductive material, a binder, and the like as necessary.
- the positive electrode active material those commonly used in this field can be used, and examples include lithium-containing composite metal oxides, olivine-type lithium salts, chalcogen compounds, and manganese dioxide.
- the lithium-containing composite metal oxide is a metal oxide containing lithium and a transition metal or a metal oxide in which a part of the transition metal in the metal oxide is substituted with a different element.
- examples of the different element include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, V, and B.
- Mn, Al, Co, Ni, Mg and the like are preferable.
- One kind of different elements may be used alone, or two or more kinds may be used in combination as required.
- lithium-containing composite metal oxides are preferable.
- the lithium-containing composite metal oxide include Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co y Ni 1-y O 2 , and Li x Co y M 1 1-y O z (Li In x Co y M 1 1-y O z , M 1 is selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Ni, Cu, Zn, Al, Cr, Pb, Sb, V, and B at least one element.), Li x Ni 1- y M 2 y O z (Li x Ni in 1-y M 2 y O z , M 2 is Na, Mg, Sc, Y, Mn, Fe, And at least one element selected from the group consisting of Co, Cu, Zn, Al, Cr, Pb, Sb, V, and B.), Li x Mn 2 O 4 , Li x Mn 2-y M 3 y O 4
- x is in the range of 0 ⁇ x ⁇ 1.2
- y is in the range of 0 to 0.9
- z is in the range of 2.0 to 2.3.
- the x value indicating the molar ratio of lithium increases or decreases due to charge / discharge.
- the olivine type lithium salts for example, LiFePO 4, and the like.
- the chalcogen compound include titanium disulfide and molybdenum disulfide.
- Li 2 MPO 4 F (in Li 2 MPO 4 F, M is Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb , Sb, V and B represents at least one element selected from the group consisting of B).
- a positive electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type as needed.
- Examples of the conductive material that may be used for the positive electrode active material layer include carbon black, graphite, carbon fiber, and metal fiber.
- Examples of carbon black include acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black.
- Examples of graphite include natural graphite and artificial graphite.
- a conductive material may be used individually by 1 type, or may be used in combination of 2 or more type as needed.
- binder examples include polyethylene, polypropylene, polyvinyl acetate, polymethyl methacrylate, nitrocellulose, fluororesin, and rubber particles.
- fluororesin examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and vinylidene fluoride-hexafluoropropylene copolymer.
- rubber particles examples include styrene-butadiene rubber particles and acrylonitrile rubber particles.
- a binder can be used individually by 1 type, or can be used in combination of 2 or more type as needed.
- the positive electrode active material layer can be formed, for example, by applying a positive electrode mixture paste on the conductive layer, drying it, and rolling it as necessary.
- the positive electrode mixture paste can be prepared by adding a positive electrode active material to a dispersion medium together with a binder, a conductive material, and the like and mixing them.
- the dispersion medium for example, N-methyl-2-pyrrolidone (NMP), tetrahydrofuran, dimethylformamide or the like can be used.
- NMP N-methyl-2-pyrrolidone
- tetrahydrofuran dimethylformamide or the like
- the packing density of the positive electrode active material layer becomes too high.
- the non-aqueous electrolyte is less likely to penetrate into the positive electrode active material layer, and the diffusion of lithium ions during charging / discharging with a large current may be delayed, resulting in deterioration of cycle characteristics.
- the packing density of the positive electrode active material layer is low, sufficient contact between the positive electrode active material and the conductive material cannot be ensured, resulting in an increase in electrical resistance and a decrease in discharge rate.
- the packing density (positive electrode mixture density) of the positive electrode active material layer is preferably in the range of 2.2 g / cm 3 to 2.8 g / cm 3 , and 2.3 g / cm 3 to 2.7 g / A range of cm 3 is more preferable, and a range of 2.4 g / cm 3 to 2.6 g / cm 3 is more preferable.
- the lithium ion secondary battery of the present disclosure when a positive electrode active material layer is applied to a positive electrode current collector to produce a positive electrode, the amount of the positive electrode active material layer applied increases, and the positive electrode active material layer becomes thicker. If it is too high, when charging / discharging with a large current, non-uniform reaction occurs in the thickness direction, and the cycle characteristics may deteriorate. On the other hand, if the positive electrode active material layer becomes too thin because the amount of the positive electrode active material layer applied is small, a sufficient battery capacity may not be obtained.
- the coating amount of the positive electrode active material layer with respect to the conductive layer is preferably in the range of 50 g / m 2 to 300 g / m 2 , more preferably in the range of 80 g / m 2 to 250 g / m 2 , and 100 g / m 2. More preferably, it is in the range of m 2 to 220 g / m 2 .
- the thickness of the positive electrode active material layer is preferably 30 ⁇ m to 200 ⁇ m, more preferably 50 ⁇ m to 180 ⁇ m, and even more preferably 70 ⁇ m to 150 ⁇ m.
- the negative electrode is provided to face the positive electrode with the separator interposed therebetween, and includes a negative electrode current collector and a negative electrode active material layer.
- the negative electrode current collector include sheets and foils containing stainless steel, nickel, copper, and the like.
- the thickness of the sheet and foil is not particularly limited, and is preferably 1 ⁇ m to 500 ⁇ m, more preferably 2 ⁇ m to 100 ⁇ m, and more preferably 5 ⁇ m from the viewpoint of ensuring the strength and workability required for the current collector. More preferably, it is ⁇ 50 ⁇ m.
- the negative electrode active material layer is formed on one or both surfaces in the thickness direction of the negative electrode current collector, contains the negative electrode active material, and further contains a binder, a conductive material, a thickener and the like as necessary. It may be.
- the negative electrode active material a material that can occlude and release lithium ions and that is commonly used in the field of lithium ion secondary batteries can be used.
- metal lithium, a lithium alloy, an intermetallic compound, a carbon material, an organic compound, an inorganic compound, a metal complex, an organic polymer compound, and the like can be given.
- a negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type as needed.
- a carbon material is preferable. Examples of the carbon material include graphite such as natural graphite (such as flake graphite) and artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black, and carbon fiber.
- the average particle size of the carbon material is preferably 0.1 ⁇ m to 60 ⁇ m, and more preferably 0.5 ⁇ m to 30 ⁇ m.
- the BET specific surface area of the carbon material is preferably 1 m 2 / g to 10 m 2 / g.
- graphite having a carbon hexagonal plane spacing (d 002 ) of 3.35 to 3.40 and a c-axis direction crystallite (Lc) of 100 or more. Is preferred.
- amorphous carbon having an interval (d 002 ) between carbon hexagonal planes in the X-ray wide-angle diffraction method of 3.5 to 3.95 cm. Is preferred.
- the average particle diameter of the negative electrode active material is measured with a laser diffraction particle size distribution analyzer (for example, SALD-3000J manufactured by Shimadzu Corporation) by dispersing a sample in purified water containing a surfactant.
- a laser diffraction particle size distribution analyzer for example, SALD-3000J manufactured by Shimadzu Corporation
- the value (median diameter (D50)) when the integration from the small diameter side is 50% is used.
- a BET specific surface area can be measured from nitrogen adsorption capacity according to JIS Z 8830: 2013, for example.
- AUTOSORB-1 trade name
- QUANTACHROME can be used.
- pretreatment for moisture removal by heating.
- a measurement cell charged with 0.05 g of a measurement sample is depressurized to 10 Pa or less with a vacuum pump, heated at 110 ° C. and held for 3 hours or more, and then kept at a normal temperature ( Cool to 25 ° C).
