Patent Application
20200067138
An embodiment of the present invention relates to a separator and a secondary battery including the separator. For example, an embodiment of the present invention relates to a separator capable of being used in a nonaqueous electrolyte-solution secondary battery and a nonaqueous electrolyte-solution secondary battery including the separator.
As a typical example of a nonaqueous electrolyte-solution secondary battery, a lithium ion secondary battery is represented. Since a lithium-ion secondary battery has a high energy density, it has been widely used in electronic devices such as a personal computer, a mobile phone, and a mobile information terminal. A lithium ion secondary battery includes a positive electrode, a negative electrode, an electrolyte solution charged between the positive electrode and the negative electrode, and a separator. The separator separates the positive electrode and the negative electrode from each other and also functions as a film transmitting the electrolyte solution and carrier ions. For example, Patent Literature 1 discloses a separator including a polyolefin.
In the nonaqueous electrolyte-solution secondary battery, since the electrode repeats expansion and contraction with charge and discharge, stress is generated between the electrode and the separator, the electrode active material is dropped, and the internal resistance is increased, thus, there was a problem that the cycling characteristics decreased. Then, the method of improving the adhesiveness of a separator and an electrode is proposed by coating adhesive substances, such as a polyvinylidene fluoride, on the surface of a separator (Patent Literatures 2 and 3).
On the other hand, in recent years, with the improvement in performance of the nonaqueous electrolyte-solution secondary battery, a nonaqueous electrolyte-solution secondary battery having higher safety is required. In order to ensure the safety and productivity of the battery, it is known that it is effective to control the tearing strength of the separator, which is measured by the Trouser Tear method (in accordance with JIS K 7128-1), in response to such requirements (Patent Literatures 4 and 5).
In addition, it is known that controlling the tearing strength is also effective for film routing and the like (Patent Literatures 6 and 7).
An object of the present invention is to provide a separator capable of being used in a secondary battery such as a nonaqueous electrolyte-solution secondary battery and a secondary battery including the separator.
In addition, an object of the present invention is to provide a separator capable of suppressing an increase in internal resistance when charging and discharging are repeated and suppressing the occurrence of an internal short circuit against an external impact, and a secondary battery including the separator.
An embodiment of the present invention includes a first layer consisting of a porous polyolefin. The first layer has a parameter X calculated by the following equation equal to or less than 20 from MD tan δ, which is tan δ of MD obtained by a viscoelastic measurement at a frequency of 10 Hz and a temperature of 90° C., and TD tan δ, which is tan δ of TD. Further, in the first layer, a tearing strength of the first layer measured by the Elmendorf tearing method (in accordance with JIS K 7128-2) is equal to or higher than 1.5 mN/μm, and in a load-tensile elongation curve in a tearing strength measurement (based on JIS K 7128-3) of the first layer by the right-angled tearing method, a value of the tensile elongation from a point when a load reaches the maximum load to a point when it attenuates to 25% of the maximum load is equal to or longer that 0.5 mm.
X=100×|MD tan δ−TD tan δ|/[(MD tan δ+TD tan δ)/2]
According to the present invention, it is possible to provide a separator capable of suppressing an increase in internal resistance when charging and discharging are repeated, and suppressing the occurrence of an internal short circuit against an external impact, and a secondary battery including the separator.
Hereinafter, the embodiments of the present invention are explained with reference to the drawings and the like. The invention can be implemented in a variety of different modes within its concept and should not be interpreted only within the disclosure of the embodiments exemplified below.
The drawings may be illustrated so that the width, thickness, shape, and the like are illustrated more schematically compared with those of the actual modes in order to provide a clearer explanation. However, they are only an example, and do not limit the interpretation of the invention.
In the specification and the claims, unless specifically stated, when a state is expressed where a structure is arranged “on” another structure, such an expression includes both a case where the substrate is arranged immediately above the “other structure” so as to be in contact with the “other structure” and a case where the structure is arranged over the “other structure” with an additional structure therebetween.
In the specification and the claims, an expression “substantially including only A” or an expression “consisting of A” includes a state where no substance is included other than A, a state where A and an impurity are included, and a state misidentified as a state where a substance other than A is included due to a measurement error. When this expression means the state where A and an impurity are included, there is no limitation to the kind and concentration of the impurity.
A schematic cross-sectional view of a secondary battery 100 according to an embodiment of the present invention is shown in
The separator 130 is disposed between the positive electrode 110 and the negative electrode 120 and serves as a film having a role of separating the positive electrode 110 and the negative electrode 120 and transporting the electrolyte solution 140 in the secondary battery 100. A schematic cross-sectional view of the separator 130 is shown in
The first layer 132 has internal pores linked to each other. This structure allows the electrolyte solution 140 to permeate the first layer 132 and enables carrier ions such as lithium ions to be transported via the electrolyte solution 140. At the same time, physical contact between the positive electrode 110 and the negative electrode 120 is inhibited. On the other hand, when the secondary battery 100 has a high temperature, the first layer 132 melts and the pores disappear, thereby stopping the transportation of the carrier ions. This behavior is called shutdown. This behavior prevents heat generation and ignition caused by a short-circuit between the positive electrode 110 and the negative electrode 120, by which high safety is secured.
The first layer 132 includes a porous polyolefin. Alternatively, the first layer 132 may be structured with a porous polyolefin. Namely, the first layer 132 may be configured so as to include only a porous polyolefin or substantially include only a porous polyolefin. The porous polyolefin may contain an additive. In this case, the first layer 132 may be structured only with the polyolefin and the additive or substantially only with the polyolefin and the additive. When the porous polyolefin contains the additive, the polyolefin may be included in the porous polyolefin at a composition equal to or higher than 95 wt %, equal to or higher than 97 wt % or equal to or higher than 99 wt %. Furthermore, the polyolefin may be included in the first layer 132 at a composition equal to or higher than 95 wt % or equal to or higher than 97 wt %. The content of polyolefin in the first layer 132 may be 100 wt % or may be less than 100 wt %. As the additive, an organic compound (organic additive) is represented, and the organic compound may be an antioxidant (organic antioxidant) or a lubricant.
As the polyolefin structuring the porous polyolefin, a homopolymer obtained by polymerizing an α-olefin such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene or a copolymer thereof is represented. A mixture of these homopolymers and copolymers may be included in the first layer 132 and a mixture of homopolymers and copolymers having different molecular weights may be included. That is, the molecular weight distribution of the polyolefin may have a plurality of peaks. The organic additive may have a function to prevent oxidation of the polyolefin, and phenols or phosphoric esters may be employed as the organic additive, for example. Phenols having a bulky substituent such as t-butyl group at an α-position and/or a β-position of a phenolic hydroxy group may be also used.
As a typical polyolefin, a polyethylene-based polymer is represented. When a polyethylene-based polymer is used, a low-density polyethylene or a high-density polyethylene may be used. Alternatively, a copolymer of ethylene with an α-olefin may be used. These polymers or copolymers may be a high-molecular weight polymer with a weight-average molecular weight equal to or higher than 100,000 or an ultrahigh-molecular weight polymer with a weight-average molecular weight of equal to or higher than 1,000,000. The use of a polyethylene-based polymer enables the shutdown function to be realized at a lower temperature, thereby providing high safety to the secondary battery 100 and a mechanical strength of the separator can be improved by using ultra-high molecular weight substances higher than 1,000,000, which is preferable.
A thickness of the first layer 132 may be appropriately determined in consideration of a thickness and the like of other members in the secondary battery 100 and may be equal to or larger than 4 μm and equal to or smaller than 40 μm, equal to or larger than 5 μm and equal to or smaller than 30 μm, or equal to or larger than 6 μm and equal to or smaller than 15 μm.
