JP5478733B2 - Nonaqueous electrolyte battery separator and nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte battery separator and nonaqueous electrolyte battery Download PDFInfo
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- JP5478733B2 JP5478733B2 JP2012538708A JP2012538708A JP5478733B2 JP 5478733 B2 JP5478733 B2 JP 5478733B2 JP 2012538708 A JP2012538708 A JP 2012538708A JP 2012538708 A JP2012538708 A JP 2012538708A JP 5478733 B2 JP5478733 B2 JP 5478733B2
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- separator
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- fine particles
- resistant
- porous layer
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- UBTITNUVKXQFBF-UHFFFAOYSA-N ethanesulfonic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CCS(O)(=O)=O UBTITNUVKXQFBF-UHFFFAOYSA-N 0.000 description 1
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- 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
Description
本発明は、高温時の信頼性に優れた非水電解液電池と、該非水電解液電池を構成し得るセパレータに関するものである。 The present invention relates to a non-aqueous electrolyte battery excellent in reliability at high temperatures and a separator that can constitute the non-aqueous electrolyte battery.
非水電解液電池の一種であるリチウムイオン二次電池は他の電池に比べてエネルギー密度が高く、また、メモリー効果も見られないことから、携帯電話やノート型パーソナルコンピュータなどの携帯機器用電源として幅広く利用されている。また、近年では、地球温暖化防止策として、ＣＯ2削減を推進する動きが世界規模で展開されているが、その一環として、例えば自動車業界において、電気自動車やハイブリッド電気自動車のモータ駆動用バッテリーとしてのリチウムイオン二次電池の開発が進められている。 Lithium ion secondary batteries, which are a type of non-aqueous electrolyte battery, have a higher energy density than other batteries and do not have a memory effect, so power supplies for mobile devices such as mobile phones and notebook personal computers Is widely used. In recent years, as a measure to prevent global warming, a movement to promote CO 2 reduction has been developed on a global scale. As a part of this, for example, in the automobile industry, as a battery for driving a motor of an electric vehicle or a hybrid electric vehicle. Development of lithium ion secondary batteries is underway.
現行のリチウムイオン二次電池では、正極と負極の間に介在させるセパレータとして、例えば厚みが１５〜３０μｍ程度のポリオレフィン系の多孔性フィルムが使用されている。また、セパレータの素材としては、電池の熱暴走温度以下でセパレータの構成樹脂を溶融させて空孔を閉塞させ、これにより電池の内部抵抗を上昇させて短絡の際などに電池の安全性を向上させる所謂シャットダウン効果を確保するため、融点の低いポリエチレンが適用されることがある。 In current lithium ion secondary batteries, a polyolefin-based porous film having a thickness of, for example, about 15 to 30 μm is used as a separator interposed between a positive electrode and a negative electrode. In addition, as separator material, the constituent resin of the separator is melted below the thermal runaway temperature of the battery to close the pores, thereby increasing the internal resistance of the battery and improving the safety of the battery in the event of a short circuit. In order to ensure the so-called shutdown effect, polyethylene having a low melting point may be applied.
こうしたセパレータとしては、例えば、多孔化と強度向上のために一軸延伸または二軸延伸したフィルムが用いられている。このようなセパレータは、単独で存在する膜として供給されるため、作業性などの点で一定の強度が要求され、これを前記延伸によって確保している。しかし、このような延伸フィルムでは結晶化度が増大しており、シャットダウン温度も、電池の熱暴走温度に近い温度にまで高まっているため、電池の安全性確保のためのマージンが十分とは言い難い。 As such a separator, for example, a uniaxially or biaxially stretched film is used to increase the porosity and improve the strength. Since such a separator is supplied as a single film, a certain strength is required in terms of workability and the like, and this is secured by the stretching. However, with such a stretched film, the degree of crystallinity has increased, and the shutdown temperature has increased to a temperature close to the thermal runaway temperature of the battery. Therefore, it can be said that the margin for ensuring the safety of the battery is sufficient. hard.