- the evaluation temperature is 77K
- the evaluation pressure range is measured as a relative pressure (equilibrium pressure with respect to saturated vapor pressure) of less than 1.
- the conductive material that may be used for the negative electrode active material layer the same conductive material as that contained in the positive electrode active material layer can be used.
- a binder which may be used for a negative electrode active material layer what is commonly used in the field of lithium ion secondary batteries can be used. Examples thereof include polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene rubber, acrylic rubber, and the like.
- the thickener that may be used in the negative electrode active material layer include carboxymethyl cellulose.
- the negative electrode active material layer can be formed, for example, by applying a negative electrode mixture paste to the surface of the negative electrode current collector, drying, and rolling as necessary.
- the negative electrode mixture paste can be prepared, for example, by adding a negative electrode active material to a dispersion medium together with a binder, a conductive material, a thickener, and the like as necessary.
- a dispersion medium for example, N-methyl-2-pyrrolidone (NMP), water and the like can be used.
- electrolyte examples include a liquid non-aqueous electrolyte, a gel-like non-aqueous electrolyte, a solid electrolyte (for example, a polymer solid electrolyte), and the like.
- the liquid non-aqueous electrolyte contains a solute (supporting salt) and a non-aqueous solvent, and further contains various additives as necessary. Solutes usually dissolve in non-aqueous solvents.
- the separator is impregnated with the liquid non-aqueous electrolyte.
- borates include lithium bis (1,2-benzenediolate (2-)-O, O ′) borate, bis (2,3-naphthalenedioleate (2-)-O, O ′) boric acid.
- imide salts include lithium bistrifluoromethanesulfonate imide ((CF 3 SO 2 ) 2 NLi), lithium trifluoromethanesulfonate nonafluorobutanesulfonate ((CF 3 SO 2 ) (C 4 F 9 SO 2 ) NLi ), Lithium bispentafluoroethanesulfonate imide ((C 2 F 5 SO 2 ) 2 NLi), and the like.
- a solute may be used individually by 1 type, or may be used in combination of 2 or more type as needed.
- the amount of the solute dissolved in the nonaqueous solvent is preferably 0.5 mol / L to 2 mol / L.
- non-aqueous solvent examples thereof include a cyclic carbonate ester, a chain carbonate ester, and a cyclic carboxylate ester.
- examples of the cyclic carbonate include propylene carbonate (PC) and ethylene carbonate (EC).
- examples of the chain carbonate include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and the like.
- examples of the cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
- a non-aqueous solvent may be used individually by 1 type, or may be used in combination of 2 or more type as needed.
- VC vinylene carbonate
- the content when vinylene carbonate (VC) is contained is preferably 0.1% by mass to 2% by mass, and more preferably 0.2% by mass to 1.5% by mass with respect to the total amount of the nonaqueous solvent.
- the separator is disposed between the positive electrode and the negative electrode.
- the first separator used in the present disclosure has a heat shrinkage rate at 160 ° C. of 30% or less.
- the second separator used in the present disclosure includes a porous substrate and inorganic particles, and the porous substrate is a laminate in which polypropylene and polyethylene are alternately laminated.
- the third separator used in the present disclosure includes a polyethylene terephthalate woven or nonwoven fabric and inorganic particles as a porous substrate.
- the first separator, the second separator, and the third separator may be collectively referred to as a separator of the present disclosure.
- the first separator may have a heat shrinkage rate at 160 ° C. of 30% or less, preferably 20% or less, more preferably 10% or less, still more preferably 7% or less, 2% or less is particularly preferable.
- the heat shrinkage rate of the second separator and the third separator is not limited, and may be, for example, 30% or less, preferably 20% or less, and more preferably 10% or less. 7% or less is more preferable, and 2% or less is particularly preferable.
- the lower limit of the heat shrinkage rate at 160 ° C. is preferably 0%, but from a practical viewpoint, it is 1% or more.
- the heat shrinkage rate at 160 ° C. is that the separator having a length of 30 mm (MD) and a width of 30 mm (TD) is subjected to heat treatment for 60 minutes in an oven at 160 ° C. It is obtained as follows from the measured value of the length.
- Thermal shrinkage (%) (length before heat treatment (TD) ⁇ length after heat treatment (TD)) / length before heat treatment (TD) ⁇ 100
- TD direction means a perpendicular direction (lateral direction) with respect to the take-up direction at the time of film manufacture
- MD direction means a take-up direction.
- the heat shrinkage rate at 160 ° C. is determined by cutting a separator into a size of 30 mm (MD) in length and 30 mm (TD) in width, sandwiching the separator using two glass substrates, and a 160 ° C. oven.
- the separator area before and after the heat treatment may be calculated by performing a heat treatment for 60 minutes, and may be obtained as follows.
- Thermal shrinkage (area shrinkage) (%) (area before heating ⁇ area after heating) / area before heating ⁇ 100
- the Gurley value [second / 100 cc] of the separator of the present disclosure may be 1000 seconds / 100 cc or less, 800 seconds / 100 cc or less, 600 seconds / 100 cc or less, 300 seconds / It may be 100 cc or less, 200 seconds / 100 cc or less, or 100 seconds / 100 cc or less. Further, the Gurley value [second / 100 cc] of the separator of the present disclosure may be 1 second / 100 cc to 1000 seconds / 100 cc, 1 second / 100 cc to 800 seconds / 100 cc, or 1 second / 100 cc.
- the Gurley value of the separator of the present disclosure is in the range of 1 second / 100 cc to 300 seconds / 100 cc, the ion permeability tends to be good and the discharge rate characteristics tend to be excellent.
- the Gurley value is the air permeability resistance calculated by the Gurley test method and represents the difficulty of passing ions in the thickness direction of the separator. Specifically, the time required for 100 cc of ions to pass through the separator is expressed. That is, if the Gurley value is small, it means that ions are easy to pass through, and if the value is large, it is difficult to pass ions.
- the Gurley value is a value measured according to the Gurley test method (JIS P8117: 2009).
- the fourth lithium ion secondary battery of the present disclosure is a lithium ion secondary battery including a positive electrode, a negative electrode, and a separator, and the positive electrode is a current collector and a conductive layer formed on the current collector. And a positive electrode active material layer formed on the conductive layer, the conductive layer including conductive particles, polymer particles, and a water-soluble polymer, and the Gurley value of the separator is 300 seconds / 100 cc or less. Is.
- the thermal contraction rate of the separator according to the fourth lithium ion secondary battery for example, it may be 30% or less, preferably 20% or less, and more preferably 10% or less. 7% or less is more preferable, and 2% or less is particularly preferable.
- the separator of the present disclosure may include a porous substrate and inorganic particles.
- the resin contained in the porous substrate include olefin resins such as polypropylene and polyethylene, fluorine resins such as polytetrafluoroethylene, polyesters such as polyethylene terephthalate (PET), aramid, polyacrylonitrile, polyvinyl alcohol, and polyimide.
- PET polyethylene terephthalate
- a porous base material may be used individually by 1 type, or may be used in combination of 2 or more type as needed.
- the separator includes a porous substrate and inorganic particles, the porous substrate includes two or more different resins, and the resin is made of polypropylene, polyethylene, polyvinyl alcohol, polyethylene terephthalate, polyacrylonitrile, and aramid. It may be selected from the group and preferably contains polyethylene and polypropylene.
- the separator may include a porous substrate and inorganic particles, and the porous substrate may include polyester.
- the polyesters contained in the porous substrate polyethylene terephthalate (PET) is suitable as a porous substrate because it is excellent in heat resistance and electrical insulation.