A weight per unit area of the first layer 132 is appropriately determined in view of its strength, thickness, weight, and handleability. For example, the weight per unit area may be equal to or more than 4 g/m2 and equal to or less than 20 g/m2, equal to or more than 4 g/m2 and equal to or less than 12 g/m2, or equal to or more than 5 g/m2 and equal to or less than 10 g/m2, by which a weight-energy density and a volume-energy density of the secondary battery 100 can be increased. Note that a weight per unit area is a weight per unit area.
With respect to gas permeability of the first layer 132, its Gurley value may be selected from a range equal to or higher than 30 s/100 mL and equal to or lower than 500 s/100 mL or equal to or higher than 50 s/100 mL and equal to or lower than 300 s/100 mL so that sufficient ion-permeability can be obtained.
A porosity of the first layer 132 may be selected from a range equal to or more than 20 vol % and equal to or less than 80 vol % or equal to or more than 30 vol % and equal to or less than 75 vol % so that a retention volume of the electrolyte solution 140 is increased and the shutdown function is surely realized. A diameter of the pore (average pore diameter) in the first layer 132 may be selected from a range equal to or larger than 0.01 μm and equal to or smaller than 0.3 μm or equal to or larger than 0.01 μm and equal to or smaller than 0.14 μm so that a sufficient ion-permeability and a high shutdown function can be obtained.
The first layer 132 has a parameter X calculated by the following equation of 20 or less from MD tan δ, which is tan δ of MD obtained by a viscoelastic measurement at a frequency of 10 Hz and a temperature of 90° C., and TD tan δ, which is tan δ of TD. Further, a tearing strength of the first layer 132 measured by the Elmendorf tearing method (in accordance with JIS K 7128-2) is equal to or higher than 1.5 mN/μm, and in a load-tensile elongation curve in a strength measurement (JIS K 7128-3) of the first layer 132 by the right angle tearing method, the value E of the tensile elongation until it attenuates to 25% of the maximum load from a point when the load reaches the maximum load is equal to or longer than 0.5 mm.
X=100×|MD tan δ−TD tan δ|/[(MD tan δ+TD tan δ)/2]
Here, MD tan δ is a loss tangent in the flow direction (MD: Machine Direction; also called machine direction) obtained by a viscoelastic measurement of the first layer 132 at a temperature of 90° C. and a frequency of 10 Hz, and TD tan δ is a loss tangent in the width direction (TD: Transverse Direction, also referred to as lateral direction) obtained by a viscoelastic measurement of the first layer 132 at a temperature of 90° C. and a frequency of 10 Hz.
The present inventors found for the first time that the anisotropy of tan δ obtained by a dynamic viscoelasticity measurement at a frequency of 10 Hz and a temperature of 90° C. relates to an increase in internal resistance when charging and discharging are repeated for the first layer 132 containing a polyolefin resin as a main component.
tan δ obtained by a dynamic viscoelasticity measurement is represented by the equation below based on a storage modulus E′ and a loss modulus E″.
tan δ=E″/E′
The loss modulus indicates irreversible deformability under stress, and the storage modulus indicates reversible deformability under stress. Therefore, tan δ indicates a followability of the deformation of the first layer 132 to the change of the external stress. In addition, as the anisotropy of tan δ in the in-plane direction of the first layer 132 is smaller, the deformation followability of the first layer 132 with respect to the change of the external stress becomes more isotropic, and it is possible to deform uniformly in the surface direction.
In a secondary battery such as a nonaqueous electrolyte-solution secondary battery, since the electrodes (positive electrode 110 and negative electrode 120) expand and contract during charge and discharge, stress is applied to the separator 130. At this time, if the deformation followability of the first layer 132 constituting the separator 130 is isotropic, it deforms uniformly. Therefore, the anisotropy of the stress generated in the first layer 132 along with the periodic deformation of the electrode in the charge and discharge cycle is also reduced. As a result, the electrode active material is less likely to come off, so that the increase in internal resistance of the secondary battery 100 can be suppressed, and cycle characteristics are improved.
In addition, as expected from the time-temperature conversion law regarding the stress relaxation process of a polymer, the frequency when the dynamic viscoelasticity measurement at a frequency of 10 Hz and a temperature of 90° C. corresponds to a reference temperature at a temperature within the temperature range of about 20 to 60° C. at which the secondary battery 100 operates is the wave number much lower than 10 Hz, which is close to the time scale of the expansion and contraction movement of the electrode accompanying the charge and discharge cycle of the secondary battery 100. Therefore, by measuring the dynamic viscoelasticity at 10 Hz and 90° C., it is possible to perform a rheological evaluation corresponding to the time scale to the extent of the charge and discharge cycle in the operating temperature range of the secondary battery 100.
In the present invention, the anisotropy of tan δ is evaluated by the parameter X defined by the above equation, and when the parameter X is equal to or larger than 0 and equal to or less than 20, or equal to or larger than 2 and equal to or less than 20, an increase in internal resistance of the secondary battery 100 can be suppressed in the charge and discharge cycle.
In the specification and claims, the tensile strength is a tearing force measured according to “JIS K 7128-2 Tearing Strength Test Method of Plastic Film and Sheet-2nd Part: Elmendorf Tearing Method” regulated by the Japan Industrial Standards (JIS). Specifically, the tearing force is measured using the separator 130 having a rectangular shape based on the JIS Regulation where the swing angle of a pendulum is set to be 68.4° and the tearing direction in the measurement is set in the TD of the separator 130. The measurement is carried out in a state where 4 to 8 separators are stacked, and the obtained tearing load is divided by the number of the measured separators to calculate the tearing strength per one separator 130. The tearing strength per one separator 130 is further divided by the thickness of the separator 130 to calculate the tearing strength T per 1 μm thickness of the separator 130.
That is, the tearing strength T is calculated by the following equation.
T=(F/d)
where F is the tearing load (mN) per one separator 130 obtained by the measurement, d is the thickness (μm) of the separator 130, and the unit of the tearing strength T is mN/μm.
In the specification and claims, the tensile elongation E is an elongation of the separator 130 calculated from the load-elongation curve obtained by the measurement based on the “JIS K 7128-3 Tearing Strength Test Method of Plastic Film and Sheet-3rd Part: Rectangular Tearing Method” regulated by the JIS. The separator 130 is processed into the shape based on the JIS Regulation and is stretched at an elongating rate of 200 mm/min while arranging the tearing direction in the TD. Since the stretching direction and the tearing direction are reversed, the stretching direction is the MD, while the tearing direction is the TD. That is, the separator 130 becomes a shape long in the MD. The load-elongation curve obtained by the measurement under these conditions is schematically shown in
In the first layer 132, the tearing strength by the Elmendorf tearing method is equal to or larger than 1.5 mN/μm, preferably equal to or larger than 1.75 mN/μm, more preferably equal to or larger than 2.0 mN/μm. Further. It is preferably equal to or smaller than 10 mN/μm, more preferably equal to or smaller than 4.0 mN/μm. When the tearing strength (tear direction: TD direction) by the Elmendorf tearing method is equal to or larger than 1.5 mN/μm, the first layer 132, that is, the separator 130 and the separator 130 having the first layer 132 and the porous layer 134 is less likely to generate an internal short circuit even when it receives an impact.
