JP2021077488A - Manufacturing method of separator for non-aqueous electrolyte secondary battery, manufacturing method of member for non-aqueous electrolyte secondary battery, and manufacturing method of non-aqueous electrolyte secondary battery - Google Patents
Manufacturing method of separator for non-aqueous electrolyte secondary battery, manufacturing method of member for non-aqueous electrolyte secondary battery, and manufacturing method of non-aqueous electrolyte secondary battery Download PDFInfo
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- JP2021077488A JP2021077488A JP2019201722A JP2019201722A JP2021077488A JP 2021077488 A JP2021077488 A JP 2021077488A JP 2019201722 A JP2019201722 A JP 2019201722A JP 2019201722 A JP2019201722 A JP 2019201722A JP 2021077488 A JP2021077488 A JP 2021077488A
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- Prior art keywords
- secondary battery
- aqueous electrolyte
- separator
- electrolyte secondary
- stretching
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- 238000004519 manufacturing process Methods 0.000 title claims description 47
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、非水電解液二次電池用セパレータの製造方法、非水電解液二次電池用部材の製造方法および非水電解液二次電池の製造方法に関する。 The present invention relates to a method for manufacturing a separator for a non-aqueous electrolyte secondary battery, a method for manufacturing a member for a non-aqueous electrolyte secondary battery, and a method for manufacturing a non-aqueous electrolyte secondary battery.
リチウム二次電池等の非水電解液二次電池は、現在、パーソナルコンピュータ、携帯電話および携帯情報端末等の機器に用いる電池、または車載用の電池として広く使用されている。 Non-aqueous electrolyte secondary batteries such as lithium secondary batteries are currently widely used as batteries used in devices such as personal computers, mobile phones and mobile information terminals, or batteries for vehicles.
このような非水電解液二次電池におけるセパレータとしては、ポリオレフィンを主成分とする多孔質フィルムが主に用いられている。その製造方法としては、ポリオレフィン系樹脂を含む樹脂組成物を延伸する工程を含む方法が挙げられる（特許文献１）。 As a separator in such a non-aqueous electrolytic solution secondary battery, a porous film containing polyolefin as a main component is mainly used. Examples of the production method include a method including a step of stretching a resin composition containing a polyolefin-based resin (Patent Document 1).
しかしながら、上述のような従来技術は、空孔のくねり度を低減する観点から改善の余地があった。 However, the above-mentioned prior art has room for improvement from the viewpoint of reducing the degree of waviness of the pores.
そこで、本発明の一態様は、空孔のくねり度に優れる非水電解液二次電池用セパレータを実現することを目的とする。 Therefore, one aspect of the present invention is to realize a separator for a non-aqueous electrolytic solution secondary battery having an excellent degree of bending of pores.
前述の事項を鑑み、鋭意研究を重ねた結果、本発明者は、第１の方向への延伸を経たシートを特定の緩和率にて第１の方向に収縮させながら第２の方向に延伸することによって、得られる多孔質フィルムにおける空孔のくねり度を好適な範囲に制御できることを見出した。 In view of the above-mentioned matters, as a result of repeated diligent research, the present inventor stretches the sheet that has undergone stretching in the first direction in the second direction while contracting in the first direction at a specific relaxation rate. By doing so, it was found that the degree of waviness of the pores in the obtained porous film can be controlled within a suitable range.
本発明の一態様は、以下の［１］〜［７］に示す発明を含む。
［１］ポリオレフィン系樹脂を含む樹脂組成物を第１の方向に延伸することによって得た１次シートを、前記第１の方向へ収縮させながら前記第１の方向と異なる第２の方向に延伸する延伸工程を含む、非水電解液二次電池用セパレータの製造方法。
［２］前記第１の方向への収縮における以下の式（１）にて表される緩和率が５％以上５０％未満である、［１］に記載の非水電解液二次電池用セパレータの製造方法。
［３］前記ポリオレフィン系樹脂が、１分子あたりの長鎖分岐度が２０個以下のポリオレフィンを含む、［１］または［２］に記載の非水電解液二次電池用セパレータの製造方法。
（ここで、前記ポリオレフィンの分岐度は、ＧＰＣ−ＭＡＬＳを使用したコンフォメーションプロットから計算した値である。）
［４］前記延伸工程の後に得られるシートの片面または両面に、ポリオレフィン、（メタ）アクリレート系樹脂、含フッ素樹脂、ポリアミド系樹脂、ポリエステル系樹脂および水溶性ポリマーからなる群より１種以上選択される樹脂を含む多孔質層を積層する工程をさらに含む、［１］〜［３］の何れか１つに記載の非水電解液二次電池用セパレータの製造方法。
［５］前記ポリアミド系樹脂がアラミド樹脂である、［４］に記載の非水電解液二次電池用セパレータの製造方法。
［６］［１］〜［５］の何れか１つに記載の非水電解液二次電池用セパレータの製造方法にて、非水電解液二次電池用セパレータを得る工程、および、
正極、前記非水電解液二次電池用セパレータおよび負極をこの順に配置する工程を含む、非水電解液二次電池用部材の製造方法。
［７］［１］〜［５］の何れか１つ記載の非水電解液二次電池用セパレータの製造方法にて、非水電解液二次電池用セパレータを得る工程、
正極、前記非水電解液二次電池用セパレータおよび負極をこの順に配置して、非水電解液二次電池用部材を得る工程、および
前記非水電解液二次電池用部材を容器の内部に入れ、次いで、前記容器の内部を非水電解液で満たした後、前記容器の内部を減圧しつつ、前記容器を密閉する工程を含む、非水電解液二次電池の製造方法。
One aspect of the present invention includes the inventions shown in the following [1] to [7].
[1] The primary sheet obtained by stretching the resin composition containing the polyolefin-based resin in the first direction is stretched in a second direction different from the first direction while shrinking in the first direction. A method for producing a separator for a non-aqueous electrolyte secondary battery, which comprises a stretching step.
[2] The separator for a non-aqueous electrolyte secondary battery according to [1], wherein the relaxation rate represented by the following formula (1) in the shrinkage in the first direction is 5% or more and less than 50%. Manufacturing method.
[3] The method for producing a separator for a non-aqueous electrolytic solution secondary battery according to [1] or [2], wherein the polyolefin-based resin contains a polyolefin having a long-chain branching degree of 20 or less per molecule.
(Here, the degree of branching of the polyolefin is a value calculated from a conformation plot using GPC-MALS.)
[4] One or more types are selected from the group consisting of polyolefins, (meth) acrylate resins, fluororesins, polyamide resins, polyester resins and water-soluble polymers on one or both sides of the sheet obtained after the stretching step. The method for producing a separator for a non-aqueous electrolyte secondary battery according to any one of [1] to [3], further comprising a step of laminating a porous layer containing a resin.
[5] The method for producing a separator for a non-aqueous electrolytic solution secondary battery according to [4], wherein the polyamide resin is an aramid resin.
[6] The step of obtaining a separator for a non-aqueous electrolyte secondary battery by the method for producing a separator for a non-aqueous electrolyte secondary battery according to any one of [1] to [5], and
A method for manufacturing a member for a non-aqueous electrolyte secondary battery, which comprises a step of arranging a positive electrode, a separator for the non-aqueous electrolyte secondary battery, and a negative electrode in this order.
[7] A step of obtaining a separator for a non-aqueous electrolyte secondary battery by the method for producing a separator for a non-aqueous electrolyte secondary battery according to any one of [1] to [5].
A step of arranging the positive electrode, the separator for the non-aqueous electrolyte secondary battery and the negative electrode in this order to obtain a member for the non-aqueous electrolyte secondary battery, and the member for the non-aqueous electrolyte secondary battery inside the container. A method for producing a non-aqueous electrolytic solution secondary battery, which comprises a step of filling the inside of the container with a non-aqueous electrolytic solution and then sealing the container while reducing the pressure inside the container.
本発明の一態様によれば、空孔のくねり度に優れる非水電解液二次電池用セパレータを提供できる。 According to one aspect of the present invention, it is possible to provide a separator for a non-aqueous electrolytic solution secondary battery having an excellent degree of waviness of pores.
本発明の一実施形態に関して以下に説明するが、本発明はこれに限定されるものではない。本発明は、以下に説明する各構成に限定されるものではなく、特許請求の範囲に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態に関しても本発明の技術的範囲に含まれる。なお、本明細書において特記しない限り、数値範囲を表す「Ａ〜Ｂ」は、「Ａ以上、Ｂ以下」を意味する。 An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims, and the technical means disclosed in the different embodiments may be appropriately combined. The obtained embodiments are also included in the technical scope of the present invention. Unless otherwise specified in the present specification, "A to B" representing a numerical range means "A or more and B or less".
［実施形態１：非水電解液二次電池用セパレータの製造方法］
本発明の実施形態１に係る非水電解液二次電池用セパレータの製造方法は、ポリオレフィン系樹脂を含む樹脂組成物を第１の方向に延伸することによって得た１次シートを、前記第１の方向へ収縮させながら前記第１の方向と異なる第２の方向に延伸する延伸工程を含む。
[Embodiment 1: Method for Manufacturing Separator for Non-Aqueous Electrolyte Secondary Battery]
In the method for producing a separator for a non-aqueous electrolytic solution secondary battery according to the first embodiment of the present invention, the first sheet obtained by stretching a resin composition containing a polyolefin resin in the first direction is obtained. Includes a stretching step of stretching in a second direction different from the first direction while contracting in the direction of.
前記１次シートを前記第２の方向に延伸する際に、前記１次シートを前記第１の方向へ収縮させる操作を「緩和操作」とも称する。また、非水電解液二次電池用セパレータを単に「セパレータ」とも称する。また、ポリオレフィン系樹脂を含む樹脂組成物を「ポリオレフィン樹脂組成物」とも称する。 The operation of contracting the primary sheet in the first direction when the primary sheet is stretched in the second direction is also referred to as a "relaxation operation". Further, the separator for a non-aqueous electrolyte secondary battery is also simply referred to as a "separator". Further, a resin composition containing a polyolefin-based resin is also referred to as a "polyolefin resin composition".
前記１次シートを前記第２の方向に延伸する際に、前記緩和操作を行うことによって、得られるセパレータにおける空孔のくねり度を好適な範囲に制御することができる。空孔のくねり度が低いセパレータは、非水電解液二次電池に用いたときにイオン透過性に優れる傾向がある。つまり、セパレータの空孔のくねり度を低減することによって、電池特性に優れる非水電解液二次電池を得ることができる。 When the primary sheet is stretched in the second direction, the degree of waviness of the pores in the obtained separator can be controlled within a suitable range by performing the relaxation operation. A separator having a low degree of waviness of pores tends to have excellent ion permeability when used in a non-aqueous electrolyte secondary battery. That is, by reducing the degree of bending of the pores of the separator, a non-aqueous electrolyte secondary battery having excellent battery characteristics can be obtained.
