JP5551525B2 - Separator made of ultrafine nonwoven fabric - Google Patents

Description

  In the present invention, for example, in an electrochemical device such as a lithium ion secondary battery or an aluminum electrolytic capacitor, an electric double layer capacitor, or a lithium ion capacitor, the positive electrode material and the negative electrode material are isolated, and the electrolyte or ions in the electrolytic solution pass therethrough. And an electrochemical device such as a capacitor and a capacitor using the separator.

  Lithium ion secondary batteries, aluminum electrolytic capacitors, electric double layer capacitors, and lithium ion capacitors have already been put into practical use as power sources and charge / discharge devices for portable electronic devices and large devices. It is highly expected to increase capacity and withstand long-term use. In order to meet this expectation, there is a great expectation for improvement in technology and quality with respect to a member, for example, a separator as a material for a partition between electrodes.

  General characteristics required for separators include: (1) isolation of electrode material, (2) good electrolyte and ion permeability when the electrolyte is retained, (3) electrical insulation, and (4) chemistry for the electrolyte. And (5) sufficient mechanical strength, (6) sufficient wettability with respect to the electrolytic solution, and sufficient retention of the electrolytic solution. In addition, from the expectation for the miniaturization and weight reduction of the electrochemical device, it is necessary that the separator has the above-mentioned required characteristics even if it is made thin.

  Conventionally, as a separator for a lithium ion secondary battery, a porous sheet formed using a polyolefin polymer such as polyethylene or polypropylene (Patent Document 1: JP-A-63-273651), the polyolefin polymer Nonwoven fabric sheeted using fibers (Patent Document 2: Japanese Patent Laid-Open No. 2001-11761) and non-woven fabric sheeted using nylon fibers (Patent Document 3: Japanese Patent Laid-Open No. 58-147756) are widely used. Yes. This type of separator is used in a battery by stacking one layer or a plurality of layers or winding it in a roll.

  These porous sheets and non-woven fabrics have good physical properties as separators, but they can always cope with the increase in capacity and output required for lithium ion secondary batteries for electric vehicles. It is not possible. That is, a separator material having a lower resistance is required for increasing the capacity and output of a battery. Further, for applications that require higher safety, separator materials that are excellent in heat resistance and excellent in chemical stability at high temperatures are required.

  In order to solve these problems, a separator using fibrids or short fibers excellent in heat resistance, such as a separator made of a fiber sheet containing para-type aramid fibrids (Patent Document 4: Japanese Patent Application Laid-Open No. 2007-242584) is proposed. Has been. Although these separators contain aramid fibrids, their heat resistance is greatly improved. However, the ion permeability required for separators to increase the capacity and output of batteries, shorten the process time, and reduce battery dry-up. Therefore, the liquid retention of the electrolyte solution required for this is not sufficient.

  In addition, a separator (Patent Document 5: Japanese Patent Laid-Open No. 2006-59717) characterized by containing heat-resistant fibers having a fiber diameter of 5 μm or less has been proposed. In the examples, a polyimide nonwoven fabric produced by a wet papermaking method is used. Only examples of “paper” made from sheets, so-called short fibers, are shown.

  Patent Document 6 (WO 2005/057689 pamphlet) describes an electrical / electronic component characterized in that the increase rate of the internal resistance value (= Macmillan number × thickness) after heat treatment is within 25%. The separator for is shown. However, only the heat resistance index is shown, and there is no stipulation regarding the crystallinity, fiber diameter, etc. of the fibers constituting the woven fabric, non-woven fabric, paper, etc. constituting the separator.

JP-A 63-273651 JP 2001-11761 A Japanese Patent Laid-Open No. 58-147756 JP2007-242584A JP 2006-59717 A International Publication No. 2005/057689 Pamphlet

  In view of the above problems, an object of the present invention is to provide an ultrafine fiber nonwoven fabric separator that has low resistance, excellent electrolyte retention, and excellent handling properties in addition to heat resistance, chemical resistance, and insulation. It is in.

  As a result of intensive research, the present inventors have solved the above problems by using a nonwoven fabric separator mainly composed of an aramid fiber having a specific fiber diameter and a specific crystallinity or crystal size. As a result, the present invention has been completed.

Thus, according to the present invention,
A separator for an electrochemical device consisting of a nonwoven fabric comprising aramid fibers, 55% degree of crystallinity 49.4～ of the aramid fibers obtained from X-ray diffraction also is properly in crystal size 19.0~ 30 Å A separator characterized by being,
as well as,
A lithium ion secondary battery, an electric double layer capacitor, an aluminum electrolytic capacitor, and a lithium ion capacitor, including the separator
Is provided.