- PET polyethylene terephthalate
- the resin contained in the porous substrate is polyethylene terephthalate
- the “nonwoven fabric” means a sheet-like object formed by intertwining fibers without weaving them.
- a porous base material contains 2 or more types of resin, it is good also as a structure which laminated
- the porous substrate when the porous substrate has a structure in which two or more kinds of resins are laminated, the porous substrate preferably has a two-layer structure or a three-layer structure.
- the method for producing the porous substrate is not particularly limited, and can be selected from known methods.
- the porous substrate may be a woven fabric or a non-woven fabric, and is preferably a non-woven fabric.
- the melting point of the porous substrate is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, and further preferably 160 ° C. or higher.
- the separator has a shutdown function and can prevent a short circuit inside the battery.
- fusing point of a porous base material is 300 degrees C or less.
- the melting point is measured using a differential scanning calorimeter (DSC7 manufactured by PerkinElmer) in a nitrogen atmosphere with a temperature rising rate of 10 ° C./min, a measuring temperature range of 25 ° C. to 350 ° C., and a flow rate of 20 ⁇ 5 ml / min. Under the conditions, it is measured by performing differential scanning calorimetry of a 3 mg to 5 mg sample sealed in an aluminum pan. From the result obtained from the differential scanning calorimetry, the temperature at which the energy change accompanying the phase transition occurs (endothermic reaction peak) is defined as the melting point.
- DSC7 differential scanning calorimeter
- the inorganic particles include aluminum oxide (Al 2 O 3 ), silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), barium titanate (BaTiO 3 ), ZrO 2 (zirconia), boehmite and the like.
- Al 2 O 3 silicon oxide
- SiO 2 silicon oxide
- TiO 2 titanium oxide
- BaTiO 3 barium titanate
- ZrO 2 zirconia
- boehmite boehmite and the like.
- One kind of inorganic particles may be used alone, or two or more kinds may be used in combination as necessary.
- alumina aluminum oxide
- silica silicon oxide
- the inorganic particles have a function of protecting the porous substrate so that the porous substrate is not thermally deformed or contracted while maintaining the shutdown function of the porous substrate that melts due to the abnormally high temperature of the battery.
- the inorganic particles may be applied on the surface of the porous substrate, or may be impregnated in the pores of the porous substrate.
- the separator may include a layer containing inorganic particles on one surface of the porous substrate, and the separator may be arranged so that the layer containing inorganic particles faces the positive electrode.
- the layer containing inorganic particles can function as a heat-resistant layer that protects the porous substrate from thermal deformation or thermal shrinkage.
- a preferable combination in the three-layered porous substrate is a laminate of porous films containing resins having different melting temperatures, more preferably an olefin.
- the polyethylene layer is sandwiched between the polypropylene layers, so that even when the polyethylene layer is melted, the inorganic particles present on the porous substrate surface or impregnated in the pores are used as the heat-resistant layer. This function is maintained and the positive electrode and negative electrode isolation function is maintained.
- the shutdown function is efficiently exhibited.
- the polypropylene melts in the temperature range of 160 ° C. to 170 ° C., and polyethylene and polypropylene block the voids in the porous substrate, so that a safer shutdown function is exhibited.
- the average particle diameter (D50) of the inorganic particles is preferably 0.1 ⁇ m to 10 ⁇ m, and more preferably 0.2 ⁇ m to 9 ⁇ m. If the average particle diameter of the inorganic particles is within the above range, the adhesion between the inorganic particles and the porous substrate is good, and the thermal contraction rate of the separator is lowered even when the battery temperature is increased.
- the average particle size of the inorganic particles in the present specification is a volume measured with a laser diffraction particle size distribution analyzer (for example, SALD-3000J manufactured by Shimadzu Corporation) by dispersing a sample in purified water containing a surfactant.
- a laser diffraction particle size distribution analyzer for example, SALD-3000J manufactured by Shimadzu Corporation
- the value (median diameter (D50)) when the integration from the small diameter side is 50% is used.
- the mass-based ratio ( ⁇ 1: ⁇ 1) of the inorganic particle content ( ⁇ 1) and the resin content ( ⁇ 1) such as polyethylene terephthalate in the separator of the present disclosure is a viewpoint of the thermal contraction rate, flexibility, etc. of the separator. Therefore, it is preferably in the range of 1:50 to 20: 1, more preferably in the range of 1:25 to 10: 1, and still more preferably in the range of 1: 5 to 4: 1.
- the ratio ( ⁇ 2: ⁇ 2) of the thickness ( ⁇ 2) of the layer of inorganic particles (hereinafter referred to as inorganic particle layer) to the thickness ( ⁇ 2) of the porous substrate is preferably in the range of 1: 100 to 10: 1, more preferably in the range of 1:50 to 5: 1, and in the range of 1:10 to More preferably, it is in the range of 2: 1.
- the thickness of the separator is preferably in the range of 5 ⁇ m to 100 ⁇ m, more preferably 7 ⁇ m to 50 ⁇ m, and even more preferably 15 ⁇ m to 30 ⁇ m. In other embodiments, the thickness of the separator is preferably in the range of 5 ⁇ m to 100 ⁇ m, more preferably in the range of 13 ⁇ m to 70 ⁇ m, and still more preferably in the range of 15 ⁇ m to 50 ⁇ m. When the thickness of the separator is in the range of 5 ⁇ m to 100 ⁇ m, excellent volume energy density and safety can be obtained while maintaining ion permeability.
- the laminate type lithium ion secondary battery can be manufactured, for example, as follows. First, the positive electrode and the negative electrode are cut into squares, and tabs are welded to the respective electrodes to produce positive and negative electrode terminals. An electrode laminate is produced by laminating a separator between a positive electrode and a negative electrode, and accommodated in an aluminum laminate pack in that state, and the positive and negative electrode terminals are taken out of the aluminum laminate pack and sealed. Next, a nonaqueous electrolytic solution is poured into the aluminum laminate pack, and the opening of the aluminum laminate pack is sealed. Thereby, a lithium ion secondary battery is obtained.
- FIG. 1 shows a cross-sectional view of a lithium ion secondary battery to which the present disclosure is applied.
- a lithium ion secondary battery 1 of the present disclosure has a bottomed cylindrical battery container 6 made of nickel-plated steel.
- the battery case 6 accommodates an electrode group 5 in which a strip-like positive electrode plate 2 and a negative electrode plate 3 are wound in a spiral shape with a separator 4 interposed therebetween.
- the separator 4 has a width of 58 mm and a thickness of 30 ⁇ m.
- a ribbon-like positive electrode tab terminal made of aluminum and having one end fixed to the positive electrode plate 2 is led out on the upper end surface of the electrode group 5.
- the other end of the positive electrode tab terminal is joined by ultrasonic welding to the lower surface of a disk-shaped battery lid that is disposed on the upper side of the electrode group 5 and serves as a positive electrode external terminal.
- a ribbon-like negative electrode tab terminal made of copper with one end fixed to the negative electrode plate 3 is led out on the lower end surface of the electrode group 5.
- the other end of the negative electrode tab terminal is joined to the inner bottom of the battery container 6 by resistance welding. Therefore, the positive electrode tab terminal and the negative electrode tab terminal are led out to the opposite sides of the both end faces of the electrode group 5, respectively.
- omitted illustration is given to the outer peripheral surface whole periphery of the electrode group 5.
- the battery lid is caulked and fixed to the upper part of the battery container 6 via an insulating resin gasket. For this reason, the inside of the lithium ion secondary battery 1 is sealed. In addition, a non-aqueous electrolyte (not shown) is injected into the battery container 6.