本発明の一実施形態に係る非水電解液二次電池用セパレータの製造方法は、具体的には、例えば、以下に示す（Ａ）〜（Ｃ）の工程を含む。
（Ａ）ポリオレフィン系樹脂および任意で孔形成剤を混練機に加えて溶融混練し、ポリオレフィン樹脂組成物を得る工程、
（Ｂ）得られたポリオレフィン樹脂組成物をシート状に成形すると共に、第１の方向に延伸することにより、１次シートを得る工程、
（Ｃ）１次シートを、前記第１の方向へ収縮させながら前記第１の方向と異なる第２の方向に延伸する工程。
Specifically, the method for producing a separator for a non-aqueous electrolytic solution secondary battery according to an embodiment of the present invention specifically includes, for example, the steps (A) to (C) shown below.
(A) A step of adding a polyolefin resin and optionally a pore-forming agent to a kneader and melt-kneading to obtain a polyolefin resin composition.
(B) A step of obtaining a primary sheet by molding the obtained polyolefin resin composition into a sheet and stretching it in the first direction.
(C) A step of stretching a primary sheet in a second direction different from the first direction while contracting the primary sheet in the first direction.
工程（Ａ）において、前記ポリオレフィン系樹脂の使用量は、得られるポリオレフィン樹脂組成物の重量を１００重量％とした場合、６重量％〜４５重量％であることが好ましく、９重量％〜３６重量％であることがより好ましい。 In the step (A), the amount of the polyolefin resin used is preferably 6% by weight to 45% by weight, preferably 9% by weight to 36% by weight, assuming that the weight of the obtained polyolefin resin composition is 100% by weight. More preferably.
前記ポリオレフィン系樹脂には、重量平均分子量が５×１０５〜１５×１０６の高分子量成分が含まれていることがより好ましい。特に、ポリオレフィン系樹脂に重量平均分子量が１００万以上の高分子量成分が含まれていると、得られる多孔質フィルムおよび当該多孔質フィルムを含む非水電解液二次電池用セパレータの強度が向上するのでより好ましい。 The said polyolefin resin, and more preferably a weight average molecular weight are included high molecular weight component of 5 × 10 5 ~15 × 10 6 . In particular, when the polyolefin resin contains a high molecular weight component having a weight average molecular weight of 1 million or more, the strength of the obtained porous film and the separator for a non-aqueous electrolytic solution secondary battery containing the porous film is improved. So more preferable.
前記ポリオレフィン系樹脂は、特に限定されないが、例えば、エチレン、プロピレン、１−ブテン、４−メチル−１−ペンテンおよび１−ヘキセン等の単量体を重合してなる、単独重合体または共重合体といった熱可塑性樹脂を挙げることができる。前記単独重合体としては、例えばポリエチレン、ポリプロピレン、ポリブテンを挙げることができる。また、前記共重合体としては、例えばエチレン−プロピレン共重合体を挙げることができる。 The polyolefin-based resin is not particularly limited, but is, for example, a homopolymer or a copolymer obtained by polymerizing monomers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene. Such as thermoplastic resin can be mentioned. Examples of the homopolymer include polyethylene, polypropylene, and polybutene. Further, as the copolymer, for example, an ethylene-propylene copolymer can be mentioned.
このうち、非水電解液二次電池用セパレータに過大電流が流れることをより低温で阻止することができるため、ポリエチレンがより好ましい。なお、この過大電流が流れることを阻止することをシャットダウンともいう。前記ポリエチレンとしては、低密度ポリエチレン、高密度ポリエチレン、線状ポリエチレン（エチレン−α−オレフィン共重合体）、重量平均分子量が１００万以上の超高分子量ポリエチレン等が挙げられる。このうち、重量平均分子量が１００万以上の超高分子量ポリエチレンがさらに好ましい。 Of these, polyethylene is more preferable because it can prevent an excessive current from flowing through the separator for a non-aqueous electrolyte secondary battery at a lower temperature. Preventing this excessive current from flowing is also called shutdown. Examples of the polyethylene include low-density polyethylene, high-density polyethylene, linear polyethylene (ethylene-α-olefin copolymer), ultra-high molecular weight polyethylene having a weight average molecular weight of 1 million or more, and the like. Of these, ultra-high molecular weight polyethylene having a weight average molecular weight of 1 million or more is more preferable.
前記ポリオレフィン系樹脂は、１分子あたりの長鎖分岐度が、好ましくは、２０個以下、より好ましくは１０個以下であるポリオレフィンを含み得る。ここで、前記長鎖分岐度は、例えば、ＧＰＣ−ＭＡＬＳを使用したコンフォメーションプロットから計算した値である。ここで、前記コンフォメーションプロットは、分子半径と分子量の対数プロットを意味する。 The polyolefin-based resin may contain polyolefins having a long chain branching degree per molecule of preferably 20 or less, more preferably 10 or less. Here, the degree of long-chain branching is, for example, a value calculated from a conformation plot using GPC-MALS. Here, the conformation plot means a logarithmic plot of molecular radius and molecular weight.
前記孔形成剤は、特に限定されないが、例えば、無機充填剤および可塑剤等を挙げることができる。前記無機充填剤としては、特に限定されるものではなく、無機フィラー、具体的には炭酸カルシウム等が挙げられる。前記可塑剤としては、特に限定されるものではなく、流動パラフィン等の低分子量の炭化水素が挙げられる。 The pore-forming agent is not particularly limited, and examples thereof include an inorganic filler and a plasticizer. The inorganic filler is not particularly limited, and examples thereof include an inorganic filler, specifically calcium carbonate and the like. The plasticizer is not particularly limited, and examples thereof include low molecular weight hydrocarbons such as liquid paraffin.
前記添加剤としては、前記孔形成剤の他に、任意で、本発明の効果を損なわない範囲にて、公知の添加剤を挙げることができる。前記公知の添加剤としては、例えば、酸化防止剤等を挙げることができる。 Examples of the additive include, in addition to the pore-forming agent, a known additive as long as the effect of the present invention is not impaired. Examples of the known additive include an antioxidant and the like.
工程（Ｂ）において、１次シートを得る方法は特に限定されるものではなく、インフレーション加工、カレンダー加工、Ｔダイ押出加工、スカイフ法等のシート成形方法により１次シートを製造することができる。 In the step (B), the method for obtaining the primary sheet is not particularly limited, and the primary sheet can be produced by a sheet forming method such as inflation processing, calendar processing, T-die extrusion processing, or skiff method.
例えば、Ｔダイ押出加工におけるＴダイ押出温度などの、前記シート成形方法におけるシート成型温度は、２００℃以上、２８０℃以下が好ましく、２２０℃以上、２６０℃以下がより好ましい。 For example, the sheet molding temperature in the sheet molding method, such as the T die extrusion temperature in the T die extrusion process, is preferably 200 ° C. or higher and 280 ° C. or lower, and more preferably 220 ° C. or higher and 260 ° C. or lower.
より膜厚精度の高い１次シートを得る方法としては、例えば、ポリオレフィン樹脂組成物に含有されるポリオレフィン系樹脂の融点より高い表面温度に調整された一対の回転成形工具を用いて、ポリオレフィン樹脂組成物を圧延成形する方法が挙げられる。このとき、回転成形工具の表面温度は、（ポリオレフィン系樹脂の融点＋５）℃以上であることが好ましい。また表面温度の上限は、（ポリオレフィン系樹脂の融点＋３０）℃以下であることが好ましく、（ポリオレフィン系樹脂の融点＋２０）℃以下であることがさらに好ましい。一対の回転成形工具としては、ロールまたはベルトが挙げられる。両回転成形工具の周速度は必ずしも厳密に同一周速度である必要はなく、それらの差異が±５％以内程度であればよい。また、前記シート形成方法により得られる単層のシート同士を積層したものを、１次シートとしてもよい。 As a method for obtaining a primary sheet having higher film thickness accuracy, for example, a polyolefin resin composition is used by using a pair of rotary molding tools adjusted to a surface temperature higher than the melting point of the polyolefin resin contained in the polyolefin resin composition. Examples thereof include a method of rolling and molding an object. At this time, the surface temperature of the rotary forming tool is preferably (melting point of polyolefin resin + 5) ° C. or higher. The upper limit of the surface temperature is preferably (melting point of polyolefin resin +30) ° C. or lower, and more preferably (melting point of polyolefin resin +20) ° C. or lower. Examples of the pair of rotary forming tools include rolls or belts. The peripheral velocities of both rotary forming tools do not necessarily have to be exactly the same, and the difference between them may be about ± 5% or less. Further, a sheet obtained by laminating single-layer sheets obtained by the sheet forming method may be used as a primary sheet.
ポリオレフィン樹脂組成物を一対の回転成形工具により圧延成形する際には、押出機よりストランド状に吐出したポリオレフィン樹脂組成物を直接一対の回転成形工具間に導入してもよく、一旦ペレット化したポリオレフィン系樹脂組成物を用いてもよい。 When the polyolefin resin composition is rolled and molded by a pair of rotary molding tools, the polyolefin resin composition discharged in a strand shape from an extruder may be directly introduced between the pair of rotary molding tools, and the polyolefin once pelletized. A based resin composition may be used.
工程（Ｂ）における延伸倍率は、１．１倍以上、１．９倍以下が好ましく、１．２倍以上、１．８倍以下がより好ましい。また、工程（Ｂ）における延伸温度は、１２０℃以上、１６０℃以下が好ましく、１３０℃以上、１５５℃以下がより好ましい。 The draw ratio in the step (B) is preferably 1.1 times or more and 1.9 times or less, and more preferably 1.2 times or more and 1.8 times or less. The stretching temperature in the step (B) is preferably 120 ° C. or higher and 160 ° C. or lower, and more preferably 130 ° C. or higher and 155 ° C. or lower.
工程（Ｂ）におけるポリオレフィン樹脂組成物の冷却には、冷風、冷却水等の冷媒に接触させる方法、冷却ロールに接触させる方法等を用いることができる。好ましくは冷却ロールに接触させる方法である。 For cooling the polyolefin resin composition in the step (B), a method of contacting with a refrigerant such as cold air or cooling water, a method of contacting with a cooling roll, or the like can be used. A method of contacting with a cooling roll is preferable.
工程（Ｂ）における第１の方向は特に限定されないが、例えば、ＭＤ方向（Machine Direction）であり得る。ここで、ＭＤ方向とは、上述の製造方法において、前記シート状のポリオレフィン樹脂組成物、前記１次シートおよび前記多孔質フィルムが搬送される方向を意味する。また、ＴＤ方向（Transverse Direction）とは、前記シート状のポリオレフィン樹脂組成物、前記１次シートおよび前記多孔質フィルムの面に平行な方向であってＭＤ方向に垂直な方向を意味する。 The first direction in the step (B) is not particularly limited, but may be, for example, the MD direction (Machine Direction). Here, the MD direction means the direction in which the sheet-shaped polyolefin resin composition, the primary sheet, and the porous film are conveyed in the above-mentioned production method. Further, the TD direction (Transverse Direction) means a direction parallel to the planes of the sheet-shaped polyolefin resin composition, the primary sheet and the porous film, and perpendicular to the MD direction.