In the first layer 132, the tensile elongation value E based on the right-angled tearing method is equal to or longer than 0.5 mm, preferably equal to or longer than 0.75 mm and more preferably equal to or longer than 1.0 mm. Moreover, it is preferably equal to or longer than 10 mm. When the tensile elongation value E based on the right-angled tearing method is equal to or longer than 0.5 mm, the first layer 132, that is, the separator 130, and the separator 130 including the first layer 132 and the porous layer 134 tend to be able to suppress the rapid occurrence of a large internal short circuit even when receiving an external impact.
As described above, because the separator 130 according to the present invention has the parameter X equal to or less than 20 calculated by the above equation from MD tan δ, which is tan δ of MD and TD tan δ, which is tan δ of TD obtained by a viscoelastic measurement at a frequency of 10 Hz and a temperature of 90° C., tearing strength equal to or larger than 1.5 mN/μm of the first layer 132 measured by the Elmendorf tear method (in accordance with JIS K 7128-2), and the value E of the tensile elongation equal to or longer than 0.5 mm from a point when the load reaches the maximum load to a point when it attenuates to 25% of the maximum load in the load-tensile elongation curve in the tearing strength measurement (in accordance with JIS K 7128-3) of the first layer 132 by the right-angled tear method, a separator and a secondary battery including the separator capable of suppressing an increase in internal resistance when charging and discharging are repeated, and capable of suppressing the occurrence of an internal short circuit against an external impact can be provided.
Further, the puncture strength of the first layer 132 is preferably equal to or larger than 3N and equal to or less than 10N, or equal to or larger than 3N or more and equal to or less than 8N. Thereby, when external pressure is applied to the secondary battery in the assembly process, destruction of the separator 130 including the first layer 132 can be suppressed, and a short circuit of the positive and negative electrodes can be prevented.
As described above, the positive electrode 110 may include the positive-electrode current collector 112 and the positive-electrode active-substance layer 114. Similarly, the negative electrode 120 may include the negative-electrode current collector 122 and the negative-electrode active-substance layer 124 (see
A metal such as nickel, copper, titanium, tantalum, zinc, iron, and cobalt or an alloy such as stainless including these metals can be used for the positive-electrode current collector 112 and the negative-electrode current collector 122, for example. The positive-electrode current collector 112 and the negative-electrode current collector 122 may have a structure in which a plurality of layers including these metals or alloys is stacked.
The positive-electrode active-substance layer 114 and the negative-electrode active-substance layer 124 respectively include a positive-electrode active substance and a negative-electrode active substance. The positive-electrode active substance and the negative-electrode active substance have a role to release and absorb carrier ions such as lithium ions.
As a positive-electrode active substance, a material capable of being doped or de-doped with carrier ions is represented, for example. Specifically, a lithium-based composite oxide containing at least one kind of transition metals such as vanadium, manganese, iron, cobalt, and nickel is represented. As such a composite oxide, a lithium-based composite oxide having an α-NaFeO2-type structure, such as lithium nickelate and lithium cobalate, and a lithium-based composite oxide having a spinel-type structure, such as lithium manganese spinel, are given. These composite oxides have a high average discharge potential.
The lithium-based composite oxide may contain another metal element and is exemplified by lithium nickelate (composite lithium nickelate) including an element selected from titanium, zirconium, cerium, yttrium, vanadium, chromium, manganese, iron, cobalt, copper, silver, magnesium, aluminum, gallium, indium, tin, and the like, for example. These metals may be adjusted to be equal to or more than 0.1 mol % and equal to or less than 20 mol % to the metal elements in the composite lithium nickelate. This structure provides the secondary battery 100 with an excellent rate maintenance property when used at a high capacity. For example, a composite lithium nickelate including aluminum or manganese and containing nickel at 85 mol % or more or 90 mol % or more may be used as the positive-electrode active substance.
Similar to the positive-electrode active substance, a material capable of being doped and de-doped with carrier ions can be used as the negative-electrode active substance. For example, a lithium metal or a lithium alloy is represented. Alternatively, it is possible to use a carbon-based material such as graphite exemplified by natural graphite and artificial graphite, cokes, carbon black, and a sintered polymeric compound exemplified by carbon fiber; a chalcogen-based compound capable of being doped and de-doped with lithium ions at a potential lower than that of the positive electrode, such as an oxide and a sulfide; an element capable of being alloyed or reacting with an alkaline metal, such as aluminum, lead, tin, bismuth, and silicon; an intermetallic compound of cubic system (AlSb, Mg2Si, NiSi2) undergoing alkaline-metal insertion between lattices; lithium-nitride compound (Li3-xMxN (M: transition metal)); and the like. Among the negative-electrode active substances, the carbon-based material including graphite such as natural graphite and artificial graphite as a main component provides a large energy density due to high potential uniformity and a low average discharge potential when combined with the positive electrode 110. For example, it is possible to use, as the negative-electrode active substance, a mixture of graphite and silicon with a ratio of silicon to carbon equal to or larger than 5 mol % and equal to or smaller 10 mol %.
The positive-electrode active-substance layer 114 and the negative-electrode active-substance layer 124 may each further include a conductive additive and binder other than the aforementioned positive-electrode active substance and the negative-electrode active substance.
As a conductive additive, a carbon-based material is represented. Specifically, graphite such as natural graphite and artificial graphite, cokes, carbon black, pyrolytic carbons, and a sintered polymeric compound such as carbon fiber are given. A plurality of materials described above may be mixed to use as a conductive additive.
As a binder, poly(vinylidene fluoride) (PVDF), polytetrafluoroethylene, poly(vinylidene fluoride-co-hexafluoropropylene), poly(tetrafluoroethylene-co-hexafluoropropylene), poly(tetrafluoroethylene-co-perfluoroalkyl vinyl ether), poly(ethylene-co-tetrafluoroethylene), a copolymer in which vinylidene fluoride is used as a monomer, such as a poly(vinylidene fluoride-co-hexafluoropropylene-co-tetrafluoroethylene), a thermoplastic resin such as a thermoplastic polyimide, polyethylene, and polypropylene, an acrylic resin, styrene-butadiene rubber, and the like are represented. Note that a binder may further have a function as a thickener.
The positive electrode 110 may be formed by applying a mixture of the positive-electrode active substance, the conductive additive, and the binder on the positive-electrode current collector 112, for example. In this case, a solvent may be used to form or apply the mixture. Alternatively, the positive electrode 110 may be formed by applying a pressure to the mixture of the positive-electrode active substance, the conductive additive, and the binder to process the mixture and arranging the processed mixture on the positive electrode 110. The negative electrode 120 can also be formed with a similar method.
The electrolyte solution 140 includes the solvent and an electrolyte, and at least a part of the electrolyte is dissolved in the solvent and electrically dissociated. As the solvent, water and an organic solvent can be used. In the case where the secondary battery 100 is utilized as a nonaqueous electrolyte-solution secondary battery, an organic solvent is used. As an organic solvent, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 1,2-di(methoxycarbonyloxy)ethane, ethers such as 1,2-dimethoxyethane, 1,3-dimethoxypropane, tetrahydrofuran, and 2-methyltetrahydrofuran; esters such as methyl formate, methyl acetate, and γ-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-propanesultone; a fluorine-containing organic solvent in which fluorine is introduced to the aforementioned organic solvent; and the like are represented. A mixed solvent of these organic solvents may also be employed.
As a typical electrolyte, a lithium salt is represented. For example, LiClO4, LiPF6, LiAsF6, LiSbF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2, LiC(CF3SO2)3, Li2B10Cl10, a lithium salt of a carboxylic acid having 2 to 6 carbon atoms, LiAlC14, and the like are represented. Just one kind of the lithium salts mentioned above may be used, and more than two kinds of lithium salts may be combined.