また、前記延伸によってフィルムにはひずみが生じており、これが高温に曝されると、残留応力によって収縮が起こるという問題がある。収縮温度は、シャットダウン温度と非常に近いところに存在する。このため、ポリオレフィン系の多孔性フィルムセパレータを使用するときには、充電異常時などに電池の温度がシャットダウン温度に達すると、セパレータの空孔を十分に閉塞させ電流を直ちに減少させて電池の温度上昇を防止しなければならない。セパレータの空孔が十分に閉塞せず電流を直ちに減少できなかった場合には、電池の温度は容易にセパレータの収縮温度にまで上昇するため、内部短絡による異常発熱の危険性があるからである。 In addition, the film is distorted by the stretching, and there is a problem that when it is exposed to a high temperature, shrinkage occurs due to residual stress. The shrinkage temperature is very close to the shutdown temperature. For this reason, when using a polyolefin-based porous film separator, if the battery temperature reaches the shutdown temperature, such as when there is a charging abnormality, the separator vacancies are sufficiently closed, and the current is immediately reduced to increase the battery temperature. Must be prevented. This is because if the separator holes are not sufficiently closed and the current cannot be reduced immediately, the battery temperature easily rises to the shrinkage temperature of the separator, and there is a risk of abnormal heat generation due to an internal short circuit. .
このようなセパレータの熱収縮による短絡を防止し、電池の信頼性を高める技術として、例えば、ベースとなる樹脂製の多孔質膜（微多孔膜）の表面に耐熱性の高い層を形成した多層構造のセパレータが提案されている（例えば、特許文献１〜５）。
As a technique for preventing such a short circuit due to thermal contraction of the separator and improving the reliability of the battery, for example, a multilayer in which a layer having high heat resistance is formed on the surface of a resin porous film (microporous film) serving as a base Structured separators have been proposed (for example,
また、リチウムイオン二次電池では、例えば製造工程において異物が混入することがあり、このような場合に、異物による圧力によってセパレータに小さな孔が形成されて内部短絡が起こり、電池の発熱が引き起こされる虞がある。特に、ポリオレフィン系の多孔性フィルムセパレータは局所的な発熱に弱く、セパレータの短絡箇所近傍が、短絡電流によって生じる発熱で破膜し、内部短絡が拡大して電池が危険に晒される虞がある。 In addition, in a lithium ion secondary battery, for example, foreign matter may be mixed in the manufacturing process. In such a case, a small hole is formed in the separator due to the pressure of the foreign matter, causing an internal short circuit, which causes heat generation of the battery. There is a fear. In particular, the polyolefin-based porous film separator is vulnerable to local heat generation, and the vicinity of the short-circuited portion of the separator is broken by heat generated by the short-circuit current, so that the internal short circuit is enlarged and the battery may be exposed to danger.
そこで、こうした問題を解決し、電池の信頼性を高める技術として、正極の表面にカルボキシメチルセルロースの薄膜を形成した電池（特許文献６）や、集電体上に絶縁物を有し、且つこの絶縁物の上に活物質を設けた領域と設けない領域とを形成した電極を用いた電池（特許文献７）が提案されている。 Therefore, as a technique for solving these problems and improving the reliability of the battery, a battery (Patent Document 6) in which a thin film of carboxymethylcellulose is formed on the surface of the positive electrode, an insulator on the current collector, and this insulation There has been proposed a battery (Patent Document 7) using an electrode in which a region where an active material is provided and a region where no active material is provided on an object.
また、電極活物質粒子の表面に架橋高分子コーティング層を形成して、電池の安全性向上と電池性能の低下抑制とを図る技術も提案されている（特許文献８）。 In addition, a technique has been proposed in which a cross-linked polymer coating layer is formed on the surface of electrode active material particles to improve battery safety and suppress battery performance degradation (Patent Document 8).
更に、シャットダウン特性の確保と強度向上とを図るために、シャットダウン特性を確保するための遮断層の両面を、微細多孔質の強度層で挟んだ構成のセパレータも提案されている（特許文献９）。 Furthermore, in order to secure shutdown characteristics and improve strength, a separator having a structure in which both sides of a blocking layer for securing shutdown characteristics are sandwiched between fine porous strength layers has been proposed (Patent Document 9). .
特許文献１〜９の技術によれば、各種の異常事態に遭遇しても、熱暴走などの問題が生じ難い高い信頼性を有する電池を提供することができる。
According to the techniques of
ところで、特に前記のような大容量で高出力型のリチウムイオン二次電池の場合には、従来のリチウムイオン二次電池にも増して信頼性の向上が要求される。 By the way, especially in the case of the large capacity and high output type lithium ion secondary battery as described above, it is required to improve the reliability as compared with the conventional lithium ion secondary battery.