- Example 1A (1) Production of conductive layer Acetylene black (conductive particles, trade name: HS-100, average particle size 48 nm (Denki Kagaku Kogyo Co., Ltd. catalog), manufactured by Denki Kagaku Kogyo Co., Ltd.) and polyethylene particles (polymer particles, Product name: Chemipearl (registered trademark) W400, average particle size 4 ⁇ m (Mitsui Chemicals, Inc. catalog value), Mitsui Chemicals, Inc.) and carboxymethyl cellulose (CMC, manufactured by Daicel Corporation, # 2200) The mixture was mixed so that the mass ratio (acetylene black: polyethylene particles: CMC) was 5: 94: 1 and dispersed uniformly.
- conductive particles trade name: HS-100, average particle size 48 nm (Denki Kagaku Kogyo Co., Ltd. catalog), manufactured by Denki Kagaku Kogyo Co., Ltd.)
- polyethylene particles polymer particles, Product name: Chemi
- a conductive layer slurry was applied to both sides of an aluminum foil (positive electrode current collector, manufactured by Mitsubishi Aluminum Co., Ltd.) having a thickness of 15 ⁇ m and dried at 60 ° C. to prepare a conductive layer having a thickness of 5 ⁇ m.
- an aluminum foil positive electrode current collector, manufactured by Mitsubishi Aluminum Co., Ltd.
- the positive electrode plate was manufactured as follows. To the layered lithium / nickel / manganese / cobalt composite oxide, which is a positive electrode active material, acetylene black (average particle diameter 50 nm) as a conductive material and polyvinylidene fluoride (PVDF) as a binder are sequentially added and mixed. Thus, a positive electrode mixture paste was prepared.
- acetylene black average particle diameter 50 nm
- PVDF polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- PVDF Polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- coating type PP 18650 type battery Separator
- silica is applied to a polypropylene / polyethylene / polypropylene three-layer porous substrate having a thickness of 30 ⁇ m and a width of 58.5 mm between the produced positive electrode and negative electrode.
- PE / PP separator also referred to as PE / PP separator
- the electrode group was designed so that the capacity of the battery was 900 mAh.
- the electrode group was inserted into the battery container, and a negative electrode tab terminal previously welded to the negative electrode current collector was welded to the bottom of the can.
- the coating type PP / PE / PP separator has a heat-resistant layer containing silica formed on one surface of the porous substrate, and the coating type PP / PE / PP separator is interposed between the positive electrode and the negative electrode. In addition, the heat-resistant layer was disposed so as to face the positive electrode.
- the thermal shrinkage (area shrinkage) of the coating type PP / PE / PP separator was measured by the above-mentioned method and found to be 18%.
- ethylene carbonate / ethyl methyl carbonate / dimethyl carbonate 2/2/3 mixed solution (volume ratio) containing 1.2 M LiPF 6 was added with 0.8% by mass of vinylene carbonate based on the total amount of the mixed solution.
- a water electrolyte was used. 6 ml of non-aqueous electrolyte was injected into the battery container. Thereafter, the upper part of the battery container was crimped to seal the battery.
- a 18650 type lithium ion secondary battery was produced as described above.
- Example 2A Instead of polyethylene particles (polymer particles, trade name: Chemipearl (registered trademark) W400, average particle diameter 4 ⁇ m (Mitsui Chemicals catalog value), Mitsui Chemicals, Inc.), polyethylene particles (polymer particles, trade name: Chemipearl ( A 18650 type battery was fabricated in the same manner as in Experimental Example 1A, except that (registered trademark) W300, an average particle size of 3 ⁇ m (catalog value from Mitsui Chemicals, Inc., manufactured by Mitsui Chemicals, Inc.) was used.
- Example 3A Instead of polyethylene particles (polymer particles, trade name: Chemipearl (registered trademark) W400, average particle diameter 4 ⁇ m (Mitsui Chemicals catalog value), Mitsui Chemicals, Inc.), polyethylene particles (polymer particles, trade name: Chemipearl ( A 18650 type battery was fabricated in the same manner as in Experimental Example 1A, except that (registered trademark) WP100, average particle size of 1 ⁇ m (catalog value from Mitsui Chemicals, Inc., manufactured by Mitsui Chemicals, Inc.) was used.
- WP100 average particle size of 1 ⁇ m
- Example 4A A 18650 type battery was fabricated in the same manner as in Experimental Example 1A, except that the conductive layer was not provided on the surface of the positive electrode current collector.
- Example 5A A 18650 type battery was fabricated in the same manner as in Experimental Example 4A, except that a conductive layer was not provided on the surface of the positive electrode current collector and a polyethylene (PE) separator having a thickness of 30 ⁇ m was used.
- the heat shrinkage (area shrinkage) of the polyethylene separator was measured by the above-mentioned method and found to be 98%.
- Example 6A A 18650 type battery was fabricated in the same manner as in Experimental Example 1A, except that a polyethylene separator having a thickness of 30 ⁇ m was used.
- C means “current value (A) / battery capacity (Ah)”.
- Experimental Example 4A in which the conductive layer was not provided and Experimental Example 5A in which the conductive layer was not provided and the polyethylene separator was used were found to have poor overcharge characteristics and volume energy density.
- Experimental Example 6A using a polyethylene separator and having a conductive layer was superior to Experimental Examples 4A and 5A, but was inferior to Experimental Examples 1A to 3A.
- Example 1B In Experimental Example 1A, instead of the coating type PP / PE / PP separator, a separator having a heat-resistant layer in which alumina and silica are mixed with a polyethylene terephthalate nonwoven fabric having a thickness of 28 ⁇ m and a width of 58.5 mm (hereinafter, polyethylene terephthalate nonwoven fabric, PET nonwoven fabric).
- the 18650 type lithium ion secondary battery was fabricated in the same manner as in Experimental Example 1A except that the above was used.
- the Gurley value of the PET nonwoven fabric was measured by the above method, it was 20 seconds / 100 cc.
- Example 2B Instead of polyethylene particles (polymer particles, trade name: Chemipearl (registered trademark) W400, average particle diameter 4 ⁇ m (Mitsui Chemicals catalog value), Mitsui Chemicals, Inc.), polyethylene particles (polymer particles, trade name: Chemipearl ( A 18650 type battery was fabricated in the same manner as in Experimental Example 1B except that (registered trademark) W300, an average particle size of 3 ⁇ m (catalog value from Mitsui Chemicals, Inc., manufactured by Mitsui Chemicals, Inc.) was used.
- Example 3B Instead of polyethylene particles (polymer particles, trade name: Chemipearl (registered trademark) W400, average particle diameter 4 ⁇ m (Mitsui Chemicals catalog value), Mitsui Chemicals, Inc.), polyethylene particles (polymer particles, trade name: Chemipearl ( A 18650 type battery was fabricated in the same manner as in Experimental Example 1B except that (registered trademark) WP100, average particle diameter of 1 ⁇ m (catalog value from Mitsui Chemicals, Inc., manufactured by Mitsui Chemicals, Inc.) was used.
- WP100 average particle diameter of 1 ⁇ m
- Example 4B A 18650 type battery was fabricated in the same manner as in Experimental Example 1B, except that the conductive layer was not provided on the surface of the positive electrode current collector.
- Example 5B A 18650 type battery was fabricated in the same manner as in Experimental Example 4B, except that a conductive layer was not provided on the surface of the positive electrode current collector, a polyethylene (PE) separator having a thickness of 30 ⁇ m and a Gurley value of 600 seconds / 100 cc was used. .