Since the separator of the present invention is made of an aramid fiber, it is excellent in heat resistance and can be easily made into an ultrafine fiber diameter, so that it is dense and can suppress a short circuit. In addition, the non-woven fabric structure has low resistance and excellent electrolyte retention, which is advantageous for increasing the battery capacity and output.
Further, by having a specific crystallinity or crystal size, the electrolyte solution retention is high. For example, when used as a separator for a lithium secondary battery, there are advantages such as excellent cycle characteristics. Furthermore, it is easy to handle when used as a separator because it has flexibility and is easy to bend.

Hereinafter, the present invention will be described in detail.
In the present invention, the aramid polymer used for the fibers constituting the separator is excellent in heat resistance, flame retardancy, chemical resistance and insulation, and one or more divalent aromatic groups are directly amides. A polymer linked by a bond, wherein the aromatic group may be one in which two aromatic rings are linked by an oxygen, sulfur or alkylene group. In addition, these divalent aromatic groups may include a lower alkyl group such as a methyl group or an ethyl group, a halogen group such as a methoxy group, or a chloro group. Furthermore, these amide bonds are not limited and may be either para-type or meta-type.

  As such an aramid polymer, polyparaphenylene terephthalamide, copolyparaphenylene-3,4'oxydiphenylene-terephthalamide, polymetaphenylene isophthalamide, polymetaphenylene terephthalamide and the like are preferably selected.

  Since the separator of the present invention contains an aramid polymer, it has high heat resistance. Therefore, for example, when used as a separator for a lithium ion battery, even if the internal temperature of the battery reaches a high temperature of 200 ° C. or more due to abnormal heat generation, the separator does not contract and it is possible to prevent a short circuit between the electrodes due to the contraction of the separator. When used in applications where moisture drying in activated carbon is important, such as for electric double layer capacitors, the element drying temperature can be raised, so that drying can be performed efficiently. In addition, an electrochemical device that can be used at a higher temperature than before can be produced.

  The separator of the present invention has a non-woven structure, so that it has higher air permeability than polyolefin microporous membranes conventionally used as separators for lithium ion secondary batteries, and therefore has high ionic conductivity and low resistance. It becomes. That is, a lithium ion secondary battery having high output density and energy density suitable for high-rate discharge, or an electric double layer capacitor having a lower resistance or a lower profile than conventional ones can be produced.

  Moreover, electrolyte solution retention property becomes high by having a nonwoven fabric structure, and the process time by electrolyte solution impregnation time shortening can be shortened. In addition, it can be expected to improve the cycle characteristics, durability and safety of the device by reducing the dry-up speed of the electrolyte.

  As a method for producing the nonwoven fabric, a method of producing a nonwoven fabric by spinning and direct connection, a dry blending method in which a short fiber and a fibrid are dry-blended and then a sheet is formed using an air stream, or a short fiber and a fibrid are once submerged in water Examples include a wet papermaking method in which the paper is dispersed and manufactured on a paper machine. In the case of a method of producing a nonwoven fabric by direct coupling with spinning, it is preferable because a separator having less fuzz on the fracture surface can be obtained by entanglement with continuous fibers.

  The fiber diameter of the aramid fiber constituting the separator of the present invention is preferably 5 μm or less, more preferably 2 μm or less, in order to reduce the pore diameter of the separator and to enable thinning. More preferably, it is 1 μm or less. By being made of fine fibers, it is possible to obtain a separator excellent in short-circuit prevention even in a thin leaf.

  The aramid fiber constituting the separator of the present invention can be obtained by spinning an aramid polymer solution. As a preferred method for producing small-diameter aramid fibers, a method of applying explosive spinning technology (WO 2002/052070 pamphlet) for bursting a polymer solution into fine fibers and applying it to an aramid polymer, generally performed with a meltable polymer. Electrospinning described in Japanese Patent Application Laid-Open No. 2005-200779 and Japanese Patent Application Laid-Open No. 2006-336173, a method in which the melt blown technology is improved and effectively fined (US Pat. No. 6,013,223) is applied to solution spinning of aramid polymer Law.

By selecting an appropriate range from the above spinning conditions, selecting a non-woven fabric post-treatment condition from an appropriate range, and adjusting the crystallinity to an optimal range, a nonwoven fabric suitable for a separator can be obtained. it can. Specifically, the degree of crystallinity of the aramid fiber is 49.4 to 55 % by selecting the draw ratio of the fiber during spinning from an appropriate range, or by selecting the heat treatment condition of the nonwoven fabric from the appropriate range , or If the crystal size and 19.0~ 30 Å, it is particularly to handling, liquid retention excellent nonwoven.