Note that, in a broad sense, an electrolyte may mean a solution of an electrolyte. However, in the present specification and claims, a narrow sense is employed. That is, an electrolyte is a solid and is electrically dissociated upon dissolving in a solvent to provide an ion conductivity to the resulting solution.
As shown in
In the present embodiment, a method for preparing the first layer 132 described in the First Embodiment is described. An explanation of the structures the same as those of the First Embodiment may be omitted.
A method for preparing the first layer 132 includes (1) a process for obtaining a polyolefin resin composite by kneading an ultrahigh-molecular weight polyethylene, a low-molecular weight polyolefin, and a pore-forming agent, (2) a process for forming a sheet by rolling the polyolefin resin composite with a rolling roll (rolling process), (3) a process for removing the pore-forming agent from the sheet obtained in the process (2), and (4) a process for processing into a film state by stretching the sheet obtained in the process (3). The order of the process (3) and the process (4) may be reversed.
There is no limitation on the shape of the ultrahigh-molecular weight polyethylene, and for example, a polyolefin processed into powder can be used. The weight average molecular weight of the low-molecular weight polyolefin is, for example, 200 or more and 3,000 or less. Thus, the volatilization of the low-molecular weight polyolefin can be suppressed, and the low-molecular weight polyolefin can be uniformly mixed with the ultrahigh-molecular weight polyolefin. In the present specification and claims, polymethylene is also defined as a type of polyolefin.
The pore-forming agent includes an organic filler and an inorganic filler. As the organic filler, for example, a plasticizer may be used, and as the plasticizer, a low-molecular weight hydrocarbon such as a liquid paraffin and a mineral oil can be exemplified as a plasticizer.
As an inorganic filler, an inorganic material soluble in a neutral, acidic, or alkaline solvent is represented, and calcium carbonate, magnesium carbonate, barium carbonate, and the like are exemplified. Other than these materials, an inorganic compound such as calcium chloride, sodium chloride, and magnesium sulfate is represented.
The pore-forming agent may be used alone or in combination of two or more. Calcium carbonate is exemplified as a typical pore-forming agent.
The weight ratio of each material can be, for example, the low molecular weight polyolefin equal to or more than 5 weight portions and equal to or less than 200 weight portions and the pore-forming agent equal to or more than 100 weight portions and equal to or less than 400 weight portions to 100 weight portions of the ultrahigh-molecular weight polyethylene. At this time, an organic additive may be added. The amount of the organic additive can be equal to or less than 1 weight portions and equal to or less than 10 weight portions, equal to or more than 2 weight portions and equal to or less than 7 weight portions, or equal to or more than 3 weight portions and equal to or less than 5 weight portions to 100 weight portions of the ultrahigh-molecular weight polyethylene.
In the process (1), for example, the ultrahigh-molecular weight polyolefin and the low-molecular weight polyolefin may be mixed (first stage mixing) by a mixer, and the pore-forming agent may be added to the mixture and mixed again (second stage mixing). In the first stage mixing, an organic compound such as an antioxidant may be added. By mixing in two steps, mixing of the ultra-high molecular weight polyolefin and the low-molecular weight polyolefin becomes uniform, and furthermore, the ultrahigh-molecular weight polyolefin, the low-molecular weight polyolefin and the pore-forming agent can be uniformly mixed. These uniform mixtures, in particular, uniform mixtures of ultrahigh-molecular weight polyolefin and low-molecular weight polyolefin, can be confirmed by an increase in bulk density of the mixture and the like. With uniform mixing, uniform crystallization proceeds, and as a result, the crystal distribution becomes uniform, and the anisotropy of Tan δ can be reduced. After the first stage mixing, it is preferable that there is an interval equal to or more than one minute until the pore-forming agent is added.
A factor influencing tan δ includes the crystal structure of a polymer, and in polyolefins, particularly polyethylene, a detailed study has been conducted on the relationship between tan δ and the crystal structure (Refer to “Takayanagi M., J. of Macromol. Sci.-Phys., 3, 407-431 (1967)” or “The Basics of Polymer Science” Second Edition, edited by the Society of Polymer Science, Tokyo Kagaku Dojin (1994)”). According to these, the peak of tan δ observed at 0 to 130° C. of polyethylene is attributed to crystal relaxation (αC relaxation) and is viscoelastic crystal relaxation involved in an harmonicity of crystal lattice vibration. In the crystal relaxation temperature range, crystals are viscoelastic, and internal friction when molecular chains are extracted from lamellar crystals is the origin of viscosity (loss elasticity). That is, the anisotropy of tan δ reflects not the anisotropy of crystals but the anisotropy of internal friction when molecular chains are extracted from lamellar crystals. Therefore, by controlling the crystal-amorphous distribution more uniformly, the anisotropy of tan δ can be reduced, and a porous film having a parameter X equal to or less than 20 can be produced.
In step (2), the polyolefin resin composition is extended by applying pressure using a pair of rolls at a temperature, for example, equal to or higher than 245° C. and equal to or lower than 280° C., or equal to or higher than 245° C. and equal to or lower than 260° C. and it can process it into a sheet shape by cooling in steps while pulling with a roll whose speed ratio is changed.
In the process (3) in which the pore-forming agent is removed, a solution of water or organic solvent to which an acid or a base is added, or the like is used as a cleaning solution. A surfactant may be added to the cleaning solution. An addition amount of the surfactant can be arbitrarily selected from a range equal to or more than 0.1 wt % to 15 wt % or equal to or more than 0.1 wt % and equal to or less than 10 wt %. It is possible to secure a high cleaning efficiency and prevent the surfactant from being left by selecting the addition amount from this range. A cleaning temperature may be selected from a temperature range equal to or higher than 25° C. and equal to or lower than 60° C., equal to or higher than 30° C. and equal to or lower than 55° C., or equal to or higher than 35° C. and equal to or lower than 50° C., by which a high cleaning efficiency can be obtained and evaporation of the cleaning solution can be avoided.
In the process (3), water cleaning may be further conducted after removing the pore-forming agent with the cleaning solution. The temperature in the water cleaning may be selected from a temperature range equal to or higher than 25° C. and equal to or lower than 60° C., equal to or higher than 30° C. and equal to or lower than 55° C., or equal to or higher than 35° C. and equal to or lower than 50° C. By the process (3), the first layer 132 containing no pore-forming agent can be obtained.
In the process (4), the stretched first layer 132 may be annealed (thermally fixed). In the first layer 132 after stretching, a region where oriented crystallization has occurred due to stretching and an amorphous region are mixed. Annealing causes reconstruction of amorphous parts (clustering) and eliminates mechanical nonuniformity in a micro area.
The annealing temperature can be selected from the range equal to or higher than (Tm-30° C.) and lower than Tm, equal to or higher than (Tm-20° C.) and lower than Tm, or equal to or higher than (Tm-10° C.) and lower than Tm, where a melting point of the ultrahigh-molecular weight polyolefin is set to Tm in consideration of the mobility of the polyolefin molecule. This eliminates mechanical nonuniformity and prevents the pores from being clogged by melting.
As a method of improving the values of the tearing strength and the tensile elongation of the first layer 132 in the present invention, (a) improving the internal uniformity of the first layer 132, (b) reducing the proportion of the skin layer on the surface of the first layer 132, or (c) reducing the difference in crystal orientation in the TD direction and the MD direction of the first layer 132, can be exemplified.