- the Gurley value of the polyethylene separator was measured by the method described above.
- the heat shrinkage (area shrinkage) of the polyethylene separator was measured by the above-mentioned method and found to be 98%.
- Example 6B A 18650 type battery was fabricated in the same manner as in Experimental Example 1B, except that a polyethylene separator having a thickness of 30 ⁇ m and a Gurley value of 600 seconds / 100 cc was used.
- the battery When the result of the overcharge test was C, the battery was charged at a constant current (CC) of up to 4.2 V at 0.5 C and then charged to a constant voltage (CV) of 0.01 C.
- the overcharge test results of D and E were charged at constant current (CC) to 4.1 V at 0.5 C and then charged to constant voltage (CV) to 0.01 C.
- constant current (CC) discharge was performed to 0.5V at 0.5 C, and the volume energy density at the time of discharge was evaluated according to the following evaluation criteria.
- C means “current value (A) / battery capacity (Ah)”.
- Discharge rate characteristic (%) (discharge capacity at 5 C / discharge capacity at 0.5 C) ⁇ 100 A: 91% or more B: 89% or more and less than 91% C: 80% or more and less than 89% D: Less than 80%
- Experimental Examples 1B to 3B it was found that excellent effects were obtained in terms of overcharge characteristics, volume energy density, and discharge rate characteristics as compared with Experimental Example 6B using a polyethylene separator and having a conductive layer.
- the separator made of polyethylene terephthalate in addition to the effect of increasing the voltage of the conductive layer (PTC layer), the separator made of polyethylene terephthalate has a high melting point and does not cause meltdown, that is, the voltage does not decrease. It is considered that charging characteristics were obtained.
- Experimental Example 4B using a polyethylene terephthalate separator that does not include a conductive layer may be inferior in terms of overcharge characteristics, although the battery characteristics are the same as Experimental Example 5B using a polyethylene separator. all right.
- the lithium ion secondary battery of the present invention has high safety.
- it can be suitably used as a power source for various portable electronic devices such as a mobile phone, a notebook personal computer, a portable information terminal, an electronic dictionary, and a game device.
- portable electronic devices such as a mobile phone, a notebook personal computer, a portable information terminal, an electronic dictionary, and a game device.
- the lithium ion secondary battery of this invention is applicable also to uses, such as for transportation apparatuses, such as an object for electric power storage, an electric vehicle, and a hybrid vehicle.
Abstract
Description
代表的なリチウムイオン二次電池では、セパレータを介して正極と負極を交互に積層して電極群が構成されている。負極の活物質としては、リチウムイオンの層間への挿入及び放出が可能な多層構造を有する炭素材料が主に用いられている。また、正極の活物質としては、リチウム含有複合金属酸化物が主に用いられている。また、セパレータにはポリオレフィン製多孔質膜が主に用いられている。このような材料から構成されるリチウムイオン二次電池は、電池容量及び出力が高く、充放電サイクル特性も良好である。
<1> 正極、負極及びセパレータを備えるリチウムイオン二次電池であって、
前記正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有し、
前記導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、
前記セパレータは、160℃における熱収縮率が30%以下であるリチウムイオン二次電池。
<2> 前記セパレータは多孔質基材と無機物粒子とを含み、前記多孔質基材は異なる2種以上の樹脂を含み、前記樹脂は、ポリプロピレン、ポリエチレン、ポリビニルアルコール、ポリエチレンテレフタレート、ポリアクリロニトリル及びアラミドからなる群より選択される<1>に記載のリチウムイオン二次電池。
<3> 前記多孔質基材は、ポリエチレンとポリプロピレンとを含む<2>に記載のリチウムイオン二次電池。
<4> 前記セパレータのガーレー値が1000秒/100cc以下である<1>に記載のリチウムイオン二次電池。
<5> 前記セパレータは多孔質基材と無機物粒子とを含み、前記多孔質基材はポリエステルを含む<1>又は<4>に記載のリチウムイオン二次電池。
<6> 前記ポリエステルはポリエチレンテレフタレートを含む<5>に記載のリチウムイオン二次電池。
<7> 前記ポリマー粒子はポリエチレン粒子を含む<1>~<6>のいずれか1項に記載のリチウムイオン二次電池。
<8> 前記導電性粒子及び前記ポリマー粒子の混合粒子と前記水溶性高分子との含有割合が、質量比(混合粒子:水溶性高分子)で、99.9:0.1~95:5である<1>~<7>のいずれか1項に記載のリチウムイオン二次電池。
<9> 前記導電性粒子と前記ポリマー粒子との含有割合が、質量比(導電性粒子:ポリマー粒子)で2:98~20:80である<1>~<8>のいずれか1項に記載のリチウムイオン二次電池。
<10> 正極、負極及びセパレータを備えるリチウムイオン二次電池であって、
前記正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有し、
前記導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、
前記セパレータは多孔質基材と無機物粒子とを含み、前記多孔質基材はポリプロピレン及びポリエチレンが交互に積層された積層体であるリチウムイオン二次電池。