  In the case of non-woven fabric made of aramid fibers having a degree of crystallinity higher than 55% or a crystal size grown larger than 30 mm, partly when laminated with other members at the time of electrochemical device production, or when lithium dendride occurs Stress concentration is likely to occur, and when used as a separator for a long period of time, microshorts are likely to occur.

Further, when the crystallinity of the aramid fiber is 49.4 to 55% , the affinity with the electrolytic solution is further increased, so that it is considered that the dry-up of the electrolytic solution can be further reduced. Moreover, the separator of the present invention is easy to handle when used as a separator because it has flexibility and is easy to bend by setting the crystallinity within a specific range.

The separator of the present invention may be a composite containing a fiber other than an aramid polymer and an inorganic material.
For example, as polymers other than aramid polymer, polyolefins such as polypropylene and polyethylene, polyester, nylon, vinyl chloride, polyphenylene sulfide, wholly aromatic polyester, polyparaphenylene benzobisoxazole, polyamide, semi-aromatic polyamide, polyimide, polyamideimide, Examples include melamine, polybenzimidazole, polyketone (polyetheretherketone, etc.), polyacrylonitrile, polyvinyl alcohol, polyacetal, polytetrafluoroethylene, polyvinylidene fluoride, other fluoropolymers, cellulose, cellulose modified products (carboxymethylcellulose, etc.), etc. be able to.

  Further, as inorganic materials, silica, alumina, titanium dioxide, barium titanate, alumina-silica composite oxide, silicon carbide, zirconia, glass, etc., clay particles such as talc, montmorillonite, boehmite, zeolite, apatite, kaolin, Mention may be made of substances derived from mineral resources such as mullite, spinel, olivine, sericite, bentonite and mica, or artificial products thereof.

The separator of the present invention may have a single layer structure or a multilayer structure composed of a layer containing the above polymer and inorganic material and a layer made of an aramid polymer.
By combining other components or forming a multilayer structure with other components, effects such as increasing the strength of the separator can be obtained. When the other component is a polyolefin, the polyolefin melts in a temperature range (about 100 to 160 ° C.) where an electrochemical reaction runs away in an electrochemical device such as a lithium ion secondary battery. And the abnormal electrochemical reaction can be suppressed.

Although the thickness of the separator of the present invention is appropriately selected depending on the type and application of the electrochemical device, it is preferably 5 to 200 μm, more preferably 10 to 100 μm, and 15 to 80 μm. Further preferred. Further, the porosity is preferably 30 to 80%, more preferably 50 to 75%. Here, the porosity is a value calculated from the basis weight M (g / cm 2), thickness T (μm), and polymer density D (g / cm 3) by the following formula.
Porosity (%) = [1- (M / T) / D] × 100

When the thickness of the separator and the porosity are within such ranges, a separator having a good balance between electrolyte solution retention and low resistance can be obtained.
The weight per unit area of the separator, that is, the weight of the unit area is not particularly limited as long as it is a range that functions as a partition wall between the electrodes, but is usually preferably 4 to 160 g / m2, and preferably 8 to 80 g / m2. It is more preferable that it is 10-65 g / m2.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples. Each item in the examples was measured by the following method.

<Intrinsic viscosity (IV)>
Dissolve the polymer in NMP at 100 mg / 20 mL and use an Ostwald viscometer 30
Measured at ° C.

<Average fiber diameter>
An arbitrary sample was obtained from the obtained fibers, and 50 fibers were scanned using a scanning electron microscope JS.
Observation and length measurement were performed with M6330F (manufactured by JEOL), and the average fiber diameter was calculated. The observation was performed at a magnification of 3,000 times.

<Thickness>
Ono Sokki Using a digital linear gauge DG-925 (measurement terminal diameter 1 cm), the thickness was measured at 20 arbitrarily selected locations, and the average value was obtained.

<Unit weight>
Measurement was performed according to the weight test method per unit area of JIS L1906.

<Air permeability (Gurley)>
The measurement was performed according to the air permeability test method (Gurley type method) of JIS L1906.

<Observation of fuzz>
The cross section when the separator was cut was lightly rubbed with a finger, and the presence or absence of fluffing and / or fluffing was observed visually and with a microscope.