As a method of improving the internal uniformity of the first layer 132, a method of removing the aggregate in the mixture using the metallic mesh from the mixture obtained by kneading the raw material of the first layer 132 in the process (1) is exemplified. By removing the aggregate, it is considered that the internal uniformity of the obtained first layer 132 is improved and the first layer 132 becomes locally difficult to tear and its tearing strength is improved. In addition, since the aggregate in the polyolefin resin composition obtained by the process (1) decreases, it is preferable that the mesh of the metallic mesh is fine.
The rolling in the process (2) generates a skin layer on the surface of the obtained first layer 132. Since the skin layer is fragile to an external impact, the first layer 132 is weak against tearing and its tearing strength is reduced if the proportion occupied by the skin layer is large. As a method for reducing the proportion of the skin layer in the first layer 132, it is exemplified that a sheet to be a target of the step (3) becomes a single layer sheet.
It is considered that, due to the small difference in crystal orientation between the TD direction and the MD direction in the first layer 132, the first layer 132 becomes uniform in elongation against impacts and tension from the outside and becomes difficult to split. As a method of reducing the difference in crystal orientation in the TD direction and the MD direction in the first layer 132, rolling with a thick film thickness in the step (2) can be exemplified. It is thought that when rolled with a thin film thickness, the obtained porous film has a very strong orientation in the MD direction and has high strength against impacts in the TD direction, but when it begins to split it tears in the orientation direction (MD direction) at once. In other words, It is believed that when rolling with a thick film thickness, the rolling speed increases, the crystal orientation in the MD direction decreases, the difference in crystal orientation in the TD direction and the MD direction decreases, and the obtained first layer 132 does not tear at a stretch after it begins to tear, and its tensile elongation value improves.
As described above, the first layer 132 according to the present embodiment has a tensile elongation value equal to or longer than 0.5 mm because the difference in crystal orientation between the TD direction and the MD direction is small. In other words, the first layer 132 has a good balance of crystal orientation in the TD direction and the MD direction. Due to this, the first layer 132 has a good pin-releasability which serves as a measure of ease of pulling out the pin from the first layer 132 wound around the pin as a core. Therefore, the separator 130 including the first layer 132 can be suitably used for the production of a wound secondary battery such as cylindrical or square, etc. by manufacturing with an assembly method including the step of superposing the separator 130 and the positive and negative electrodes and winding on a pin.
In addition, the amount of extension of the separator 130 is preferably less than 0.2 mm, more preferably less than 0.15 mm, and still more preferably less than 0.1 mm. If the pin-releasability is poor, when removing the pin at the time of manufacturing the battery, the force is concentrated between the base and the pin, and the separator 130 may be damaged. Further, if the amount of extension of the separator 130 is large, the positions of the electrode and the separator 130 may be shifted at the time of battery manufacture, which may cause problems in manufacturing.
Through the above steps, the first layer 132 can be obtained which can suppress an increase in internal resistance when charging and discharging are repeated, and can suppress the occurrence of an internal short circuit against an external impact.
In the present embodiment, an embodiment in which the separator 130 has the porous layer 134 in addition to the first layer 132 is explained.
As described in the First Embodiment, the porous layer 134 may be disposed on one side or both sides of the first layer 132 (see
The porous layer 134 is insoluble in the electrolyte solution 140 and is preferred to include a material chemically stable in a usage range of the second battery 100. As such a material, it is possible to represent a polyolefin such as polyethylene, polypropylene, polybutene, poly(ethylene-co-propylene); a fluorine-containing polymer such as poly(vinylidene fluoride) (PVDF), polytetrafluoroethylene, poly(vinylidene fluoride-co-hexafluoropropylene), poly(tetrafluoroethylene-co-hexafluoropropylene), polyvinylidene fluoride and polytetrafluoroethylene; a fluorine-containing polymer such as vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer; an aromatic polyamide (aramide); rubber such as poly(styrene-co-butadiene) and a hydride thereof, a copolymer of methacrylic esters, a poly(acrylonitrile-co-acrylic ester), a poly(styrene-co-acrylic ester), ethylene-propylene rubber, and poly(vinyl acetate); a polymer having a melting point and a glass-transition temperature of 180° C. or more, such as poly(phenylene ether), a polysulfone, a poly(ether sulfone), polyphenylenesulfide, a poly(ether imide), a polyamide-imide, a polyether-amide, and a polyester; a water-soluble polymer such as poly(vinyl alcohol), poly(ethylene glycol), a cellulose ether, sodium alginate, poly(acrylic acid), polyacrylamide, poly(methacrylic acid); and the like.
As an aromatic polyamide, poly(paraphenylene terephthalamide), poly(metaphenylene isophthalamide), poly(parabenzamide), poly(metabenzamide), poly(4,4′-benzanilide terephthalamide), poly(paraphenylene-4,4′-biphenylenecarboxylic amide), poly(metaphenylene-4,4′-biphenylenecarboxilic amide), poly(paraphenyelnee-2,6-natphthalenedicarboxlic amide), poly(metaphenyelnee-2,6-natphthalenedicarboxlic amide), poly(2-chloroparaphenylene terephthalamide), a copolymer of paraphenylene terephthalamide with 2,6-dichloroparaphenylene terephthalamide, a copolymer of metaphenylene terephthalamide with 2,6-dichloroparaphenylene terephthalamide, and the like are represented, for example.
The porous layer 134 may include a filler. A filler consisting of an organic substance or an inorganic substance is represented as a filler. A filler called a filling agent and consisting of an inorganic substance is preferred. A filler consisting of an inorganic oxide such as silica, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, zeolite, aluminum hydroxide, boehmite, and the like is more preferred, at least one kind of filler selected from a group consisting of silica, magnesium oxide, titanium oxide, aluminum hydroxide, boehmite, and alumina is further preferred, and alumina is especially preferred. Alumina has a number of crystal forms such as α-alumina, β-alumina, γ-alumina, θ-alumina, and the like, and any of the crystal forms can be appropriately used. Among them, α-alumina is most preferable due to its particularly high thermal stability and chemical stability. Just one kind of filler may be used, or two or more kinds of filler may be combined in the porous layer 134.
No limitation is provided to a shape of the filler, and the filler may have a sphere shape, a cylindrical shape, an elliptical shape, a gourd shape, and the like. Alternatively, a filler in which these shapes are mixed may be used.
When the porous layer 134 includes the filler, an amount of the filler to be included may be equal to or larger than 1 vol % and equal to or smaller than 99 vol % or equal to or larger than 5 vol % and equal to or smaller than 95 vol % with respect to the porous layer 134. The aforementioned range of the amount of the filler to be included prevents the space formed by contact between the fillers from being closed by the material of the porous layer 134, which leads to sufficient ion permeability and allows its weight per unit area to be adjusted.
A thickness of the porous layer 134 can be selected from a range equal to or larger than 0.5 μm and equal to or smaller than 15 μm or equal to or larger than 2 μm and equal to or smaller than 10 μm. Hence, when the porous layers 134 are formed on both sides of the first layer 132, a total thickness of the porous layers 134 may be selected from a range equal to or larger than 1.0 μm and equal to or smaller than 30 μm or equal to or larger than 4 μm and equal to or smaller than 20 μm.
When the total thickness of the porous layers 134 is arranged to be equal to or larger than 1.0 μm, internal short-circuits caused by damage to the secondary battery 100 can be more effectively prevented. The total thickness of the porous layers 134 equal to or smaller than 30 μm prevents an increase in permeation resistance of the carrier ions, thereby preventing deterioration of the positive electrode 110 and a decrease in rate property resulting from an increase in permeation resistance of the carrier ions. Moreover, it is possible to avoid an increase in distance between the positive electrode 110 and the negative electrode 120, which contributes to miniaturization of the secondary battery 100.