<11> 正極、負極及びセパレータを備えるリチウムイオン二次電池であって、
前記正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有し、
前記導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、
前記セパレータは多孔質基材としてポリエチレンテレフタレートの織布又は不織布及び無機物粒子を含むリチウムイオン二次電池。
<12> 前記無機物粒子が酸化アルミニウム(Al2O3)及び酸化ケイ素(SiO2)の少なくとも一方である<2>、<3>、<5>、<6>、<10>及び<11>のいずれか1項に記載のリチウムイオン二次電池。
<13> 前記セパレータは前記多孔質基材の一方の面に前記無機物粒子を含む層を備え、前記無機物粒子を含む層が前記正極と対向する<2>、<3>、<5>、<6>、及び<10>~<12>のいずれか1項に記載のリチウムイオン二次電池。
<14> 前記セパレータの厚みが5μm~100μmである<1>~<13>のいずれか1項に記載のリチウムイオン二次電池。
<15> 前記導電層の厚みが0.1μm~10μmである<1>~<14>のいずれか1項に記載のリチウムイオン二次電池。
また、本開示の第二のリチウムイオン二次電池は、正極、負極及びセパレータを備えるリチウムイオン二次電池であって、前記正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有し、前記導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、前記セパレータは多孔質基材と無機物粒子とを含み、前記多孔質基材はポリプロピレン及びポリエチレンが交互に積層された積層体とされたものである。
また、本開示の第三のリチウムイオン二次電池は、正極、負極及びセパレータを備えるリチウムイオン二次電池であって、前記正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有し、前記導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、前記セパレータは多孔質基材としてポリエチレンテレフタレートの織布又は不織布及び無機物粒子を含むものである。
以下、第一のリチウムイオン二次電池、第二のリチウムイオン二次電池及び第三のリチウムイオン二次電池を併せて本開示のリチウムイオン二次電池と称することがある。
正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有する。正極は、正極活物質層、導電層及び集電体(正極集電体)をこの順番で重ね合わせた積層体であってもよい。導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、導電性粒子とポリマー粒子と水溶性高分子との集合体として構成される。
また、ある態様では、導電層の厚みは、電池特性とPTC機能の両立の観点から、0.1μm~10μmであることが好ましく、1μm~10μmであることがより好ましく、2μm~8μmであることがさらに好ましく、3μm~6μmであることが特に好ましい。
これらの中でも、アルミニウムを含有するシート又は箔が好ましい。シート及び箔の厚さは特に限定されず、集電体として必要な強度及び加工性を確保する観点から、例えば、1μm~500μmであることが好ましく、2μm~80μmであることがより好ましく、5μm~50μmであることがさらに好ましい。
ポリマー粒子の平均粒子径は特に制限されず、電池特性をより向上できる観点から、0.1μm~5μmであることが好ましく、0.2μm~4μmであることがより好ましい。
ポリオレフィン粒子の平均粒子径が小さい程、正極活物質層を均一に正極集電体上に形成できる傾向にあり、ポリオレフィン粒子の平均粒子径が大きい程、電池特性が向上する傾向にある。
また、オリビン型リチウム塩としては、例えば、LiFePO4等が挙げられる。カルコゲン化合物としては、例えば、二硫化チタン、二硫化モリブデン等が挙げられる。また、その他の正極活物質としては、Li2MPO4F(Li2MPO4F中、MはNa、Mg、Sc、Y、Mn、Fe、Co、Ni、Cu、Zn、Al、Cr、Pb、Sb、V及びBからなる群より選ばれる少なくとも1種の元素を示す。)が挙げられる。正極活物質は1種を単独で用いてもよく、又は必要に応じて2種以上を組み合わせて用いてもよい。
フッ素樹脂としては、ポリテトラフルオロエチレン(PTFE)、ポリフッ化ビニリデン(PVDF)、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体(FEP)、フッ化ビニリデン-ヘキサフルオロプロピレン共重合体等が挙げられる。
ゴム粒子としては、スチレン-ブタジエンゴム粒子、アクリロニトリルゴム粒子等が挙げられる。
これらの中でも、正極活物質層の耐酸化性を向上させること等を考慮すると、フッ素を含む結着材が好ましい。結着材は1種を単独で使用でき、又は必要に応じて2種以上を組み合わせて使用できる。
負極は、セパレータを介して正極に対向するように設けられ、負極集電体及び負極活物質層を含む。負極集電体としては、例えば、ステンレス鋼、ニッケル、銅等を含むシート、箔などが挙げられる。シート及び箔の厚さは特に限定されず、集電体として必要な強度及び加工性を確保する観点から、例えば、1μm~500μmであることが好ましく、2μm~100μmであることがより好ましく、5μm~50μmであることがさらに好ましい。負極活物質層は、負極集電体の厚み方向における一方又は両方の面に形成され、負極活物質を含有し、さらに必要に応じて、結着材、導電材、増粘剤等を含有していてもよい。
BET比表面積は、例えば、JIS Z 8830:2013に準じて窒素吸着能から測定することができる。評価装置としては、例えば、QUANTACHROME社製:AUTOSORB-1(商品名)を用いることができる。BET比表面積の測定を行う際には、試料表面及び構造中に吸着している水分がガス吸着能に影響を及ぼすと考えられることから、まず、加熱による水分除去の前処理を行うことが好ましい。
前処理では、0.05gの測定試料を投入した測定用セルを、真空ポンプで10Pa以下に減圧した後、110℃で加熱し、3時間以上保持した後、減圧した状態を保ったまま常温(25℃)まで自然冷却する。この前処理を行った後、評価温度を77Kとし、評価圧力範囲を相対圧(飽和蒸気圧に対する平衡圧力)にて1未満として測定する。
電解質としては、例えば、液状非水電解質、ゲル状非水電解質、固体状電解質(例えば高分子固体電解質)等が挙げられる。液状非水電解質は、溶質(支持塩)と非水溶媒とを含み、さらに必要に応じて各種添加剤を含む。溶質は通常非水溶媒中に溶解する。液状非水電解質は、例えば、セパレータに含浸される。
セパレータは、正極と負極との間に配置される。
本開示で用いられる第一のセパレータは、160℃における熱収縮率が30%以下とされる。
本開示で用いられる第二のセパレータは、多孔質基材と無機物粒子とを含み、前記多孔質基材はポリプロピレン及びポリエチレンが交互に積層された積層体とされる。
本開示で用いられる第三のセパレータは、多孔質基材としてポリエチレンテレフタレートの織布又は不織布及び無機物粒子を含む。
以下、第一のセパレータ、第二のセパレータ及び第三のセパレータを併せて本開示のセパレータと称することがある。
なお、第二のセパレータ及び第三のセパレータについての熱収縮率に限定はなく、例えば、30%以下であってもよく、20%以下であることが好ましく、10%以下であることがより好ましく、7%以下であることがさらに好ましく、2%以下であることが特に好ましい。
なお、TD方向とは、フィルム製造時の引取方向に対して垂直方向(横方向)を意味し、MD方向とは引取方向を意味する。
熱収縮率(面積収縮率)(%)=(加熱前の面積-加熱後の面積)/加熱前の面積×100
また、本開示のセパレータのガーレー値[秒/100cc]は、1秒/100cc~1000秒/100ccであってもよく、1秒/100cc~800秒/100ccであってもよく、1秒/100cc~600秒/100ccであってもよく、1秒/100cc~300秒/100ccであってもよく、1秒/100cc~200秒/100ccであってもよく、1秒/100cc~100秒/100ccであってもよい。
本明細書においてガーレー値は、ガーレー試験法(JIS P8117:2009)に準じて測定される値である。
多孔質基材に含まれる樹脂としては、ポリプロピレン、ポリエチレン等のオレフィン系樹脂、ポリテトラフルオロエチレン等のフッ素系樹脂、ポリエチレンテレフタレート(PET)等のポリエステル、アラミド、ポリアクリロニトリル、ポリビニルアルコール、ポリイミドなどが挙げられる。多孔質基材は、1種を単独で用いてもよく、又は必要に応じて2種以上を組み合わせて用いてもよい。
また、多孔質基材が2種以上の樹脂を含む場合、2種以上の樹脂を交互に積層した構造としてもよい。本開示において多孔質基材が2種以上の樹脂を積層した構造である場合、多孔質基材は二層構造又は三層構造であることが好ましい。