<Measurement of crystallization size and crystallinity>
Using an X-ray diffractometer (D8 DISCOVER with GADDS Super Speed, manufactured by Bruker AXS), measurement in the range of 2θ = 10 to 40 ° was performed. At this time, the profile in all directions of the sample was measured. According to the method of Hindeleh et al. (AM Hideleh and D. J. Johnson, Polymer, 19, 27 (1978)), peak separation is performed based on the omnidirectional diffraction curve of commercially available metaaramid, and the highest intensity after separation is obtained. From the full width at half maximum of the peak (in the case of polymetaphenylene isophthalamide, around 2θ = 23.5 °), the crystal size (unit: Å) was calculated by the Scherrer equation shown below.
Crystal size = Kλ / (β × cos θ)
(Where K is a constant of 0.94, λ is the wavelength of the X-ray used, 1.54 mm (CuK _α- ray), β is the half-value width in radians of the reflection profile, the measured value is β _M , and the device constant is β _E was obtained from β = β _M −β _E. θ is the Bragg angle of the diffraction line.
The crystallinity was determined from the ratio of the crystalline peak intensity after the separation to the total peak intensity. The crystallinity peak was based on the peak position of the diffraction intensity curve of a commercially available aramid fiber that was highly crystallized.

<Liquid suction height>
In accordance with the water absorption rate measuring method (Byreck method) defined in JIS-L1907, the height of the propylene carbonate after 1 minute was measured.

<Battery evaluation test>
LiNi _1/3 Mn _1/3 Co _1/3 O2 (average particle size 6 μm) as the positive electrode active material is 89 wt%, graphite is 6 wt% as the conductive agent, and polyvinylidene fluoride is 5 wt% as the binder, Further, N-methyl-2-pyrrolidone as a solvent for dispersion was added and mixed to prepare a paste-like slurry. This slurry was applied to an aluminum foil (thickness: 15 μm) serving as a positive electrode current collector, dried, and then compression molded with a roller press to form a positive electrode.
Also, graphite (average particle size 20 μm) as a negative electrode active material is 90% by weight, polyvinylidene fluoride is 10% by weight as a binder, and N-methyl-2-pyrrolidone is added and mixed as a dispersion solvent. A pasty slurry was prepared. This slurry was applied to an electrolytic copper foil (thickness: 10 μm) serving as a negative electrode current collector, and after drying, compression molding was performed with a roller press to form a negative electrode.
Subsequently, the positive electrode and the negative electrode formed as described above are punched out to a predetermined size (about 30 mm × about 60 mm), laminated through the separators of the examples and comparative examples, and the tabs are bonded and the exterior is applied to obtain a laminate. Was made. This laminate was dried under reduced pressure at 80 ° C. for 8 hours. An electrolyte solution in which LiPF ₆ was added at a concentration of 1 mol / L to a mixed solvent of 30% by weight of propylene carbonate and 70% by weight of ethyl methyl carbonate was injected into this laminate. Thereafter, the liquid inlet of the exterior material was sealed to produce a single-layer laminate cell. The work after electrode drying was performed in a dry box having a dew point of −50 ° C. or lower.

Test 1 (impedance measurement):
The single-layer laminated cell produced as described above was fully charged at 20 ° C. under the conditions of a charging voltage of 4.2 V and a charging time of 17 hours. Thereafter, the charge was adjusted to 3.8 V, and AC impedance measurement was performed. The measurement was performed under the conditions of a measurement frequency of 1 kHz and an applied voltage of 10 mV.
Compared to the control product (polypropylene microporous membrane, manufactured by Celgard), the case where the impedance was equal was indicated by Δ, and the case where the impedance was low was indicated by ○.

Test 2 (cycle characteristics):
The single-layer laminate cell produced as described above was charged at 20 ° C. under the conditions of a charging voltage of 4.2 V and a charging time of 1.5 hours, and then discharged. This cycle was repeated to determine the 200th charge capacity retention rate with respect to the initial charge capacity.
The case where the capacity retention rate was 85% or more was rated as “◯”, the case where it was less than 85% and 80% or more as Δ, and the case where it was less than 80% as “X”.

<Electric double layer capacitor evaluation test>
A granular activated carbon, carbon black, and an N-methyl-2-pyrrolidone solution of polyvinylidene fluoride as a binder were mixed and kneaded to prepare a paste slurry. In addition, aluminum foil as a current collector, separators of Examples and Comparative Examples as separators, and tetraethylammonium tetrafluoroborate ((C ₂ H ₅ ) ₄ N · BF ₄ ) as electrolytes were dissolved in propylene carbonate. I prepared something.
Coin cell type electric double layer capacitors were prepared from these materials, and their internal resistance was measured. A case where the internal resistance was lower than that of the control product (cellulose paper, Nippon Advanced Paper Co., Ltd.) was evaluated as ◯.