前記ポリオレフィン樹脂組成物および前記１次シートに孔形成剤が含まれている場合、工程（Ｂ）および工程（Ｃ）の間、または、工程（Ｃ）の後に、延伸されたシートを、洗浄液を用いて洗浄して、前記孔形成剤を除去する工程を含む。 When the polyolefin resin composition and the primary sheet contain a pore-forming agent, a cleaning solution is applied to the stretched sheet during or after the steps (B) and (C) or after the step (C). Including a step of removing the pore-forming agent by washing with a product.
前記洗浄液は、前記孔形成剤を除去できる溶媒であれば特に限定されないが、例えば、塩酸水溶液、ヘプタン、ジクロロメタンなどを挙げることができる。 The cleaning liquid is not particularly limited as long as it is a solvent capable of removing the pore-forming agent, and examples thereof include an aqueous hydrochloric acid solution, heptane, and dichloromethane.
工程（Ｃ）における第２の方向は、前記第１の方向と異なる方向であり、好ましくは第１の方向と直交する方向である。例えば、前記第１の方向がＭＤ方向の場合、前記第２の方向は、ＴＤ方向である。 The second direction in the step (C) is a direction different from the first direction, preferably a direction orthogonal to the first direction. For example, when the first direction is the MD direction, the second direction is the TD direction.
工程（Ｃ）における、１次シートを、前記第１の方向へ収縮させながら前記第１の方向と異なる第２の方向に延伸する工程とは、以下の（Ｉ）および（ＩＩ）に示す態様も含みうる。
（Ｉ）１次シートを、前記第１の方向へ収縮させると同時に前記第１の方向と異なる第２の方向に延伸する工程
（ＩＩ）１次シートを、前記第１の方向へ収縮させる間に前記第１の方向と異なる第２の方向に延伸する工程（すなわち第１の方向への収縮の開始と第２の方向への延伸の開始が同時とは限らない）
工程（Ｃ）における、前記第２の方向に延伸する際の延伸温度は、８０℃以上、１２０℃以下が好ましく、８０℃以上、１１５℃以下がより好ましい。また、前記第２の方向に延伸する際の延伸倍率は、２倍以上、１２倍以下が好ましく、４倍以上、１０倍以下がより好ましい。
The step of stretching the primary sheet in the second direction different from the first direction while contracting in the first direction in the step (C) is the embodiment shown in the following (I) and (II). Can also be included.
(I) Step of shrinking the primary sheet in the first direction and at the same time stretching in a second direction different from the first direction (II) While shrinking the primary sheet in the first direction The step of stretching in a second direction different from the first direction (that is, the start of contraction in the first direction and the start of stretching in the second direction are not always simultaneous).
The stretching temperature at the time of stretching in the second direction in the step (C) is preferably 80 ° C. or higher and 120 ° C. or lower, and more preferably 80 ° C. or higher and 115 ° C. or lower. Further, the stretching ratio when stretching in the second direction is preferably 2 times or more and 12 times or less, and more preferably 4 times or more and 10 times or less.
前記緩和操作における緩和率は、以下の式（１）で表される：
緩和率（％）＝［｛（延伸工程前の１次シートの第１の方向の長さ）−（延伸工程後の多孔質フィルムの第１の方向の長さ）｝／（延伸工程前の１次シートの第１の方向の長さ）］×１００ （１）
なお、１次シートの長さとしては、必ずしも全長を測定しなくてもよい。緩和率の算出方法の具体例を以下に説明する。
The relaxation rate in the relaxation operation is represented by the following equation (1):
Relaxation rate (%) = [{(length of primary sheet before stretching step in first direction)-(length of porous film after stretching step in first direction)} / (before stretching step) Length of primary sheet in first direction)] × 100 (1)
The total length of the primary sheet does not necessarily have to be measured. A specific example of the method for calculating the mitigation rate will be described below.
比較的小さなサイズに切断された１次シートに対して前記延伸工程を施す場合、緩和率は以下のように算出できる。ここで、１次シートは正方形または長方形であると想定する。この場合、１次シートの４辺を把持部材によって把持する。第１の方向に垂直な２辺を把持する把持部材間の距離を縮めることによって１次シートを第１の方向に収縮させる。換言すれば第１の方向において対向する把持部材間の距離を縮めることによって１次シートを第１の方向に収縮させる。また、同時に、第１の方向に平行な２辺、すなわち、第２の方向に垂直な２辺を把持する把持部材間の距離を広げることによって１次シートを第２の方向に延伸する。換言すれば第２の方向において対向する把持部材間の距離を広げることによって１次シートを第２の方向に延伸する。この場合、緩和率は下記式（１ａ）にて算出される。 When the stretching step is applied to a primary sheet cut to a relatively small size, the relaxation rate can be calculated as follows. Here, it is assumed that the primary sheet is square or rectangular. In this case, the four sides of the primary sheet are gripped by the gripping members. The primary sheet is contracted in the first direction by reducing the distance between the gripping members that grip the two sides perpendicular to the first direction. In other words, the primary sheet is contracted in the first direction by reducing the distance between the gripping members facing each other in the first direction. At the same time, the primary sheet is stretched in the second direction by increasing the distance between the gripping members that grip the two sides parallel to the first direction, that is, the two sides perpendicular to the second direction. In other words, the primary sheet is stretched in the second direction by increasing the distance between the gripping members facing each other in the second direction. In this case, the relaxation rate is calculated by the following formula (1a).
緩和率（％）＝［｛（延伸工程前の第１の方向において対向する把持部材間の距離）−（延伸工程後の第１の方向において対向する把持部材間の距離）｝／（延伸工程前の第１の方向において対向する把持部材間の距離）］×１００ （１ａ）
また、長尺の１次シートに対して前記延伸工程を施す場合、緩和率は以下のように算出できる。ここで、第１の方向はＭＤ方向、第２の方向はＴＤ方向であると想定する。この場合、第２の方向の両端を把持部材によって把持する。ここで、複数の把持部材が第１の方向に並んでいる。第１の方向に隣接する把持部材間の距離を縮めることによって１次シートを第１の方向に収縮させる。また、同時に、第２の方向において対向する把持部材間の距離を広げることによって１次シートを第２の方向に延伸する。この場合、緩和率は下記式（１ｂ）にて算出される。
Relaxation rate (%) = [{(distance between gripping members facing each other in the first direction before the stretching step)-(distance between gripping members facing each other in the first direction after the stretching step)} / (stretching step) Distance between gripping members facing each other in the previous first direction)] × 100 (1a)
Further, when the stretching step is applied to a long primary sheet, the relaxation rate can be calculated as follows. Here, it is assumed that the first direction is the MD direction and the second direction is the TD direction. In this case, both ends in the second direction are gripped by the gripping members. Here, a plurality of gripping members are arranged in the first direction. The primary sheet is contracted in the first direction by reducing the distance between the gripping members adjacent to each other in the first direction. At the same time, the primary sheet is stretched in the second direction by increasing the distance between the gripping members facing each other in the second direction. In this case, the mitigation rate is calculated by the following formula (1b).
緩和率（％）＝［｛（延伸工程前の第１の方向において隣接する把持部材間の距離）−（延伸工程後の第１の方向において隣接する把持部材間の距離）｝／（延伸工程前の第１の方向において隣接する把持部材間の距離）］×１００ （１ｂ）
上述の空孔のくねり度を低減するとの観点から、前記緩和率は、５％以上であることが好ましく、１０％以上であることがより好ましく、１５％以上であることがさらに好ましい。一方、セパレータの突き刺し強度の低下を抑制するとの観点からは、前記緩和率は、５０％未満であることが好ましく、４０％以下であることがより好ましく、３５％以下であることがさらに好ましい。
Relaxation rate (%) = [{(distance between adjacent gripping members in the first direction before the stretching step)-(distance between adjacent gripping members in the first direction after the stretching step)} / (stretching step) Distance between adjacent gripping members in the previous first direction)] x 100 (1b)
From the viewpoint of reducing the degree of waviness of the above-mentioned pores, the relaxation rate is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more. On the other hand, from the viewpoint of suppressing the decrease in the piercing strength of the separator, the relaxation rate is preferably less than 50%, more preferably 40% or less, and further preferably 35% or less.
従って、前述の緩和率にて前記緩和操作を行うことによって、得られるセパレータの空孔のくねり度を好適に低減することができる。また、前述の緩和率を好適な範囲に調製することによって、セパレータの突き刺し強度の低下を好適に抑制することができ、空孔のくねり度および突き刺し強度の双方に優れる非水電解液二次電池用セパレータを製造することができる。 Therefore, by performing the relaxation operation at the relaxation rate described above, the degree of bending of the pores of the obtained separator can be suitably reduced. Further, by adjusting the above-mentioned relaxation rate within a suitable range, it is possible to suitably suppress a decrease in the piercing strength of the separator, and a non-aqueous electrolyte secondary battery excellent in both the degree of bending of the pores and the piercing strength. Separator can be manufactured.
緩和操作を行うことによってセパレータの空孔のくねり度が低下する理由は明らかではないが、１次シートを第２の方向に延伸する際に、同時に第１の方向に収縮させることによって、シート内の空孔が、シートの面方向でなく厚み方向に繋がり易くなるためと考えられる。 It is not clear why the degree of waviness of the pores of the separator is reduced by performing the relaxation operation, but when the primary sheet is stretched in the second direction, it is simultaneously contracted in the first direction, so that the inside of the sheet is reduced. It is considered that the holes in the sheet are easily connected not in the surface direction of the sheet but in the thickness direction.
工程（Ｃ）において前記第２の方向に延伸された１次シートに対して、特定の温度にて熱処理することによって熱固定を行って、セパレータを得てもよい。前記熱固定は、好ましくは１１０℃以上、１４０℃以下、より好ましくは１１５℃以上、１３５℃以下の温度にて実施される。また、前記熱固定は、好ましくは１０秒以上、２０分未満、より好ましくは２０秒以上、１５分以下の時間をかけて実施される。 The primary sheet stretched in the second direction in the step (C) may be heat-fixed by heat treatment at a specific temperature to obtain a separator. The heat fixation is preferably carried out at a temperature of 110 ° C. or higher and 140 ° C. or lower, more preferably 115 ° C. or higher and 135 ° C. or lower. Further, the heat fixing is preferably carried out over a period of 10 seconds or more and less than 20 minutes, more preferably 20 seconds or more and 15 minutes or less.
本発明の一実施形態に係る非水電解液二次電池用セパレータの製造方法は、前記延伸工程後に得られたシートの片面または両面に、樹脂を含む多孔質層を積層する工程をさらに含んでもよい。当該樹脂を含む多孔質層を積層する工程は、通常、前記孔形成剤を除去する工程の後に行われる。 The method for producing a separator for a non-aqueous electrolytic solution secondary battery according to an embodiment of the present invention may further include a step of laminating a porous layer containing a resin on one side or both sides of the sheet obtained after the stretching step. Good. The step of laminating the porous layer containing the resin is usually performed after the step of removing the pore-forming agent.