The weight per unit area of the porous layer 134 may be selected from a range equal to or more than 1 g/m2 and equal to or less than 20 g/m2 or equal to or more than 2 g/m2 and equal to or less than 10 g/m2. This range increases an energy density per weight and energy density per volume of the secondary battery 100.
A porosity of the porous layer 134 may be equal to or more than 20 vol % and equal to or less than 90 vol % or equal to or more than 30 vol % and equal to or less than 80 vol %. This range allows the porous layer 134 to have sufficient ion permeability. An average porous diameter of the pores included in the porous layer 134 may be selected from a range equal to or larger than 0.01 μm and equal to or smaller than 1 μm or equal to or larger than 0.01 μm and equal to or smaller than 0.5 μm, by which a sufficient ion permeability is provided to the secondary battery 100 and the shutdown function can be improved.
A gas permeability of the separator 130 including the aforementioned first layer 132 and the porous layer 134 may be equal to or higher than 30 s/100 mL and equal to or lower than 1000 s/100 mL or equal to or higher than 50 s/100 mL and equal to or lower than 800 s/100 L in a Gurley value, which enables the separator 130 to have sufficient strength, maintain a high shape stability at a high temperature, and possess sufficient ion permeability.
When the porous layer 134 including the filler is prepared, the aforementioned polymer or resin is dissolved or dispersed in a solvent, and then the filler is dispersed in this mixed liquid to form a dispersion (hereinafter, referred to as a coating liquid). As a solvent, water; an alcohol 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,N-dimethylformamide; and the like are represented. Just one kind of solvent may be used, or two or more kinds of solvents may be used.
When the coating liquid is prepared by dispersing the filler to the mixed liquid, a mechanical stirring method, an ultrasonic dispersing method, a high-pressure dispersion method, a media dispersion method, and the like may be applied. In addition, after the filler is dispersed in the mixed liquid, the filler may be subjected to wet milling by using a wet-milling apparatus.
An additive such as a dispersant, a plasticizer, a surfactant, or a pH-adjusting agent may be added to the coating liquid.
After the preparation of the coating liquid, the coating liquid is applied on the first layer 132. For example, the porous layer 134 can be formed over the first layer 132 by directly coating the first layer 132 with the coating liquid by using a dip-coating method, a spin-coating method, a printing method, a spraying method, or the like and then removing the solvent. Instead of directly applying the coating liquid over the first layer 132, the porous layer 134 may be transferred onto the first layer 132 after being formed on another supporting member. As a supporting member, a film made of a resin, a belt or drum made of a metal may be used.
Any method selected from natural drying, fan drying, heat drying, and vacuum drying may be used to remove the solvent. Drying may be conducted after substituting the solvent with another solvent (e.g., a solvent with a low boiling point). When heating, drying may be carried out at 10° C. or higher and 120° C. or lower or at 20° C. or higher and 80° C. or lower. This temperature range avoids a reduction in gas permeability caused by shrinkage of the pores in the first layer 132.
A thickness of the porous layer 134 can be controlled by a thickness of the coating film in a wet state after coating, an amount of the filler included, a concentration of the polymer and the resin, and the like.
An example for preparing the separator 130 is described below.
To a mixture of 68.5 wt % of ultrahigh-molecular weight polyethylene powder (GUR4032 manufactured by Ticona) and 31.5 wt % of polyethylene wax (FNP-0115, manufactured by Nippon Seiro Co. Ltd.) having a weight-average molecular weight of 1000, 0.4 wt % of an antioxidant (Irg1010, manufactured by CIBA Speciality Chemicals), 0.1 wt % of an antioxidant (P168 manufactured by CIBA Speciality Chemicals®), and 1.3 wt % of sodium stearate with respect to 100 weight portions of the summation of the ultrahigh-molecular weight polyethylene and the polyethylene wax were added, these were mixed as a powder using a Henschel mixer at a rotational speed of 440 rpm for 70 seconds. Next, calcium carbonate (manufactured by Maruo Calcium Co. LTD.) with an average pore diameter of 0.1 μm was further added so that its proportion to the entire volume is 38 vol %, these were mixed using a Henschel mixer at a rotational speed of 440 rpm for 80 seconds. At that time, the light bulk density of the powder was about 500 g/L. The obtained mixture was melt-kneaded while being melted with a twin-screw kneader, and then filtered with a 300-mesh metal mesh to obtain a polyolefin-resin composite. This mixture was rolled using a pair of rolling rollers having a surface temperature of 150° C., the mixture was cooled stepwise while being drawn with a winding roller different in speed from the rolling rollers (drawing ratio (winding speed/rolling speed)=1.4), resulting in a single-layered sheet.
This sheet was dipped in hydrochloric acid aqueous solution (4 mol/L hydrochloric acid, 0.5 wt % nonionic surfactant) to remove calcium carbonate and sequentially stretched to 7.0 times in the TD direction at 100° C., and annealed at 123° C. (a melting temperature of 133° C.-10° C. of a polyolefin resin contained in the sheet) to obtain the separator 130 (first layer 132).
70 wt % of ultrahigh-molecular weight polyethylene powder (GUR4032, manufactured by Ticona), 30 wt % of polyethylene wax (FNP-0115, manufactured by Nippon Seiro Co., Ltd.) with a weight average molecular weight of 1000, when the total of this ultrahigh-molecular weight polyethylene and polyethylene wax set to 100 weight portions, an antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals) 0.4 wt %, (P168 manufactured by Ciba Specialty Chemicals) 0.1 wt %, 1.3 wt % of sodium stearate were added, these were mixed as a powder using a Henschel mixer at a rotational speed of 440 rpm for 70 seconds. Next, calcium carbonate (manufactured by Maruo Calcium Co. LTD.) with an average pore diameter of 0.1 μm was further added so that its proportion to the entire volume is 38 vol %, these were mixed using a Henschel mixer at a rotational speed of 440 rpm for 80 seconds. At that time, the light bulk density of the powder was about 500 g/L. The obtained mixture was melt-kneaded with a twin-screw kneader, and passed through a 200-mesh metal mesh to obtain a polyolefin resin composition. The polyolefin resin composition is rolled with a pair of rolls having a surface temperature of 150° C., and is gradually cooled while being pulled by rolls having different speed ratios, and 1.4 times of draw ratio (winding roll speed/rolling roll speed) to produce a single-layered sheet having a thickness of about 41 μm.
The sheet is immersed in a hydrochloric acid aqueous solution (4 mol/L of hydrochloric acid, 0.5 wt % of a nonionic surfactant) to remove calcium carbonate, and subsequently stretched in TD by 6.2 times at 100° C., and annealed at 120° C. (melting point 133° C.-13° C. of the polyolefin resin contained in the sheet) to obtain a separator 130 (first layer 132) of Example 2.
An Example of the preparation of a separator used as a Comparative Example will be described below.
To a mixture of 70 wt % of ultrahigh-molecular weight polyethylene powder (GUR4032 manufactured by Ticona) and 30 wt % of polyethylene wax (FNP-0115, manufactured by Nippon Seiro Co. Ltd.) having a weight-average molecular weight of 1000, 0.4 wt % of an antioxidant (Irg1010, manufactured by CIBA Speciality Chemicals), 0.1 wt % (P168 manufactured by CIBA Speciality Chemicals®), and 1.3 wt % of sodium stearate with respect to 100 weight portions of the summation of the ultrahigh-molecular weight polyethylene and the polyethylene wax were added, and calcium carbonate (manufactured by Maruo Calcium Co. LTD.) with an average pore diameter of 0.1 μm was added at the same time so that its proportion to the entire volume is 38 vol %. These materials were mixed with a Henschel mixer at a rotational speed of 440 rpm for 150 seconds. At that time, the light bulk density of the powder was about 350 g/L. The obtained mixture was kneaded while being melted, and then filtered with a 200-mesh metal mesh to obtain a polyolefin-resin composite. This mixture was rolled using a pair of rollers having a surface temperature of 150° C. and cooled stepwise while being drawn with a winding roller different in speed from the rollers (drawing ratio (winding speed/rolling speed)=1.4), resulting in a sheet with a thickness of 29 μm.