本明細書において、融点は、示差走査熱量測定装置(パーキンエルマ製DSC7)を用い、昇温速度10℃/分、測定温度範囲25℃~350℃、流量20±5ml/minの窒素雰囲気下の条件で、アルミパンに密閉した3mg~5mgの試料の示差走査熱量測定を行うことで測定される。示差走査熱量測定から得られた結果より、相転移に伴うエネルギー変化が起こる温度(吸熱反応ピーク)を融点とする。
セパレータは多孔質基材の一方の面に無機物粒子を含む層を備え、無機物粒子を含む層が正極と対向するようにセパレータを配置してもよい。無機物粒子を含む層は、多孔質基材を熱変形又は熱収縮から保護する耐熱層として機能することができる。
また、セパレータに三層構造の多孔質基材を用いる場合、三層構造の多孔質基材において好ましい組み合わせは、溶融温度の異なる樹脂を含む多孔質膜を積層したものであり、より好ましくはオレフィン系樹脂を含む多孔質基材の組み合わせであり、さらに好ましくは、ポリプロピレン/ポリエチレン/ポリプロピレン(以下、「PP/PE/PP」と称することがある。)の順で積層されたものである。多孔質基材を上記組み合わせにすることで、セパレータがシャットダウン機能を有し、かつ電気化学的安定性にも優れているため好ましい。
この3層の構成により、ポリエチレン層はポリプロピレン層間に挟持されている為、ポリエチレン層が溶融した場合でも、多孔質基材表面に存在するか又は空孔に含浸されている無機物粒子が耐熱層としての機能を発揮し、正極と負極の隔離機能を保持する。加えて、ポリエチレンが溶融しても流れ出さないため、効率よくシャットダウン機能が発揮される。さらに高温にさらされた場合、160℃~170℃の温度範囲においてポリプロピレンが溶融して、ポリエチレンとポリプロピレンが多孔質基材の空隙を閉塞させる為、より安全なシャットダウン機能が発揮される。
セパレータの厚みが、5μm~100μmの範囲であると、イオン透過性を保ちつつ、優れた体積エネルギー密度及び安全性を得ることができる。
図1に示すように、本開示のリチウムイオン二次電池1は、ニッケルメッキが施されたスチール製で有底円筒状の電池容器6を有している。電池容器6には、帯状の正極板2及び負極板3がセパレータ4を介して断面渦巻状に捲回された電極群5が収容されている。セパレータ4は、例えば、幅が58mm、厚さが30μmに設定される。電極群5の上端面には、一端部を正極板2に固定されたアルミニウム製でリボン状の正極タブ端子が導出されている。正極タブ端子の他端部は、電極群5の上側に配置され正極外部端子となる円盤状の電池蓋の下面に超音波溶接で接合されている。一方、電極群5の下端面には、一端部を負極板3に固定された銅製でリボン状の負極タブ端子が導出されている。負極タブ端子の他端部は、電池容器6の内底部に抵抗溶接で接合されている。従って、正極タブ端子及び負極タブ端子は、それぞれ電極群5の両端面の互いに反対側に導出されている。なお、電極群5の外周面全周には、図示を省略した絶縁被覆が施されている。電池蓋は、絶縁性の樹脂製ガスケットを介して電池容器6の上部にカシメ固定されている。このため、リチウムイオン二次電池1の内部は密封されている。また、電池容器6内には、図示しない非水電解液が注液されている。
(1)導電層の作製
アセチレンブラック(導電性粒子、商品名:HS-100、平均粒子径48nm(電気化学工業株式会社カタログ値)、電気化学工業株式会社製)と、ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)W400、平均粒子径4μm(三井化学株式会社カタログ値)、三井化学株式会社製)と、カルボキシメチルセルロース(CMC、株式会社ダイセル製、#2200)とを、固形分の質量比(アセチレンブラック:ポリエチレン粒子:CMC)が5:94:1になるように混合し、均一に分散させた。得られた混合物に、水を加えて導電層スラリーを作製した。この導電層スラリーを厚さ15μmのアルミニウム箔(正極集電体、三菱アルミニウム株式会社製)の両面に塗布し、60℃で乾燥させ、厚さ5μmの導電層を作製した。
正極板の作製を以下のように行った。正極活物質である層状型リチウム・ニッケル・マンガン・コバルト複合酸化物に、導電材としてアセチレンブラック(平均粒子径50nm)と、結着材としてポリフッ化ビニリデン(PVDF)とを順次添加し、混合することにより正極合剤ペーストを調整した。
負極板の作製を以下のように行った。負極活物質として易黒鉛化炭素(d002=0.35nm、平均粒子径(D50)=18μm)に結着材としてポリフッ化ビニリデン(PVDF)を添加した。これらの質量比は、負極活物質:結着材=92:8とした。これに分散溶媒であるN-メチル-2-ピロリドン(NMP)を添加し、混練することによりスラリーを形成した。このスラリーを負極用の集電体である厚さ10μmの圧延銅箔の両面に実質的に均等かつ均質に塗布した。尚、負極合材密度は1.15g/cm3とし、負極合剤の片面塗布量は90g/m2とした。
作製した正極と負極の間に、厚さ30μm、幅58.5mmのポリプロピレン/ポリエチレン/ポリプロピレン三層の多孔質基材にシリカを塗布したセパレータ(以下、コーティング型PP/PE/PPセパレータともいう)を挟んで捲回し、電極群を作製した。その際、電池の容量は900mAhとなるよう電極群を設計した。電極群を電池容器に挿入し、予め負極集電体に溶着した負極タブ端子を缶底に溶着した。次に、予め正極集電体に溶着した正極タブ端子を正極外部端子に電気的に接続するように溶着し、正極キャップを缶上部に配置させ、絶縁性のガスケットを挿入した。
なお、コーティング型PP/PE/PPセパレータは多孔質基材の一方の面にシリカを含む耐熱層が形成されており、正極と負極の間にコーティング型PP/PE/PPセパレータを介在させた際に、耐熱層が正極と対向するように配置した。
コーティング型PP/PE/PPセパレータの熱収縮率(面積収縮率)を上述の方法により測定したところ、18%であった。
ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)W400、平均粒子径4μm(三井化学株式会社カタログ値)、三井化学株式会社製)に代えて、ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)W300、平均粒子径3μm(三井化学株式会社カタログ値)、三井化学株式会社製)を使用する以外は、実験例1Aと同様にして、18650型電池を作製した。
ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)W400、平均粒子径4μm(三井化学株式会社カタログ値)、三井化学株式会社製)に代えて、ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)WP100、平均粒子径1μm(三井化学株式会社カタログ値)、三井化学株式会社製)を使用する以外は、実験例1Aと同様にして、18650型電池を作製した。
正極集電体表面に導電層を設けない以外は、実験例1Aと同様にして、18650型電池を作製した。
正極集電体表面に導電層を設けず、厚みが30μmのポリエチレン(PE)製セパレータを用いた以外は、実験例4Aと同様にして、18650型電池を作製した。
ポリエチレン製セパレータの熱収縮率(面積収縮率)を上述の方法により測定したところ、98%であった。
厚みが30μmのポリエチレン製セパレータを用いた以外は、実験例1Aと同様にして、18650型電池を作製した。
実験例1A~6Aで得られた18650型電池について、25℃の雰囲気下、3CA(2.7A)の定電流条件で過充電試験を実施した。過充電が進行するに従い電池温度が上昇し、それに伴い導電層中のポリマー粒子が溶解して内部抵抗が上昇する。内部抵抗の上昇により、大きな過電圧が生ずる。このとき電池の電圧をプロファイリングし、以下の基準で熱暴走する前の最高到達電圧を求め、これを過充電特性とした。この値が高いほど、電池の内部抵抗が上昇しており、良好な電流遮断性を示し、安全性に優れる。
A:6.1V以上
B:5.5V以上6.1V未満
C:5.5V未満
実験例1A~6Aで得られた18650型電池について、25℃での放電容量を基にした体積エネルギー密度を、充放電装置(東洋システム株式会社、商品名:TOSCAT-3200)を用いて以下の充放電条件で測定し、体積エネルギー密度を求めた。過充電試験の結果がA~Cのものは0.5Cで4.2Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。次いで、0.5Cで3Vまで定電流(CC)放電を行い、以下の評価基準で放電時の体積エネルギー密度を評価した。尚、Cとは“電流値(A)/電池容量(Ah)”を意味する。
A:235Wh/dm3以上
B:225Wh/dm3以上235Wh/dm3未満
C:225Wh/dm3未満
これは、導電層のPTC機能に加え、コーティング型PP/PE/PPセパレータは3層セパレータであることによって、セパレータがメルトダウンする温度を160℃程度まで向上させており、さらにセパレータ表面にシリカがコーティングされていることによって、セパレータがメルトダウンした際の短絡面積が縮小されているためであると考えられる。