[Examples 1 to 6, 9]
20 parts by weight of polymetaphenylene isophthalamide powder having an intrinsic viscosity (IV) = 1.35, produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863, is −10 ° C.
The slurry was suspended in 80 parts by weight of dimethylacetamide (DMAc) that had been cooled to 45 ° C., made into a slurry, and then heated to 45 ° C. to dissolve to obtain a transparent polymer solution.
The above polymer solution was supplied to the spinning device of Japanese Patent Application No. 2009-194917 using a gear pump, and spinning was performed at a spinning temperature of 35 ° C. Water was used as a coagulation liquid, sprayed onto the polymer solution after discharge, and the polymer solution was solidified to obtain continuous fibers. Further, a non-woven fabric having a fiber diameter shown in Table 1 was obtained by installing a supplementary belt below the spinning device and adjusting the belt conveyance speed while laminating continuous fibers.
The obtained nonwoven fabric was heat-treated with a metal calender roll at a temperature of 250 ° C. (linear pressure setting: 50 kg / cm). The linear pressure was arbitrarily adjusted by providing a clearance between the upper and lower rolls, and separators having thicknesses shown in Tables 1 and 2 were obtained.

[Example 7]
A non-woven fabric was prepared in the same manner as in the example except that a non-woven fabric was prepared using a water / DMAc mixed solution (mixing ratio 50/50) as a coagulating liquid, and a separator was obtained by performing the same heat treatment.

[Example 8]
The separator obtained in Example 1 was fixed and heat-treated at 250 ° C. for 10 minutes. The heat treatment was performed according to Japanese Patent Application Laid-Open No. 2007-84956.

[Comparative Example 1]
The separator obtained in Example 5 was fixed, and heat treatment was performed at 250 ° C. for 60 minutes in the same manner as in Example 8.

[Comparative Example 2]
In Example 1, a nonwoven fabric made of stretched fibers was produced by stretching the aramid fibers after discharge. In the stretching method, the coagulated yarn is stretched 3.4 times in a stretching bath made of a 30% by weight NMP aqueous solution at 40 ° C., then immersed in warm water at 70 ° C. for about 50 seconds, and then the surface temperature is 130. After drying along a roller of ° C., it was performed by a method of heat treatment 1.00 times with a hot plate having a surface temperature of 340 ° C.

[Comparative Example 3]
A polypropylene microporous membrane (Celgard TM2400, manufactured by Celgard) was used to evaluate the performance as a separator.

[Comparative Example 4]
A cellulose separator (TF4050, manufactured by Nippon Kogyo Paper Industries) was used to evaluate the performance as a separator.
Table 1 shows the basic characteristics and battery characteristics (cycle characteristics) evaluation results of the separator used for the battery characteristics evaluation.

  Table 2 shows the basic characteristics of the separator used for capacitor evaluation and the evaluation results of capacitor characteristics (capacitor resistance).

  The separator according to the present invention has low heat resistance, chemical resistance, insulation, low resistance, and excellent electrolyte retention. For electrochemical elements that require large capacity, high output, or low profile. And extremely useful.

Claims (15)

A separator for an electrochemical device consisting of a nonwoven fabric comprising aramid fibers, 55% degree of crystallinity 49.4～ of the aramid fibers obtained from X-ray diffraction also is properly in crystal size 19.0 to 30 Å A separator characterized by being. The separator according to claim 1 , wherein the crystal size of the aramid fiber is 19.0 to 22 Å .   The separator according to claim 1, wherein the aramid fibers are contained in the nonwoven fabric in the form of continuous fibers.   The separator according to claim 1, wherein the aramid fiber is polymetaphenylene isophthalamide fiber.   The separator according to claim 1, wherein the aramid fiber is a polyparaphenylene terephthalamide fiber.   The separator according to claim 1, wherein the aramid fiber is a copolyparaphenylene-3,4'oxydiphenylene-terephthalamide fiber.   The separator according to any one of claims 1 to 6, wherein the continuous fibers have an average fiber diameter of 5 µm or less.   The separator according to any one of claims 1 to 6, wherein an average fiber diameter of the continuous fibers is 2 µm or less.   The separator according to any one of claims 1 to 6, wherein an average fiber diameter of the continuous fibers is 1 µm or less.   The separator according to any one of claims 1 to 9, which has a thickness of 5 µm or more and 200 µm or less.   The separator according to any one of claims 1 to 9, wherein the porosity is 30% or more and 80% or less.   A lithium ion secondary battery comprising the separator according to any one of claims 1 to 11.   The electric double layer capacitor characterized by including the separator of any one of Claim 1 to 11.   An aluminum electrolytic capacitor comprising the separator according to any one of claims 1 to 11.   The lithium ion capacitor characterized by including the separator of any one of Claim 1 to 11.