The sheet is immersed in a hydrochloric acid aqueous solution (4 mol/L of hydrochloric acid, 0.5 wt % of a nonionic surfactant) to remove calcium carbonate, and subsequently stretched in TD by 6.2 times at 100° C., the separator 130 (first layer 132) of Comparative Example 1 was obtained by annealing at 115° C. (melting point of 133° C.-18° C. of the polyolefin resin contained in the sheet).
A method for fabricating the secondary batteries including the separators of the Examples 1 and 2 and Comparative Example 1 are described below.
A commercially available positive electrode manufactured by applying a stack of LiNi0.5Mn0.3Co0.2O2/conductive material/PVDF (weight ratio of 92/5/3) on an aluminum foil was processed. Here, LiNi0.5Mn0.3Co0.2O2 is an active-substance layer. Specifically, the aluminum foil was cut so that a size of the positive-electrode active-substance layer is 45 mm×30 mm and that a portion with a width of 13 mm, in which the positive-electrode active-substance layer is not formed, was left in a periphery and was used as a positive electrode in the following fabrication process. A thickness, a density, and a positive-electrode capacity of the positive-electrode active-substance layer were 58 μm, 2.50 g/cm3, and 174 mAh/g, respectively.
A commercially available negative electrode manufactured by applying graphite/poly(styrene-co-1,3-butadiene)/carboxymethyl cellulose sodium salt (weight ratio of 98/1/1) on a copper foil was used. Here, the graphite functions as a negative-electrode active-substance layer. Specifically, the copper foil was cut so that a size of the negative-electrode active-substance layer is 50 mm×35 mm and that a portion with a width of 13 mm, in which the negative-electrode active-substance layer is not formed, was left in a periphery and was used as a negative electrode in the following fabrication process. A thickness, a density, and a negative-electrode capacity of the negative-electrode active-substance layer were 49 μm, 1.40 g/cm3, and 372 mAh/g, respectively.
The positive electrode, the separator, and the negative electrode were stacked in the order in a laminated pouch to obtain a stacked body. At this time, the positive electrode and the negative electrode were arranged so that the entire top surface of the positive-electrode active-substance layer overlaps with a main surface of the negative-electrode active-substance layer.
Next, the stacked body was arranged in an envelope-shaped housing formed by stacking an aluminum layer and a heat-seal layer, and 0.25 mL of an electrolyte solution was added into the housing. A mixed solution in which LiPF6 was dissolved at 1.0 mol/L in a mixed solvent of ethyl methyl carbonate, diethyl carbonate, and ethylene carbonate with a volume ratio of 50:20:30 was used as the electrolyte solution. The secondary battery was fabricated by heat-sealing the housing while reducing the pressure in the housing. A designed capacity of the secondary battery was 20.5 mAh.
The methods for evaluating the physical properties of the separators according to the Examples 1 and 2 and the Comparative Example 1 and the performance of the secondary batteries including the separators are described below.
The thickness was measured using a High-Resolution Digital Measuring Unit manufactured by Mitsutoyo Corporation.
Light bulk density was measured in accordance with JIS R9301-2-3.
About 50 mg of a separator was packed in an aluminum pan, and a DSC (Differential Scanning calorimetry) thermogram was measured at a temperature rising rate of 20° C./min using a Seiko Instruments differential scanning calorimeter EXSTAR 6000. The peak of the melting peak near 140° C. was obtained as the melting point Tm of the separator.
The dynamic viscoelasticity of the separator was measured under the conditions of a measurement frequency of 10 Hz and a measurement temperature of 90° C. using a dynamic viscoelasticity measurement apparatus itk DVA-225 manufactured by ITK Co., Ltd.
Specifically, a tensile force of 30 cN is applied to the test pieces obtained by cutting the separators of Examples 1 to 3 and Comparative Examples 1 and 2 into strips 5 mm wide in which the flow direction is the longitudinal direction, with the distance between chucks being 20 mm to measure the tan δ (MD tan δ) in the flow direction. Similarly, a tensile force of 30 cN was applied to a test piece cut into a strip of 5 mm wide in which the width direction is a longitudinal direction from the separator with a distance between chucks of 20 mm to measure tan (TD tan δ) in the longitudinal direction. The measurement was performed while raising the temperature from room temperature at a rate of 20° C./min, and the parameter X was calculated using the value of tan δ when the temperature reached 90° C.
The tearing strength of the porous film (first layer 132) was measured according to “JIS K 7128-2 Test method for tearing strength of a plastic film and sheet-Part 2: Elmendorf tear method”. The measuring equipment and conditions used were as follows:
Equipment: Digital Elmendorf tear tester (manufactured by Toyo Seiki Seisaku-sho, Ltd., SA-WP type);
Sample size: Rectangular test piece shape based on JIS standard;
Condition: flying angle: 68.4°, number of measurements n=5;
The sample used for evaluation is cut out so that the direction to be torn at the time of measurement is perpendicular to the flow direction when the porous film to be measured is formed (hereinafter referred to as the TD direction). In addition, the measurement is carried out in a state where four to eight sheets of the porous film are stacked, and the measured tear load value is divided by the number of porous films to calculate the tearing strength per porous film. Thereafter, the tearing strength T per 1 μm thickness of the porous film was calculated by dividing the tearing strength per porous film by the thickness per film.
Specifically, the tearing strength T was measured according to the following equation.
T=(F/d)
(In the expression, T: fracturing strength (mN/μm)
F: Tear load (mN/piece)
d: Film thickness (μm/sheet))
The average value of the tearing strength at 5 points obtained after 5 measurements was taken as the true tearing strength (however, it was calculated excluding data with a deviation equal to or more than ±50% from the average value).
The tearing strength of the porous film was measured based on “JIS K 7128-3 Test method for tearing strength of a plastic film and sheet—part 3: right-angled tear method” to create a load-tensile elongation curve. Thereafter, the value E of tensile elongation was calculated from the load-tensile elongation curve. In the measurement of tearing strength based on the right-angled tearing method, the measuring equipment and measurement conditions used are as follows:
Equipment: Universal material tester (manufactured by INSTRON, model 5582);
Sample size: Test piece shape based on JIS standard;
Conditions: tensile speed 200 mm/min, measurement number n=5 (however, except for the number of times the data with a deviation equal to or more than ±50% from the average value is excluded);
The sample used for evaluation was cut out so that the tearing direction was the TD direction. That is, the sample was cut out so as to have a long shape in the MD direction.
From the load-tensile elongation curve prepared based on the results of the above measurements, the value E (mm) of tensile elongation from the time the load reaches the maximum load until it attenuates to 25% of the maximum load was calculated with the method shown below.
A load-tension elongation curve was created, and the maximum load (load at the start of tearing) was defined as X (N). 0.25 times the value of X (N) was defined as Y (N). The value of tensile elongation until X attenuates to Y was defined as E0 (mm) (see the description of
Each of the separators obtained in Examples and Comparative Examples was cut into a size of 13 cm×13 cm, and a withstand voltage test was performed using a withstand voltage tester TOS-9201 manufactured by Kikusui Electronics. The test conditions of the withstand voltage test were as follows:
(i) The separator as the test object was sandwiched between an upper columnar electrode (φ25 mm) and a lower columnar electrode (φ75 mm).