前記多孔質層を積層する工程をさらに含む方法にて製造される非水電解液二次電池用セパレータは、前記延伸工程後に得られたシート（以下、「多孔質フィルム」ということがある）の片面または両面に前記多孔質層が積層されている。以下、前述の前記多孔質フィルムの片面または両面に前記多孔質層が積層されている非水電解液二次電池用セパレータを、「非水電解液二次電池用積層セパレータ」とも称する。 The separator for a non-aqueous electrolytic solution secondary battery produced by a method further including a step of laminating the porous layer is a sheet (hereinafter, may be referred to as “porous film”) obtained after the stretching step. The porous layer is laminated on one side or both sides. Hereinafter, the separator for a non-aqueous electrolyte secondary battery in which the porous layer is laminated on one side or both sides of the above-mentioned porous film is also referred to as a “laminated separator for a non-aqueous electrolyte secondary battery”.
前記多孔質層を前記多孔質フィルムの片面または両面に積層する方法としては、例えば、前記多孔質層に含まれる樹脂を含む塗工液を前記多孔質フィルムの片面または両面に塗布し、乾燥させることによって多孔質層を析出させる方法が挙げられる。 As a method of laminating the porous layer on one side or both sides of the porous film, for example, a coating liquid containing a resin contained in the porous layer is applied to one side or both sides of the porous film and dried. This includes a method of precipitating a porous layer.
なお、前記多孔質フィルムの両面に多孔質層を析出させる場合は、（ａ）前記多孔質フィルムの両面にて前記多孔質層を同時に析出させてもよく、（ｂ）前記多孔質フィルムの片面に前記塗工液を塗布し、乾燥させることによって、前記多孔質フィルムの片面に多孔質層を析出させた後、前記多孔質フィルムのもう一方の片面に前記塗工液を塗布し、乾燥させることによって、前記多孔質フィルムのもう一方の片面に多孔質層を析出させてもよい。 In addition, when the porous layer is precipitated on both sides of the porous film, (a) the porous layer may be deposited on both sides of the porous film at the same time, and (b) one side of the porous film. The coating liquid is applied to and dried to precipitate a porous layer on one side of the porous film, and then the coating liquid is applied to the other side of the porous film and dried. Thereby, the porous layer may be precipitated on the other side of the porous film.
また、前記塗工液を前記多孔質フィルムの片面または両面に塗布する前に、当該ポリオレフィン多孔質フィルムの塗工液を塗布する片面または両面に対して、必要に応じて親水化処理を行うことができる。 Further, before applying the coating liquid to one side or both sides of the porous film, the one side or both sides to which the coating liquid of the polyolefin porous film is applied is subjected to a hydrophilic treatment as necessary. Can be done.
前記塗工液は、前記多孔質層に含まれる樹脂を含む。また、前記塗工液は、前記多孔質層に含まれ得る後述の微粒子を含み得る。前記塗工液は、通常、上述の多孔質層に含まれ得る樹脂を溶媒に溶解させると共に、前記微粒子を分散させることにより調製され得る。ここで、前記樹脂を溶解させる前記溶媒は、前記微粒子を分散させる分散媒を兼ねている。また、前記溶媒により前記樹脂をエマルションとしてもよい。 The coating liquid contains a resin contained in the porous layer. In addition, the coating liquid may contain fine particles described later that can be contained in the porous layer. The coating liquid can be usually prepared by dissolving the resin that can be contained in the above-mentioned porous layer in a solvent and dispersing the fine particles. Here, the solvent for dissolving the resin also serves as a dispersion medium for dispersing the fine particles. Further, the resin may be made into an emulsion by using the solvent.
前記樹脂は、電池の電解液に不溶であり、また、その電池の使用範囲において電気化学的に安定であることが好ましい。 It is preferable that the resin is insoluble in the electrolytic solution of the battery and is electrochemically stable in the range of use of the battery.
前記樹脂としては、具体的には、例えば、ポリオレフィン；（メタ）アクリレート系樹脂；含フッ素樹脂；ポリアミド系樹脂；ポリイミド系樹脂；ポリエステル系樹脂；ゴム類；融点またはガラス転移温度が１８０℃以上の樹脂；水溶性ポリマー；ポリカーボネート、ポリアセタール、ポリエーテルエーテルケトン等が挙げられる。 Specifically, the resin includes, for example, polyolefin; (meth) acrylate resin; fluorine-containing resin; polyamide resin; polyimide resin; polyester resin; rubbers; melting point or glass transition temperature of 180 ° C. or higher. Resins; water-soluble polymers; polycarbonates, polyacetals, polyether ether ketones and the like.
上述の樹脂のうち、ポリオレフィン、（メタ）アクリレート系樹脂、含フッ素樹脂、ポリアミド系樹脂、ポリエステル系樹脂および水溶性ポリマーが好ましい。 Among the above-mentioned resins, polyolefins, (meth) acrylate-based resins, fluorine-containing resins, polyamide-based resins, polyester-based resins and water-soluble polymers are preferable.
ポリオレフィンとしては、ポリエチレン、ポリプロピレン、ポリブテンおよびエチレン−プロピレン共重合体等が好ましい。 As the polyolefin, polyethylene, polypropylene, polybutene, ethylene-propylene copolymer and the like are preferable.
含フッ素樹脂としては、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、フッ化ビニリデン−トリフルオロエチレン共重合体、フッ化ビニリデン−トリクロロエチレン共重合体、フッ化ビニリデン−フッ化ビニル共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体およびエチレン−テトラフルオロエチレン共重合体等、並びに、前記含フッ素樹脂の中でもガラス転移温度が２３℃以下である含フッ素ゴムを挙げることができる。 Examples of the fluororesin include polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and fluororesin. Vinylidene-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-trichloroethylene copolymer, vinylidene fluoride-vinyl fluoride copolymer, vinylidene fluoride-hexafluoropropylene-tetra Examples thereof include fluoroethylene copolymers, ethylene-tetrafluoroethylene copolymers, and fluoropolymers among the fluororesins having a glass transition temperature of 23 ° C. or lower.
ポリアミド系樹脂としては、芳香族ポリアミドおよび全芳香族ポリアミドなどのアラミド樹脂が好ましい。 As the polyamide-based resin, aramid resins such as aromatic polyamide and totally aromatic polyamide are preferable.
アラミド樹脂としては、具体的には、例えば、ポリ（パラフェニレンテレフタルアミド）、ポリ（メタフェニレンイソフタルアミド）、ポリ（パラベンズアミド）、ポリ（メタベンズアミド）、ポリ（４，４’−ベンズアニリドテレフタルアミド）、ポリ（パラフェニレン−４，４’−ビフェニレンジカルボン酸アミド）、ポリ（メタフェニレン−４，４’−ビフェニレンジカルボン酸アミド）、ポリ（パラフェニレン−２，６−ナフタレンジカルボン酸アミド）、ポリ（メタフェニレン−２，６−ナフタレンジカルボン酸アミド）、ポリ（２−クロロパラフェニレンテレフタルアミド）、パラフェニレンテレフタルアミド／２，６−ジクロロパラフェニレンテレフタルアミド共重合体、メタフェニレンテレフタルアミド／２，６−ジクロロパラフェニレンテレフタルアミド共重合体等が挙げられる。このうち、ポリ（パラフェニレンテレフタルアミド）がより好ましい。 Specific examples of the aramid resin include poly (paraphenylene terephthalamide), poly (metaphenylene isophthalamide), poly (parabenzamide), poly (metabenzamide), and poly (4,4'-benzanilide terephthalamide). Amide), poly (paraphenylene-4,4'-biphenylenedicarboxylic acid amide), poly (metaphenylene-4,4'-biphenylenedicarboxylic acid amide), poly (paraphenylene-2,6-naphthalenedicarboxylic acid amide), Poly (metaphenylene-2,6-naphthalenedicarboxylic acid amide), poly (2-chloroparaphenylene terephthalamide), paraphenylene terephthalamide / 2,6-dichloroparaphenylene terephthalamide copolymer, metaphenylene terephthalamide / 2 , 6-Dichloroparaphenylene terephthalamide copolymer and the like. Of these, poly (paraphenylene terephthalamide) is more preferable.
ポリエステル系樹脂としては、ポリアリレートなどの芳香族ポリエステルおよび液晶ポリエステルが好ましい。 As the polyester-based resin, aromatic polyesters such as polyarylate and liquid crystal polyesters are preferable.
ゴム類としては、スチレン−ブタジエン共重合体およびその水素化物、メタクリル酸エステル共重合体、アクリロニトリル−アクリル酸エステル共重合体、スチレン−アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリ酢酸ビニル等を挙げることができる。 Examples of rubbers include styrene-butadiene copolymers and their hydrides, methacrylate copolymers, acrylonitrile-acrylic acid ester copolymers, styrene-acrylic acid ester copolymers, ethylene propylene rubber, polyvinyl acetate and the like. Can be mentioned.
融点又はガラス転移温度が１８０℃以上の樹脂としては、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルイミド、ポリアミドイミド、ポリエーテルアミド等を挙げることができる。 Examples of the resin having a melting point or a glass transition temperature of 180 ° C. or higher include polyphenylene ether, polysulfone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyamideimide, and polyetheramide.
水溶性ポリマーとしては、ポリビニルアルコール、ポリエチレングリコール、セルロースエーテル、アルギン酸ナトリウム、ポリアクリル酸、ポリアクリルアミド、ポリメタクリル酸等を挙げることができる。 Examples of the water-soluble polymer include polyvinyl alcohol, polyethylene glycol, cellulose ether, sodium alginate, polyacrylic acid, polyacrylamide, polymethacrylic acid and the like.
なお、多孔質層に用いられる樹脂としては、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。 As the resin used for the porous layer, only one type may be used, or two or more types may be used in combination.
多孔質層は、微粒子を含んでもよい。本明細書における微粒子とは、一般にフィラーと称される有機微粒子または無機微粒子のことである。従って、多孔質層が微粒子を含む場合、多孔質層に含まれる上述の樹脂は、微粒子同士、並びに微粒子と多孔質フィルムとを結着させるバインダー樹脂としての機能を有することとなる。また、上記微粒子は、絶縁性微粒子が好ましい。 The porous layer may contain fine particles. The fine particles in the present specification are organic fine particles or inorganic fine particles generally referred to as fillers. Therefore, when the porous layer contains fine particles, the above-mentioned resin contained in the porous layer has a function as a binder resin for binding the fine particles to each other and the fine particles and the porous film. Further, the fine particles are preferably insulating fine particles.
多孔質層に含まれる有機微粒子としては、樹脂からなる微粒子が挙げられる。多孔質層に含まれる無機微粒子としては、具体的には、例えば、炭酸カルシウム、タルク、クレー、カオリン、シリカ、ハイドロタルサイト、珪藻土、炭酸マグネシウム、炭酸バリウム、硫酸カルシウム、硫酸マグネシウム、硫酸バリウム、水酸化アルミニウム、ベーマイト、水酸化マグネシウム、酸化カルシウム、酸化マグネシウム、酸化チタン、窒化チタン、アルミナ（酸化アルミニウム）、窒化アルミニウム、マイカ、ゼオライトおよびガラス等の無機物からなるフィラーが挙げられる。これらの無機微粒子は、絶縁性微粒子である。上記微粒子は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。 Examples of the organic fine particles contained in the porous layer include fine particles made of resin. Specific examples of the inorganic fine particles contained in the porous layer include calcium carbonate, talc, clay, kaolin, silica, hydrotalcite, diatomaceous earth, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, and the like. Examples thereof include fillers made of inorganic substances such as aluminum hydroxide, boehmite, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, titanium nitride, alumina (aluminum oxide), aluminum nitride, mica, zeolite and glass. These inorganic fine particles are insulating fine particles. Only one type of the fine particles may be used, or two or more types may be used in combination.