一方、導電層を設けていない実験例4A、及び導電層を設けず且つポリエチレン製のセパレータを用いた実験例5Aは、過充電特性及び体積エネルギー密度が劣ることが分かった。また、ポリエチレン製のセパレータを用い、導電層を有する実験例6Aは、実験例4A及び5Aと比較して優れるものの、実験例1A~3Aよりは劣ることが分かった。
実験例1Aにおいて、コーティング型PP/PE/PPセパレータに代えて、厚さ28μm、幅58.5mmのポリエチレンテレフタレート不織布にアルミナ及びシリカが混合した耐熱層を有するセパレータ(以下、ポリエチレンテレフタレート不織布、PET不織布、という場合もある)を用いた以外は実験例1Aと同様にして、18650型リチウムイオン二次電池を作製した。
PET不織布のガーレー値を上述の方法により測定したところ、20秒/100ccであった。また、PET不織布の熱収縮率(面積収縮率)を上述の方法により測定したところ、2%であった。
ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)W400、平均粒子径4μm(三井化学株式会社カタログ値)、三井化学株式会社製)に代えて、ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)W300、平均粒子径3μm(三井化学株式会社カタログ値)、三井化学株式会社製)を使用する以外は、実験例1Bと同様にして、18650型電池を作製した。
ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)W400、平均粒子径4μm(三井化学株式会社カタログ値)、三井化学株式会社製)に代えて、ポリエチレン粒子(ポリマー粒子、商品名:ケミパール(登録商標)WP100、平均粒子径1μm(三井化学株式会社カタログ値)、三井化学株式会社製)を使用する以外は、実験例1Bと同様にして、18650型電池を作製した。
正極集電体表面に導電層を設けない以外は、実験例1Bと同様にして、18650型電池を作製した。
正極集電体表面に導電層を設けず、厚みが30μm、ガーレー値が600秒/100ccのポリエチレン(PE)製セパレータを用いた以外は、実験例4Bと同様にして、18650型電池を作製した。
ポリエチレン製セパレータのガーレー値は上述の方法により測定した。ポリエチレン製セパレータの熱収縮率(面積収縮率)を上述の方法により測定したところ、98%であった。
厚みが30μm、ガーレー値が600秒/100ccのポリエチレン製セパレータを用いた以外は、実験例1Bと同様にして、18650型電池を作製した。
実験例1B~6Bで得られた18650型電池について、実験例1A~6Aと同様にして過充電特性を評価した。なお、評価基準は以下のように変更した。
A:7V以上
B:6.1V以上7V未満
C:5.5V以上6.1V未満
D:4.8V以上5.5V未満
E:4.8V未満
[体積エネルギー密度の評価]
実験例1B~6Bで得られた18650型電池について、25℃での放電容量を基にした体積エネルギー密度と放電レート特性を、充放電装置(東洋システム株式会社、商品名:TOSCAT-3200)を用いて以下の充放電条件で測定し、電池特性とした。過充電特性の結果がAのものは0.5Cで4.3Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。過充電試験の結果がBのものは0.5Cで4.25Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。過充電試験の結果がCのものは0.5Cで4.2Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。過充電試験の結果がD及びEのものは0.5Cで4.1Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。次いで、0.5Cで3Vまで定電流(CC)放電を行い、以下の評価基準で放電時の体積エネルギー密度を評価した。尚、Cとは“電流値(A)/電池容量(Ah)”を意味する。
A:245Wh/dm3以上
B:235Wh/dm3以上245Wh/dm3未満
C:225Wh/dm3以上235Wh/dm3未満
D:225Wh/dm3未満
過充電試験の結果がAのものは0.5Cで4.3Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。過充電試験の結果がBのものは0.5Cで4.25Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。過充電試験の結果がCのものは0.5Cで4.2Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。過充電試験の結果がD及びEのものは0.5Cで4.1Vまで定電流(CC)充電した後、0.01Cまで定電圧(CV)充電した。次いで、0.5Cで3Vまで定電流(CC)放電した。その後、充電の条件は同様にし、放電電流値を1C、3C、5Cと変化させた際の放電容量の測定を行い、下記の式から算出される値を放電レート特性とし、以下の評価基準で評価した。
放電レート特性(%)=(5Cでの放電容量/0.5Cでの放電容量)×100
A:91%以上
B:89%以上91%未満
C:80%以上89%未満
D:80%未満
導電層を含まず、ポリエチレンテレフタレート製のセパレータを用いた実験例4Bは、ポリエチレン製のセパレータを用いた実験例5Bと比較すると、電池特性は同等であるものの、過充電特性の点で劣ることがわかった。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (15)
- 正極、負極及びセパレータを備えるリチウムイオン二次電池であって、
前記正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有し、
前記導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、
前記セパレータは、160℃における熱収縮率が30%以下であるリチウムイオン二次電池。 - 前記セパレータは多孔質基材と無機物粒子とを含み、前記多孔質基材は異なる2種以上の樹脂を含み、前記樹脂は、ポリプロピレン、ポリエチレン、ポリビニルアルコール、ポリエチレンテレフタレート、ポリアクリロニトリル及びアラミドからなる群より選択される請求項1に記載のリチウムイオン二次電池。
- 前記多孔質基材は、ポリエチレンとポリプロピレンとを含む請求項2に記載のリチウムイオン二次電池。
- 前記セパレータのガーレー値が1000秒/100cc以下である請求項1に記載のリチウムイオン二次電池。
- 前記セパレータは多孔質基材と無機物粒子とを含み、前記多孔質基材はポリエステルを含む請求項1又は請求項4に記載のリチウムイオン二次電池。
- 前記ポリエステルはポリエチレンテレフタレートを含む請求項5に記載のリチウムイオン二次電池。
- 前記ポリマー粒子はポリエチレン粒子を含む請求項1~請求項6のいずれか1項に記載のリチウムイオン二次電池。
- 前記導電性粒子及び前記ポリマー粒子の混合粒子と前記水溶性高分子との含有割合が、質量比(混合粒子:水溶性高分子)で、99.9:0.1~95:5である請求項1~請求項7のいずれか1項に記載のリチウムイオン二次電池。
- 前記導電性粒子と前記ポリマー粒子との含有割合が、質量比(導電性粒子:ポリマー粒子)で2:98~20:80である請求項1~請求項8のいずれか1項に記載のリチウムイオン二次電池。
- 正極、負極及びセパレータを備えるリチウムイオン二次電池であって、
前記正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有し、
前記導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、
前記セパレータは多孔質基材と無機物粒子とを含み、前記多孔質基材はポリプロピレン及びポリエチレンが交互に積層された積層体であるリチウムイオン二次電池。 - 正極、負極及びセパレータを備えるリチウムイオン二次電池であって、
前記正極は、集電体と前記集電体上に形成された導電層と前記導電層上に形成された正極活物質層とを有し、
前記導電層は、導電性粒子とポリマー粒子と水溶性高分子とを含み、
前記セパレータは多孔質基材としてポリエチレンテレフタレートの織布又は不織布及び無機物粒子を含むリチウムイオン二次電池。 - 前記無機物粒子が酸化アルミニウム(Al2O3)及び酸化ケイ素(SiO2)の少なくとも一方である請求項2、請求項3、請求項5、請求項6、請求項10及び請求項11のいずれか1項に記載のリチウムイオン二次電池。
- 前記セパレータは前記多孔質基材の一方の面に前記無機物粒子を含む層を備え、前記無機物粒子を含む層が前記正極と対向する請求項2、請求項3、請求項5、請求項6、及び請求項10~請求項12のいずれか1項に記載のリチウムイオン二次電池。
- 前記セパレータの厚みが5μm~100μmである請求項1~請求項13のいずれか1項に記載のリチウムイオン二次電池。
- 前記導電層の厚みが0.1μm~10μmである請求項1~請求項14のいずれか1項に記載のリチウムイオン二次電池。
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