(ii) A voltage is applied between the electrodes while increasing the voltage to 800 V at a voltage-increase rate of 40 V/s, and then this voltage (800 V) was maintained for 60 seconds.
(iii) The withstand voltage test was performed to 10 positions in the same separator with the same method as those described in the steps (i) and (ii).
(iv) After the voltage resistance test described in the step (iii), the separator was placed on a thin-type trace stage equipped with a light source, and photo images were captured from a 20 to 30 cm height over the separator using a digital steel camera in a 4:3 steel-image mode (5M, 2,592×1,944), while irradiating the separator with light from a back surface, so that the 10 measuring points are entirely included in the image. Cyber-Shot DSC-W730 having approximately 16,100,000 pixels (manufactured by Sony Corporation) was used as the digital steel camera, and Treviewer A4-100 (manufactured by Trytec Japan Co., LTD) was used as the thin-type trace stage.
(v) The image data captured in the step (iv) was loaded in a personal computer and the number of voltage resistance defects was determined with a free software ImageJ provided by the National Institutes of Health (NIH) to calculate the number of the defect points. A case where the number of defect points is less than 10 was evaluated as “+”, a case where the number of defect points is equal to or more than 10 and less than 30 was evaluated as “±”, and a case where the number of defect points is more than 30 was evaluated as “−”. Note that a plurality of defect points may be generated in every measurement of the step (ii).
The separator (porous film) in Examples and Comparative Examples was cut in a TD direction of 62 mm×MD direction of 30 cm, put on a 300 g weight, and wound five times around a stainless steel ruler (Shinwa Co., Ltd. product number: 13131). At this time, the separator was wound so that the TD of the separator and the longitudinal direction of the stainless steel ruler became parallel. Subsequently, at a speed of about 8 cm/sec, the stainless steel ruler was pulled out and the width of the separator was measured with a caliper. Before and after the stainless steel ruler was pulled out, the width in the TD direction of the 5-rolled part separator was measured with a caliper and the amount of change (mm) was calculated. The amount of change indicates the amount of expansion in the drawing direction when the separator starts to move in the drawing direction of the stainless steel ruler due to the frictional force between the stainless steel ruler and the separator, and the separator is deformed in a spiral.
The amount of increase in internal resistance before and after charge and discharge cycles of the secondary battery manufactured by the above-described method was determined in the following manner. 1 cycle at a temperature range of 25° C., a voltage range of 4.1 to 2.7 V, and a current value of 0.2 C (a current value for discharging the rating capacity by the discharge capacity at a 1 hour rate is defined as 1 C, the same shall apply hereinafter) of charge and discharge were performed on the secondary battery for four cycles. After that, a voltage was applied to the secondary battery with an amplitude of 10 mV at room temperature 25° C. using an LCR meter (manufactured by HIOKI E.E. CORPORATION, chemical impedance meter: type 3532-80), and the AC impedance of the secondary battery was measured.
From the measurement results, the series equivalent resistance value (Rs1: Ω) at a frequency of 10 Hz and the series equivalent resistance value (Rs2: Ω) when the reactance is 0 were read, and the resistance value (R1: Ω) that is the difference between these was calculated according to the following equation:
R
1(Ω)=Rs1−Rs2
Here, Rs1 mainly represents the total resistance of a resistance (liquid resistance) when Li+ ions pass through the separator, the conductive resistance in the positive and negative electrodes, and the resistance of ions moving in the interface between the positive electrode and the electrolyte. Rs2 mainly indicates liquid resistance. Therefore, R1 represents the total of the conduction resistance in the positive and negative electrodes and the resistance of ions moving in the interface between the positive and negative electrodes and the electrolyte.
100 cycles of a charge and discharge cycle test for a secondary battery after measurement of a resistance value R1 with a constant current of 55° C., voltage range of 4.2 to 2.7 V, charge current value of 10 and discharge current value of 10 C as one cycle. Thereafter, a voltage was applied to the secondary battery with an amplitude of 10 mV at a room temperature of 25° C. using an LCR meter (manufactured by HIOKI E.E. CORPORATION, Chemical Impedance Meter: type 3532-80) to measure the AC impedance of the secondary battery.
Similar to the calculation of the resistance value R1, the series equivalent resistance value (Rs3: Ω) at a frequency of 10 Hz and the series equivalent resistance (Rs4: Ω) when the reactance is 0 were read from the measurement result, and the resistance value (R2: Ω) indicating the sum of the conduction resistance of the positive and negative electrodes after 100 cycles and the resistance of ions moving through the interface between the positive and negative electrodes and the electrolyte was calculated according to the following equation:
R
2(Ω)=Rs3−Rs4
Subsequently, the amount of increase in internal resistance before and after charge and discharge cycles was calculated according to the following equation:
Amount of increase in internal resistance before and after charge/discharge cycle [Ω]=R2−R1
The test results of Examples 1 and 2 and Comparative Example 1 are shown in
In Examples 1 and 2 in which the parameter X is equal to or less than 20, the amount of increase in internal resistance before and after the charge and discharge cycle test is suppressed to equal or be less than 0.8Ω, which shows excellent results as compared with Comparative Example 1. When the anisotropy of tan δ is small, the separator 130 is uniformly deformed according to the expansion and contraction of the electrode in the charge and discharge cycle test, and the anisotropy of the stress generated in the separator 130 is also reduced. Therefore, since it becomes difficult for omission of an electrode active material etc. to occur, it is thought that the increase amount of internal resistance is suppressed.
In the separators of Examples 1 and 2, the tearing strength of the first layer 132 measured by the Elmendorf tearing method (in accordance with JIS K 7128-2) is equal to or more than 1.5 mN/μm, and in the load-tensile elongation curve in the tearing strength measurement (in accordance with JIS K 7128-3) of the first layer 132 by the right-angled tearing method, it was shown that the tensile elongation value was equal to or more than 0.5 mm from when the load reaches the maximum load until it attenuates to 25% of the maximum load.
Therefore, the separators of Embodiments 1 and 2 of the present invention can suppress an increase in internal resistance when charging and discharging are repeated, and can suppress the occurrence of an internal short circuit against an external impact.
On the other hand, in the separator of Comparative Example 1, the above-described characteristics do not satisfy the above-described range. Therefore, the separator of Comparative Example 1 cannot sufficiently suppress the increase in internal resistance when charging and discharging are repeated. Moreover, the separator of the comparative example 1 cannot fully suppress the occurrence of an internal short circuit against the external impact.
The aforementioned modes described as the embodiments of the present invention can be implemented by appropriately combining with each other as long as no contradiction is caused. Furthermore, any mode which is realized by persons ordinarily skilled in the art through the appropriate addition, deletion, or design change of elements is included in the scope of the present invention as long as it possesses the concept of the present invention.
It is understood that another effect different from that provided by the modes of the aforementioned embodiments is achieved by the present invention if the effect is obvious from the description in the specification or readily conceived by persons ordinarily skilled in the art.
1: SUS plate, 2: Nail, 3: Resistance meter, 4: Negative electrode sheet, 100: Secondary battery, 110: Positive electrode, 112: Positive-electrode current collector, 114: Positive-electrode active-substance layer, 120: Negative electrode, 122: Negative-electrode current collector, 124: Negative-electrode active-substance layer, 130: Separator, 132: First layer, 134: Porous layer, 140: Electrolyte solution
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/081501 | 10/24/2016 | WO | 00 |