上記微粒子のうち、無機物からなる微粒子が好適であり、シリカ、酸化カルシウム、酸化マグネシウム、酸化チタン、アルミナ、マイカ、ゼオライト、水酸化アルミニウム、またはベーマイト等の無機酸化物からなる微粒子がより好ましく、シリカ、酸化マグネシウム、酸化チタン、水酸化アルミニウム、ベーマイトおよびアルミナからなる群から選択される少なくとも１種の微粒子がさらに好ましく、アルミナが特に好ましい。 Among the above fine particles, fine particles made of an inorganic substance are preferable, and fine particles made of an inorganic oxide such as silica, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, zeolite, aluminum hydroxide, or boehmite are more preferable, and silica is more preferable. , At least one fine particle selected from the group consisting of magnesium oxide, titanium oxide, aluminum hydroxide, boehmite and alumina is more preferable, and alumina is particularly preferable.
多孔質層における微粒子の含有量は、多孔質層の１〜９９体積％であることが好ましく、５〜９５体積％であることがより好ましい。微粒子の含有量を上記範囲とすることにより、微粒子同士の接触によって形成される空隙が、樹脂等によって閉塞されることが少なくなる。よって、十分なイオン透過性を得ることができると共に、単位面積当たりの目付を適切な値にすることができる。 The content of the fine particles in the porous layer is preferably 1 to 99% by volume, more preferably 5 to 95% by volume of the porous layer. By setting the content of the fine particles within the above range, the voids formed by the contact between the fine particles are less likely to be blocked by the resin or the like. Therefore, sufficient ion permeability can be obtained, and the basis weight per unit area can be set to an appropriate value.
微粒子は、粒径または比表面積が互いに異なる２種類以上を組み合わせて用いてもよい。 The fine particles may be used in combination of two or more types having different particle sizes or specific surface areas.
上記溶媒は、ポリオレフィン多孔質フィルムに悪影響を及ぼさず、上記樹脂を均一かつ安定に溶解し、上記微粒子を均一かつ安定に分散させることができればよく、特に限定されるものではない。上記溶媒としては、具体的には、例えば、水および有機溶媒が挙げられる。上記溶媒は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。 The solvent is not particularly limited as long as it does not adversely affect the porous polyolefin film, dissolves the resin uniformly and stably, and disperses the fine particles uniformly and stably. Specific examples of the solvent include water and an organic solvent. Only one type of the solvent may be used, or two or more types may be used in combination.
塗工液は、所望の多孔質層を得るのに必要な樹脂固形分（樹脂濃度）や微粒子量等の条件を満足することができれば、どのような方法で形成されてもよい。塗工液の形成方法としては、具体的には、例えば、機械攪拌法、超音波分散法、高圧分散法、メディア分散法等が挙げられる。また、上記塗工液は、本発明の目的を損なわない範囲で、上記樹脂および微粒子以外の成分として、分散剤や可塑剤、界面活性剤、ｐＨ調整剤等の添加剤を含んでいてもよい。尚、添加剤の添加量は、本発明の目的を損なわない範囲であればよい。 The coating liquid may be formed by any method as long as conditions such as the resin solid content (resin concentration) and the amount of fine particles required to obtain a desired porous layer can be satisfied. Specific examples of the coating liquid forming method include a mechanical stirring method, an ultrasonic dispersion method, a high-pressure dispersion method, and a media dispersion method. In addition, the coating liquid may contain additives such as a dispersant, a plasticizer, a surfactant, and a pH adjuster as components other than the resin and fine particles as long as the object of the present invention is not impaired. .. The amount of the additive added may be within a range that does not impair the object of the present invention.
塗工液の多孔質フィルムへの塗布方法、つまり、多孔質フィルムの表面への多孔質層の形成方法は、特に制限されるものではない。多孔質層の形成方法としては、例えば、塗工液を多孔質フィルムの表面に直接塗布した後、溶媒を除去する方法；塗工液を適当な支持体に塗布し、溶媒を除去して多孔質層を形成した後、この多孔質層と多孔質フィルムとを圧着させ、次いで支持体を剥がす方法；塗工液を適当な支持体に塗布した後、塗布面に多孔質フィルムを圧着させ、次いで支持体を剥がした後に溶媒を除去する方法等が挙げられる。 The method of applying the coating liquid to the porous film, that is, the method of forming the porous layer on the surface of the porous film is not particularly limited. As a method of forming the porous layer, for example, a method of directly applying the coating liquid to the surface of the porous film and then removing the solvent; the coating liquid is applied to an appropriate support, and the solvent is removed to make the porous layer porous. A method in which the porous layer is pressure-bonded to the porous film after the quality layer is formed, and then the support is peeled off; the coating liquid is applied to an appropriate support, and then the porous film is pressure-bonded to the coated surface. Then, a method of removing the solvent after peeling off the support and the like can be mentioned.
塗工液の塗布方法としては、従来公知の方法を採用することができ、具体的には、例えば、グラビアコーター法、ディップコーター法、バーコーター法、およびダイコーター法等が挙げられる。 As a method for applying the coating liquid, a conventionally known method can be adopted, and specific examples thereof include a gravure coater method, a dip coater method, a bar coater method, and a die coater method.
溶媒の除去方法は、乾燥による方法が一般的である。また、塗工液に含まれる溶媒を他の溶媒に置換してから乾燥を行ってもよい。 The solvent is generally removed by drying. Alternatively, the solvent contained in the coating liquid may be replaced with another solvent before drying.
＜非水電解液二次電池用セパレータ、多孔質フィルム、多孔質層の物性等＞
前記非水電解液二次電池用セパレータは、ポリオレフィン系樹脂を含み、ポリオレフィン系樹脂を主成分とする多孔質フィルムであり得る。「ポリオレフィン系樹脂を主成分とする」とは、セパレータに占めるポリオレフィン系樹脂の割合が、セパレータを構成する材料全体の５０体積％以上、好ましくは９０体積％以上であり、より好ましくは９５体積％以上であることを意味する。
<Separator for non-aqueous electrolyte secondary battery, porous film, physical properties of porous layer, etc.>
The separator for a non-aqueous electrolytic solution secondary battery may be a porous film containing a polyolefin-based resin and containing the polyolefin-based resin as a main component. “Containing a polyolefin resin as a main component” means that the proportion of the polyolefin resin in the separator is 50% by volume or more, preferably 90% by volume or more, and more preferably 95% by volume of the entire material constituting the separator. It means that it is the above.
前記セパレータは、その内部に連結した細孔を多数有しており、一方の面から他方の面に気体や液体を通過させることが可能となっている。 The separator has a large number of pores connected to the inside thereof, and allows gas or liquid to pass from one surface to the other.
前記多孔質フィルムからなるセパレータの膜厚は、特に限定されないが、４〜４０μｍであることが好ましく、５〜２０μｍであることがより好ましい。前記セパレータの膜厚が４μｍ以上であれば、電池の内部短絡を十分に防止することができるという観点から好ましい。一方、前記セパレータの膜厚が４０μｍ以下であれば、非水電解液二次電池の大型化を防ぐことができるという観点から好ましい。 The film thickness of the separator made of the porous film is not particularly limited, but is preferably 4 to 40 μm, and more preferably 5 to 20 μm. When the film thickness of the separator is 4 μm or more, it is preferable from the viewpoint that an internal short circuit of the battery can be sufficiently prevented. On the other hand, when the film thickness of the separator is 40 μm or less, it is preferable from the viewpoint that it is possible to prevent the non-aqueous electrolytic solution secondary battery from becoming large in size.
前記多孔質フィルムからなるセパレータの単位面積当たりの重量、すなわち重量目付は、電池の、重量エネルギー密度や体積エネルギー密度を高くすることができるように、通常、４〜２０ｇ／ｍ２であることが好ましく、５〜１２ｇ／ｍ２であることがより好ましい。 The weight per unit area of the separator made of the porous film, that is, the weight scale, is usually 4 to 20 g / m 2 so that the weight energy density and the volume energy density of the battery can be increased. It is preferably 5 to 12 g / m 2 , and more preferably 5 to 12 g / m 2.
前記多孔質フィルムからなるセパレータのガーレ値は、十分なイオン透過性を示すという観点から、５０〜２００ｓｅｃ／１００ｍＬであることが好ましく、７０〜１９０ｓｅｃ／１００ｍＬであることがより好ましい。ガーレ値とは、非水電解液二次電池用セパレータの分野において、一般に、イオン透過性の評価として使用される指標である。 The galley value of the separator made of the porous film is preferably 50 to 200 sec / 100 mL, more preferably 70 to 190 sec / 100 mL, from the viewpoint of exhibiting sufficient ion permeability. The Gale value is an index generally used as an evaluation of ion permeability in the field of separators for non-aqueous electrolyte secondary batteries.
前記多孔質フィルムからなるセパレータの突き刺し強度は、３５０ｇｆ以上であることが好ましく、４００ｇｆ以上であることがより好ましく、４５０ｇｆ以上であることがさらに好ましい。 The piercing strength of the separator made of the porous film is preferably 350 gf or more, more preferably 400 gf or more, and further preferably 450 gf or more.
なお、前記突き刺し強度は、以下の（ｉ）および（ｉｉ）に示す方法にて測定される；
（ｉ）前記セパレータを１２ｍｍΦのワッシャで固定した後、ピン（ピン径１ｍｍΦ、先端０．５Ｒ）を、突き刺し速度：２００ｍｍ／ｍｉｎの条件にて、当該セパレータに突き刺す。
（ｉｉ）（ｉ）にて前記セパレータに前記ピンを突き刺したときの最大応力（ｇｆ）を測定し、その測定値をセパレータの突き刺し強度とする。
The piercing strength is measured by the methods shown in (i) and (ii) below;
(I) After fixing the separator with a washer of 12 mmΦ, a pin (pin diameter 1 mmΦ, tip 0.5R) is pierced into the separator under the condition of piercing speed: 200 mm / min.
In (ii) and (i), the maximum stress (gf) when the pin is pierced into the separator is measured, and the measured value is taken as the piercing strength of the separator.
前記多孔質フィルムからなるセパレータの空隙率は、電解液の保持量を高めると共に、過大電流が流れることをより低温で確実に阻止（シャットダウン）する機能を得ることができるように、２０体積％〜８０体積％であることが好ましく、３０〜７５体積％であることがより好ましい。 The porosity of the separator made of the porous film is 20% by volume or more so that the retention amount of the electrolytic solution can be increased and the function of reliably blocking (shutting down) the flow of an excessive current at a lower temperature can be obtained. It is preferably 80% by volume, more preferably 30 to 75% by volume.
前記多孔質フィルムからなるセパレータが有する細孔の孔径は、十分なイオン透過性、および、電極を構成する粒子の入り込みを防止するという観点から、０．３μｍ以下であることが好ましく、０．１４μｍ以下であることがより好ましい。 The pore size of the pores of the separator made of the porous film is preferably 0.3 μm or less, preferably 0.14 μm, from the viewpoint of sufficient ion permeability and preventing the entry of particles constituting the electrode. The following is more preferable.
前記多孔質層の厚さは一層あたり、０．５〜１５μｍであることが好ましく、２〜１０μｍであることがより好ましい。多孔質層の厚さが一層あたり０．５μｍ以上であれば、非水電解液二次電池の破損等による内部短絡を充分に抑制することができ、また、多孔質層における電解液の保持量が充分となる。一方、前記多孔質層の厚さが一層あたり１５μｍ以下であれば、レート特性またはサイクル特性の低下を抑制することができる。 The thickness of the porous layer is preferably 0.5 to 15 μm, more preferably 2 to 10 μm per layer. When the thickness of the porous layer is 0.5 μm or more per layer, internal short circuits due to damage of the non-aqueous electrolytic solution secondary battery can be sufficiently suppressed, and the amount of the electrolytic solution retained in the porous layer. Will be sufficient. On the other hand, when the thickness of the porous layer is 15 μm or less per layer, deterioration of rate characteristics or cycle characteristics can be suppressed.
前記多孔質層の単位面積当たりの重量、すなわち重量目付は一層あたり、１〜２０ｇ／ｍ２であることが好ましく、４〜１０ｇ／ｍ２であることがより好ましい。 The weight per unit area of the porous layer, that is, the weight basis weight is preferably 1 to 20 g / m 2 per layer, and more preferably 4 to 10 g / m 2 .
また、前記多孔質層の１平方メートル当たりに含まれる多孔質層構成成分の体積は一層あたり、０．５〜２０ｃｍ３であることが好ましく、１〜１０ｃｍ３であることがより好ましく、２〜７ｃｍ３であることがさらに好ましい。 Further, the volume of the porous layer constituent component contained in 1 square meter of the porous layer is preferably 0.5 to 20 cm 3 per layer, more preferably 1 to 10 cm 3, and 2 to 7 cm. It is more preferably 3.
前記多孔質層の空隙率は、十分なイオン透過性を得ることができるように、２０〜９０体積％であることが好ましく、３０〜８０体積％であることがより好ましい。また、前記多孔質層が有する細孔の孔径は、前記非水電解液二次電池用積層セパレータが十分なイオン透過性を得ることができるように、３μｍ以下であることが好ましく、１μｍ以下であることがより好ましい。 The porosity of the porous layer is preferably 20 to 90% by volume, more preferably 30 to 80% by volume so that sufficient ion permeability can be obtained. The pore diameter of the pores of the porous layer is preferably 3 μm or less, preferably 1 μm or less, so that the laminated separator for a non-aqueous electrolytic solution secondary battery can obtain sufficient ion permeability. More preferably.
前記非水電解液二次電池用積層セパレータの膜厚は、５．５μｍ〜４５μｍであることが好ましく、６μｍ〜２５μｍであることがより好ましい。 The film thickness of the laminated separator for a non-aqueous electrolytic solution secondary battery is preferably 5.5 μm to 45 μm, and more preferably 6 μm to 25 μm.
前記非水電解液二次電池用積層セパレータのガーレ値は、１００〜３５０ｓｅｃ／１００ｍＬであることが好ましく、１００〜３００ｓｅｃ／１００ｍＬであることがより好ましい。 The galley value of the laminated separator for a non-aqueous electrolytic solution secondary battery is preferably 100 to 350 sec / 100 mL, and more preferably 100 to 300 sec / 100 mL.
また、前記非水電解液二次電池用積層セパレータの突き刺し強度は、３５０ｇｆ以上であることが好ましく、４００ｇｆ以上であることがより好ましく、４５０ｇｆ以上であることがさらに好ましい。なお、前記突き刺し強度は、前記多孔質フィルムと同様の方法にて測定される。 Further, the piercing strength of the laminated separator for a non-aqueous electrolytic solution secondary battery is preferably 350 gf or more, more preferably 400 gf or more, and further preferably 450 gf or more. The piercing strength is measured by the same method as that for the porous film.
尚、本発明の一実施形態における非水電解液二次電池用セパレータは、前記多孔質フィルムおよび前記多孔質層以外の別の多孔質層を、必要に応じて、本発明の目的を損なわない範囲で含んでいてもよい。前記別の多孔質層としては、耐熱層や接着層、保護層等の公知の多孔質層が挙げられる。 The separator for a non-aqueous electrolytic solution secondary battery according to the embodiment of the present invention does not impair the object of the present invention by using the porous film and another porous layer other than the porous layer, if necessary. It may be included in the range. Examples of the other porous layer include known porous layers such as a heat-resistant layer, an adhesive layer, and a protective layer.
［実施形態２：非水電解液二次電池用部材の製造方法、実施形態３：非水電解液二次電池の製造方法］
本発明の実施形態２に係る非水電解液二次電池用部材の製造方法は、本発明の一実施形態に係る非水電解液二次電池用セパレータの製造方法にて、非水電解液二次電池用セパレータを得る工程；および、正極、前記非水電解液二次電池用セパレータおよび負極をこの順に配置して、非水電解液二次電池用部材を製造する工程を含む。
[Embodiment 2: Manufacturing Method of Non-Aqueous Electrolyte Secondary Battery Member, Embodiment 3: Manufacturing Method of Non-Aqueous Electrolyte Secondary Battery]
The method for producing the non-aqueous electrolyte secondary battery member according to the second embodiment of the present invention is the method for producing the non-aqueous electrolyte secondary battery separator according to the embodiment of the present invention. A step of obtaining a separator for a secondary battery; and a step of arranging the positive electrode, the separator for the non-aqueous electrolyte secondary battery and the negative electrode in this order to manufacture a member for the non-aqueous electrolyte secondary battery.
本発明の実施形態３に係る非水電解液二次電池の製造方法は、本発明の一実施形態に係る非水電解液二次電池用セパレータの製造方法にて、非水電解液二次電池用セパレータを得る工程；正極、前記非水電解液二次電池用セパレータおよび負極をこの順に配置して、非水電解液二次電池用部材を得る工程；および前記非水電解液二次電池用部材を容器の内部に入れ、次いで、前記容器の内部を非水電解液で満たした後、前記容器の内部を減圧しつつ、前記容器を密閉して、非水電解液二次電池を製造する工程を含む。 The method for manufacturing a non-aqueous electrolyte secondary battery according to the third embodiment of the present invention is the method for manufacturing a separator for a non-aqueous electrolyte secondary battery according to the embodiment of the present invention. Step of obtaining a separator for non-aqueous electrolyte solution; a step of arranging a positive electrode, a separator for the non-aqueous electrolyte secondary battery and a negative electrode in this order to obtain a member for the non-aqueous electrolyte secondary battery; The member is placed inside the container, and then the inside of the container is filled with the non-aqueous electrolyte solution, and then the inside of the container is depressurized while the container is sealed to manufacture a non-aqueous electrolyte secondary battery. Includes steps.
本発明の実施形態２に係る非水電解液二次電池用部材の製造方法は、空孔のくねり度に優れる非水電解液二次電池用セパレータを備え、電池性能に優れる非水電解液二次電池用部材として好適な非水電解液二次電池用部材を製造できるとの効果を奏する。 The method for manufacturing a non-aqueous electrolyte secondary battery member according to the second embodiment of the present invention includes a non-aqueous electrolyte secondary battery separator having an excellent degree of bending of pores, and a non-aqueous electrolyte secondary battery having excellent battery performance. It has the effect of being able to manufacture a non-aqueous electrolyte secondary battery member suitable as a secondary battery member.
本発明の実施形態３に係る非水電解液二次電池の製造方法は、空孔のくねり度に優れる非水電解液二次電池用セパレータを備え、電池性能に優れる非水電解液二次電池を製造できるとの効果を奏する。 The method for manufacturing a non-aqueous electrolyte secondary battery according to the third embodiment of the present invention includes a separator for a non-aqueous electrolyte secondary battery having an excellent degree of bending of pores, and a non-aqueous electrolyte secondary battery having excellent battery performance. It has the effect of being able to manufacture.
＜正極＞
本発明の一実施形態に係る非水電解液二次電池部材および非水電解液二次電池における正極としては、一般に非水電解液二次電池の正極として使用されるものであれば、特に限定されないが、例えば、正極活物質および結着剤を含む活物質層が集電体上に成形された構造を備える正極シートを使用することができる。なお、上記活物質層は、更に導電剤を含んでもよい。
<Positive electrode>
The positive electrode in the non-aqueous electrolyte secondary battery member and the non-aqueous electrolyte secondary battery according to the embodiment of the present invention is particularly limited as long as it is generally used as the positive electrode of the non-aqueous electrolyte secondary battery. However, for example, a positive electrode sheet having a structure in which an active material layer containing a positive electrode active material and a binder is formed on a current collector can be used. The active material layer may further contain a conductive agent.
上記正極活物質としては、例えば、リチウムイオンをドープ・脱ドープ可能な材料が挙げられる。当該材料としては、具体的には、例えば、Ｖ、Ｍｎ、Ｆｅ、ＣｏおよびＮｉ等の遷移金属を少なくとも１種類含んでいるリチウム複合酸化物が挙げられる。 Examples of the positive electrode active material include materials capable of doping and dedoping lithium ions. Specific examples of the material include a lithium composite oxide containing at least one transition metal such as V, Mn, Fe, Co and Ni.
上記導電剤としては、例えば、天然黒鉛、人造黒鉛、コークス類、カーボンブラック、熱分解炭素類、炭素繊維および有機高分子化合物焼成体等の炭素質材料等が挙げられる。上記導電材は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。 Examples of the conductive agent include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers and calcined organic polymer compounds. Only one type of the conductive material may be used, or two or more types may be used in combination.
上記結着剤としては、例えば、ポリフッ化ビニリデン等のフッ素系樹脂、アクリル樹脂、並びに、スチレンブタジエンゴムが挙げられる。なお、結着剤は、増粘剤としての機能も有している。 Examples of the binder include a fluorine-based resin such as polyvinylidene fluoride, an acrylic resin, and styrene-butadiene rubber. The binder also has a function as a thickener.
上記正極集電体としては、例えば、Ａｌ、Ｎｉおよびステンレス等の導電体が挙げられる。中でも、薄膜に加工し易く、安価であることから、Ａｌがより好ましい。 Examples of the positive electrode current collector include conductors such as Al, Ni and stainless steel. Of these, Al is more preferable because it is easy to process into a thin film and is inexpensive.
シート状の正極の製造方法としては、例えば、正極活物質、導電剤および結着剤を正極集電体上で加圧成型する方法；適当な有機溶剤を用いて正極活物質、導電剤および結着剤をペースト状にした後、当該ペーストを正極集電体に塗工し、乾燥した後に加圧して正極集電体に固着する方法；等が挙げられる。 As a method for producing a sheet-shaped positive electrode, for example, a method of press-molding a positive electrode active material, a conductive agent and a binder on a positive electrode current collector; a positive electrode active material, a conductive agent and a binder using an appropriate organic solvent. Examples thereof include a method in which the adhesive is made into a paste, the paste is applied to the positive electrode current collector, dried, and then pressurized to be fixed to the positive electrode current collector.
＜負極＞
本発明の一実施形態に係る非水電解液二次電池部材および非水電解液二次電池における負極としては、一般に非水電解液二次電池の負極として使用されるものであれば、特に限定されないが、例えば、負極活物質および結着剤を含む活物質層が集電体上に成形された構造を備える負極シートを使用することができる。なお、上記活物質層は、更に導電剤を含んでもよい。
<Negative electrode>
The negative electrode in the non-aqueous electrolyte secondary battery member and the non-aqueous electrolyte secondary battery according to the embodiment of the present invention is particularly limited as long as it is generally used as the negative electrode of the non-aqueous electrolyte secondary battery. However, for example, a negative electrode sheet having a structure in which an active material layer containing a negative electrode active material and a binder is formed on a current collector can be used. The active material layer may further contain a conductive agent.
上記負極活物質としては、例えば、リチウムイオンをドープ・脱ドープ可能な材料、リチウム金属またはリチウム合金等が挙げられる。当該材料としては、例えば、炭素質材料等が挙げられる。炭素質材料としては、天然黒鉛、人造黒鉛、コークス類、カーボンブラック、および熱分解炭素類等が挙げられる。 Examples of the negative electrode active material include materials capable of doping and dedoping lithium ions, lithium metals, lithium alloys, and the like. Examples of the material include carbonaceous materials. Examples of carbonaceous materials include natural graphite, artificial graphite, cokes, carbon black, and pyrolytic carbons.
上記負極集電体としては、例えば、Ｃｕ、Ｎｉおよびステンレス等が挙げられ、特にリチウムイオン二次電池においてはリチウムと合金を作り難く、かつ薄膜に加工し易いことから、Ｃｕがより好ましい。 Examples of the negative electrode current collector include Cu, Ni, and stainless steel. Cu is more preferable because it is difficult to form an alloy with lithium in a lithium ion secondary battery and it is easy to process it into a thin film.
シート状の負極の製造方法としては、例えば、負極活物質を負極集電体上で加圧成型する方法；適当な有機溶剤を用いて負極活物質をペースト状にした後、当該ペーストを負極集電体に塗工し、乾燥した後に加圧して負極集電体に固着する方法；等が挙げられる。上記ペーストには、好ましくは上記導電剤および上記結着剤が含まれる。 As a method for producing a sheet-shaped negative electrode, for example, a method of press-molding a negative electrode active material on a negative electrode current collector; after making a negative electrode active material into a paste using an appropriate organic solvent, the paste is collected as a negative electrode. Examples thereof include a method in which the electric body is coated, dried, and then pressurized to be fixed to the negative electrode current collector. The paste preferably contains the conductive agent and the binder.
＜非水電解液＞
本発明の一実施形態に係る非水電解液二次電池における非水電解液は、一般に非水電解液二次電池に使用される非水電解液であれば特に限定されず、例えば、リチウム塩を有機溶媒に溶解してなる非水電解液を用いることができる。リチウム塩としては、例えば、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＣ（ＣＦ３ＳＯ２）３、Ｌｉ２Ｂ１０Ｃｌ１０、低級脂肪族カルボン酸リチウム塩およびＬｉＡｌＣｌ４等が挙げられる。上記リチウム塩は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。
<Non-aqueous electrolyte>
The non-aqueous electrolyte solution in the non-aqueous electrolyte secondary battery according to the embodiment of the present invention is not particularly limited as long as it is a non-aqueous electrolyte solution generally used in a non-aqueous electrolyte secondary battery, and is, for example, a lithium salt. A non-aqueous electrolyte solution prepared by dissolving the above in an organic solvent can be used. Examples of lithium salts include LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , Li 2 B 10 Cl. 10. Lower aliphatic carboxylic acid lithium salt and LiAlCl 4 and the like can be mentioned. Only one type of the lithium salt may be used, or two or more types may be used in combination.
非水電解液を構成する有機溶媒としては、例えば、カーボネート類、エーテル類、エステル類、ニトリル類、アミド類、カーバメート類および含硫黄化合物、並びにこれらの有機溶媒にフッ素基が導入されてなる含フッ素有機溶媒等が挙げられる。上記有機溶媒は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。 Examples of the organic solvent constituting the non-aqueous electrolyte solution include carbonates, ethers, esters, nitriles, amides, carbamates and sulfur-containing compounds, and a fluorine group introduced into these organic solvents. Fluorine organic solvent and the like can be mentioned. Only one type of the organic solvent may be used, or two or more types may be used in combination.
以下、実施例および比較例により、本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
［測定方法］
実施例１〜３および比較例１〜３にて製造された非水電解液二次電池用セパレータ（多孔質フィルム）の物性等を、以下の方法を用いて測定した。
[Measuring method]
The physical characteristics and the like of the separator (porous film) for the non-aqueous electrolytic solution secondary battery produced in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by using the following methods.
［空隙率］
（ａ）膜厚の測定
多孔質フィルムの膜厚を、株式会社ミツトヨ製の高精度デジタル測長機（ＶＬ−５０）を用いて測定した。
[Porosity]
(A) Measurement of film thickness The film thickness of the porous film was measured using a high-precision digital length measuring machine (VL-50) manufactured by Mitutoyo Co., Ltd.
（ｂ）重量目付の測定
多孔質フィルムから、一辺の長さ８ｃｍの正方形をサンプルとして切り取り、当該サンプルの重量Ｗ（ｇ）を測定した。そして、以下の式（２）に従い、多孔質フィルムの重量目付を算出した。
(B) Measurement of Weight Metsuke A square having a side length of 8 cm was cut out from the porous film as a sample, and the weight W (g) of the sample was measured. Then, the weight basis weight of the porous film was calculated according to the following formula (2).
重量目付（ｇ／ｍ２）＝Ｗ／（０．０８×０．０８） （２）
（ｃ）真密度の測定
多孔質フィルムを４ｍｍ角〜６ｍｍ角に切断し、３０℃以下で１７時間真空乾燥した後、乾式自動密度計（マイクロメリテックス社製 ＡｃｃｕＰｙｅII １３４０）を用いて、ヘリウムガス置換法により、当該多孔質フィルムの真密度を測定した。
Weight basis weight (g / m 2 ) = W / (0.08 x 0.08) (2)
(C) Measurement of true density A porous film is cut into 4 mm square to 6 mm square, vacuum dried at 30 ° C. or lower for 17 hours, and then helium gas is used using a dry automatic density meter (AccuPyeII 1340 manufactured by Micromeritex Co., Ltd.). The true density of the porous film was measured by the substitution method.
（ｄ）空隙率の算出
上記工程（ａ）〜（ｃ）にて算出・測定された多孔質フィルムの膜厚［μｍ］、重量目付［ｇ／ｍ２］および真密度［ｇ／ｍ３］から、以下の式（３）に基づき、当該多孔質フィルムの空隙率［％］を算出した。
(D) Calculation of porosity The film thickness [μm], weight scale [g / m 2 ] and true density [g / m 3 ] of the porous film calculated and measured in the above steps (a) to (c). Therefore, the porosity [%] of the porous film was calculated based on the following formula (3).
（空隙率）＝［１−（重量目付）／{（膜厚）×１０−６×１[ｍ２]×（真密度）}］×１００ （３）
［ガーレ値］
多孔質フィルムのガーレ値を、ＪＩＳ Ｐ８１１７に準拠して測定した。
(Porosity) = [1- (weight basis weight) / {(film thickness) x 10-6 x 1 [m 2 ] x (true density)}] x 100 (3)
[Gare value]
The galley value of the porous film was measured according to JIS P8117.
［緩和率］
後述の実施例および比較例においては、長尺の１次シートのＴＤ方向の両端を、ＭＤ方向に隣接する複数の把持部材によって把持した。よって、緩和率は下記式（１ｂ´）にて算出した。
[Relaxation rate]
In the examples and comparative examples described later, both ends of the long primary sheet in the TD direction were gripped by a plurality of gripping members adjacent to each other in the MD direction. Therefore, the relaxation rate was calculated by the following formula (1b').
緩和率（％）＝［｛（延伸工程前のＭＤ方向において隣接する把持部材間の距離）−（延伸工程後のＭＤ方向において隣接する把持部材間の距離）｝／（延伸工程前のＭＤ方向において隣接する把持部材間の距離）］×１００ （１ｂ´）
［空孔のくねり度］
多孔質フィルムの空孔における、当該多孔質フィルムの膜厚に対する実際の膜厚の経路長比（トーチオスティ）：τの値を、以下の式（４）に基づき算出し、その値を、多孔質フィルムにおける空孔のくねり度の値とした。
ｔＧｕｒ＝５．１８×１０−３ｓｅｃ（τ２Ｌ／εｄ） （４）
（式（４）において、ｔＧｕｒ：透気度（ガーレ値）［ｓｅｃ／ｉｎ２］（ｉｎ：インチ＝２．５４ｃｍ）、τ：トーチオスティ［無単位］、Ｌ：多孔質フィルムの膜厚［ｃｍ］、ε：多孔質フィルムの空隙率［比］およびｄ：多孔質フィルムにおける空孔の平均孔径［ｃｍ］である）
［突き刺し強度］
多孔質フィルムの突き刺し強度を、以下の（ｉ）および（ｉｉ）に示す方法にて測定した。
（ｉ）前記多孔質フィルムを１２ｍｍΦのワッシャで固定した後、ピン（ピン径１ｍｍΦ、先端０．５Ｒ）を、突き刺し速度：２００ｍｍ／ｍｉｎの条件にて、当該多孔質フィルムに突き刺した。
（ｉｉ）（ｉ）にて前記多孔質フィルムに前記ピンを突き刺したときの最大応力（ｇｆ）を測定し、その測定値をフィルムの突き刺し強度とした。
Relaxation rate (%) = [{(distance between adjacent gripping members in the MD direction before the stretching step)-(distance between adjacent gripping members in the MD direction after the stretching step)} / (MD direction before the stretching step) Distance between adjacent gripping members)] × 100 (1b ′)
[Ventilation degree of vacancies]
The value of the path length ratio (torchiosti) of the actual film thickness to the film thickness of the porous film in the pores of the porous film: τ is calculated based on the following formula (4), and the value is calculated based on the following formula (4). The value of the degree of bending of the pores in the film was used.
t Gur = 5.18 × 10 -3 sec (τ 2 L / εd) (4)
(In the formula (4), t Gur : air permeability (garle value) [sec / in 2 ] (in: inch = 2.54 cm), τ: torchosti [no unit], L: film thickness of porous film [ cm], ε: Porosity [ratio] of the porous film and d: Average pore diameter [cm] of the pores in the porous film)
[Puncture strength]
The piercing strength of the porous film was measured by the methods shown in (i) and (ii) below.
(I) After fixing the porous film with a washer of 12 mmΦ, a pin (pin diameter 1 mmΦ, tip 0.5R) was pierced into the porous film under the condition of piercing speed: 200 mm / min.
In (ii) and (i), the maximum stress (gf) when the pin was pierced into the porous film was measured, and the measured value was taken as the piercing strength of the film.
［実施例１］
超高分子量ポリエチレン粉末（固有粘度：２１ｄＬ／ｇ、粘度平均分子量３００万、東ソー株式会社製）６８重量％と、重量平均分子量１０００のポリエチレンワックス（ＦＮＰ−０１１５、日本精鑞社製）３２重量％とを準備した。この超高分子量ポリエチレンとポリエチレンワックスとの合計を１００重量部として、酸化防止剤（Ｉｒｇ１０１０、チバ・スペシャリティ・ケミカルズ社製）０．４重量部、酸化防止剤（Ｐ１６８、チバ・スペシャリティ・ケミカルズ社製）０．１重量部、および、ステアリン酸ナトリウム１．３重量部を加えた。さらに、得られた混合物の全体積に対して３８体積％となるように平均粒径０．１μｍの炭酸カルシウム（丸尾カルシウム社製）を加えた。これらを粉末のままヘンシェルミキサーで混合した後、二軸混練機で溶融混練してポリオレフィン樹脂組成物とした。
[Example 1]
Ultra-high molecular weight polyethylene powder (intrinsic viscosity: 21 dL / g, viscosity average molecular weight 3 million, manufactured by Tosoh Corporation) 68% by weight and polyethylene wax with weight average molecular weight 1000 (FNP-0115, manufactured by Nippon Seiko Co., Ltd.) 32% by weight And prepared. Taking the total of this ultra-high molecular weight polyethylene and polyethylene wax as 100 parts by weight, 0.4 parts by weight of an antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals) and an antioxidant (P168, manufactured by Ciba Specialty Chemicals). ) 0.1 parts by weight and 1.3 parts by weight of sodium stearate were added. Further, calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having an average particle size of 0.1 μm was added so as to be 38% by volume based on the total volume of the obtained mixture. These were mixed as powders with a Henschel mixer and then melt-kneaded with a twin-screw kneader to obtain a polyolefin resin composition.
当該ポリオレフィン樹脂組成物を一対のロールにてＭＤ方向に１．４倍の延伸倍率にて延伸し、シート状のポリオレフィン樹脂組成物を作製した。得られたシート状のポリオレフィン樹脂組成物を塩酸水溶液（塩酸４ｍｏｌ／Ｌ、非イオン系界面活性剤０．５重量％）に浸漬させることで前記炭酸カルシウムを除去し、１次シートを得た。続いて、得られた１次シートのＴＤ方向の両端を、ＭＤ方向に隣接する複数の把持部材によって把持した。１次シートを、ＭＤ方向に隣接する把持部材間の距離を縮めることによってＭＤ方向に緩和させながら、ＴＤ方向において対向する把持部材間の距離を広げることによってＴＤ方向に７倍の延伸倍率にて延伸し、膜厚１１μｍの多孔質フィルムを得た。得られた多孔質フィルムを非水電解液二次電池用セパレータ１とした。このとき、ＭＤ方向の緩和率は１０％であった。 The polyolefin resin composition was stretched with a pair of rolls in the MD direction at a stretching ratio of 1.4 times to prepare a sheet-shaped polyolefin resin composition. The obtained sheet-shaped polyolefin resin composition was immersed in an aqueous hydrochloric acid solution (hydrochloric acid 4 mol / L, nonionic surfactant 0.5% by weight) to remove the calcium carbonate to obtain a primary sheet. Subsequently, both ends of the obtained primary sheet in the TD direction were gripped by a plurality of gripping members adjacent to each other in the MD direction. The primary sheet is relaxed in the MD direction by reducing the distance between the gripping members adjacent in the MD direction, and at a stretching ratio of 7 times in the TD direction by increasing the distance between the gripping members facing each other in the TD direction. The film was stretched to obtain a porous film having a thickness of 11 μm. The obtained porous film was used as a separator 1 for a non-aqueous electrolyte secondary battery. At this time, the relaxation rate in the MD direction was 10%.
［実施例２］
ＭＤ方向の緩和率を２０％に変更したこと以外は、実施例１と同様にして、膜厚１０μｍの多孔質フィルムを得た。得られた多孔質フィルムを非水電解液二次電池用セパレータ２とした。
[Example 2]
A porous film having a film thickness of 10 μm was obtained in the same manner as in Example 1 except that the relaxation rate in the MD direction was changed to 20%. The obtained porous film was used as a separator 2 for a non-aqueous electrolyte secondary battery.
［実施例３］
ＭＤ方向の緩和率を３０％に変更したこと以外は、実施例１と同様にして、膜厚１１μｍの多孔質フィルムを得た。得られた多孔質フィルムを非水電解液二次電池用セパレータ３とした。
[Example 3]
A porous film having a film thickness of 11 μm was obtained in the same manner as in Example 1 except that the relaxation rate in the MD direction was changed to 30%. The obtained porous film was used as a separator 3 for a non-aqueous electrolyte secondary battery.
［比較例１］
ＭＤ方向の緩和率を０％に変更したこと以外は、実施例１と同様にして、膜厚１３μｍの多孔質フィルムを得た。得られた多孔質フィルムを非水電解液二次電池用セパレータ４とした。
[Comparative Example 1]
A porous film having a film thickness of 13 μm was obtained in the same manner as in Example 1 except that the relaxation rate in the MD direction was changed to 0%. The obtained porous film was used as a separator 4 for a non-aqueous electrolyte secondary battery.
［実施例４］
ＭＤ方向の緩和率を５０％に変更したこと以外は、実施例１と同様にして、膜厚１１μｍの多孔質フィルムを得た。得られた多孔質フィルムを非水電解液二次電池用セパレータ５とした。
[Example 4]
A porous film having a film thickness of 11 μm was obtained in the same manner as in Example 1 except that the relaxation rate in the MD direction was changed to 50%. The obtained porous film was used as a separator 5 for a non-aqueous electrolyte secondary battery.
［結論］
実施例１〜４および比較例１における緩和率、並びに、非水電解液二次電池用セパレータの物性値を、以下の表１に示す。
[Conclusion]
The relaxation rates in Examples 1 to 4 and Comparative Example 1 and the physical property values of the separator for a non-aqueous electrolyte secondary battery are shown in Table 1 below.
上記表１の記載から、実施例１〜４に記載の製造方法に得られた非水電解液二次電池用セパレータが、空孔のくねり度が好適な範囲に低減されている。ここで、実施例１〜４における非水電解液二次電池用セパレータの製造方法は、緩和処理を含み、本発明の一実施形態に係る要件を充足している。よって、本発明の一実施形態に係る非水電解液二次電池用セパレータの製造方法によれば、空孔のくねり度に優れる非水電解液二次電池用セパレータを製造できることが分かった。 From the description in Table 1 above, the degree of waviness of the pores of the separator for the non-aqueous electrolytic solution secondary battery obtained by the production methods described in Examples 1 to 4 is reduced to a suitable range. Here, the method for producing a separator for a non-aqueous electrolytic solution secondary battery in Examples 1 to 4 includes a relaxation treatment and satisfies the requirements according to an embodiment of the present invention. Therefore, it was found that according to the method for producing a separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention, a separator for a non-aqueous electrolyte secondary battery having an excellent degree of bending of pores can be produced.
また、実施例１〜３にて得られた非水電解液二次電池用セパレータは、実施例４にて得られた非水電解液二次電池用セパレータよりも、突き刺し強度が高い。よって、緩和処理を行う場合に、緩和率を５０％未満に抑えることによって、得られる非水電解液二次電池用セパレータの突き刺し強度の低下を抑制できることが分かった。 Further, the separators for non-aqueous electrolyte secondary batteries obtained in Examples 1 to 3 have higher piercing strength than the separators for non-aqueous electrolyte secondary batteries obtained in Example 4. Therefore, it was found that by suppressing the relaxation rate to less than 50% when performing the relaxation treatment, it is possible to suppress a decrease in the piercing strength of the obtained separator for a non-aqueous electrolyte secondary battery.
本発明の一態様は、空孔のくねり度に優れる非水電解液二次電池用セパレータを備える、電池性能に優れる非水電解液二次電池の製造に利用することができる。 One aspect of the present invention can be used for producing a non-aqueous electrolyte secondary battery having excellent battery performance, which comprises a separator for a non-aqueous electrolyte secondary battery having an excellent degree of bending of pores.
Claims (7)
緩和率（％）＝［｛（延伸工程前の１次シートの第１の方向の長さ）−（延伸工程後の１次シートの第１の方向の長さ）｝／（延伸工程前の１次シートの第１の方向の長さ）］×１００ （１） The method for producing a separator for a non-aqueous electrolytic solution secondary battery according to claim 1, wherein the relaxation rate represented by the following formula (1) in the shrinkage in the first direction is 5% or more and less than 50%. ..
Relaxation rate (%) = [{(length of primary sheet before stretching step in first direction)-(length of primary sheet after stretching step in first direction)} / (before stretching step) Length of primary sheet in first direction)] × 100 (1)
（ここで、前記ポリオレフィンの長鎖分岐度は、ＧＰＣ−ＭＡＬＳを使用したコンフォメーションプロットから計算した値である。） The method for producing a separator for a non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the polyolefin-based resin contains a polyolefin having a long-chain branching degree of 20 or less per molecule.
(Here, the degree of long-chain branching of the polyolefin is a value calculated from a conformation plot using GPC-MALS.)
正極、前記非水電解液二次電池用セパレータおよび負極をこの順に配置する工程を含む、非水電解液二次電池用部材の製造方法。 A step of obtaining a separator for a non-aqueous electrolyte secondary battery by the method for producing a separator for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 5, and a step of obtaining a separator for a non-aqueous electrolyte secondary battery.
A method for manufacturing a member for a non-aqueous electrolyte secondary battery, which comprises a step of arranging a positive electrode, a separator for the non-aqueous electrolyte secondary battery, and a negative electrode in this order.
正極、前記非水電解液二次電池用セパレータおよび負極をこの順に配置して、非水電解液二次電池用部材を得る工程、および
前記非水電解液二次電池用部材を容器の内部に入れ、次いで、前記容器の内部を非水電解液で満たした後、前記容器の内部を減圧しつつ、前記容器を密閉する工程を含む、非水電解液二次電池の製造方法。 A step of obtaining a separator for a non-aqueous electrolyte secondary battery by the method for producing a separator for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 5.
A step of arranging the positive electrode, the separator for the non-aqueous electrolyte secondary battery and the negative electrode in this order to obtain a member for the non-aqueous electrolyte secondary battery, and the member for the non-aqueous electrolyte secondary battery inside the container. A method for producing a non-aqueous electrolytic solution secondary battery, which comprises a step of filling the inside of the container with a non-aqueous electrolytic solution and then sealing the container while reducing the pressure inside the container.
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