例えば、特許文献５に記載されているように、シャットダウン機能層として作用する樹脂多孔質膜の表面に、耐熱性微粒子を含有する耐熱層を設けることで、１５０℃程度の温度でのセパレータの形状安定性を高め、その熱収縮を抑えることが可能である。
For example, as described in
しかしながら、その一方で、これを上回る温度（例えば２００℃程度）でのセパレータの熱収縮を抑え、その形状安定性を高めることは必ずしも容易ではなく、電池内がこのような温度となった際の安全性や信頼性を確保する点に関しては、特許文献５に記載の技術も未だ改善の余地を残している。
However, on the other hand, it is not always easy to suppress the thermal shrinkage of the separator at a temperature higher than this (for example, about 200 ° C.) and to improve its shape stability. In terms of ensuring safety and reliability, the technique described in
その一方で、例えば、特許文献９のように、多数の機能層を形成する手法で、高温下でのセパレータの形状安定性を高めることも考えられるが、その場合、セパレータの製造工程が増大して、製造が煩雑となったり、セパレータ全体が厚くなるために電池容量の低下を引き起こす問題がある。 On the other hand, for example, it is conceivable to increase the shape stability of the separator at a high temperature by a method of forming a large number of functional layers as in Patent Document 9, but in that case, the manufacturing process of the separator increases. Thus, there is a problem that the manufacturing becomes complicated and the whole separator becomes thick, which causes a decrease in battery capacity.
こうしたことから、耐熱性を高めるための機能層を単一層にしてセパレータの厚みの増大を抑えつつ、電池の信頼性をより高め得る技術の開発が求められる。 For these reasons, there is a need for the development of a technology that can further improve the reliability of the battery while suppressing an increase in the thickness of the separator by using a single functional layer for improving heat resistance.
本発明は前記事情に鑑みてなされたものであり、厚みの増大を抑制しつつ優れた耐熱性を確保し得る非水電解液電池用のセパレータと、該セパレータを用いており、高い信頼性を有する非水電解液電池を提供することにある。 The present invention has been made in view of the above circumstances, and uses a separator for a nonaqueous electrolyte battery capable of ensuring excellent heat resistance while suppressing an increase in thickness, and uses the separator, and has high reliability. It is providing the nonaqueous electrolyte battery which has.
本発明の非水電解液電池用セパレータは、樹脂多孔質膜と、前記樹脂多孔質膜の表面に配置された耐熱多孔質層とを含む非水電解液電池用セパレータであって、前記樹脂多孔質膜は、融解温度が８０〜１８０℃のポリオレフィンを主成分とする樹脂から形成され、前記耐熱多孔質層は、加熱により非水電解液を吸収して膨潤する膨潤性微粒子と、耐熱性微粒子と、バインダーとを含み、前記膨潤性微粒子と前記耐熱性微粒子との体積比率が、３０：７０〜７０：３０であり、前記バインダーは、Ｎ−ビニルアセトアミド系ポリマーを含み、前記膨潤性微粒子と前記耐熱性微粒子の合計量を１００質量部としたとき、前記Ｎ−ビニルアセトアミド系ポリマーの含有量が、０．１質量部以上であり、前記セパレータの構成成分の全体積中における全ての樹脂の比率が、５０〜９９．９体積％であり、前記耐熱多孔質層の厚みが、２〜１０μｍであることを特徴とする。
The separator for a non-aqueous electrolyte battery of the present invention is a separator for a non-aqueous electrolyte battery including a resin porous membrane and a heat-resistant porous layer disposed on the surface of the resin porous membrane, wherein the resin porous The membrane is formed from a resin whose main component is a polyolefin having a melting temperature of 80 to 180 ° C., and the heat-resistant porous layer includes swellable fine particles that swell by absorbing a non-aqueous electrolyte by heating, and heat-resistant fine particles And a binder, wherein the volume ratio of the swellable fine particles and the heat-resistant fine particles is 30:70 to 70:30 , and the binder contains an N-vinylacetamide-based polymer, When the total amount of the heat-resistant fine particles is 100 parts by mass, the content of the N-vinylacetamide-based polymer is 0.1 parts by mass or more, and the total volume of the constituent components of the separator is The ratio of all the resins is 50 to 99.9% by volume, and the heat-resistant porous layer has a thickness of 2 to 10 μm.
また、本発明の非水電解液電池は、正極、負極、セパレータおよび非水電解液を含み、前記セパレータが、上記本発明の非水電解液電池用セパレータであることを特徴とする。 The non-aqueous electrolyte battery of the present invention includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, and the separator is the separator for non-aqueous electrolyte batteries of the present invention.
本発明によれば、厚みの増大を抑制しつつ優れた耐熱性を確保し得る非水電解液電池用セパレータと、該セパレータを用いており、高い信頼性を有する非水電解液電池を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the separator for nonaqueous electrolyte batteries which can ensure the outstanding heat resistance, suppressing the increase in thickness, and the nonaqueous electrolyte battery which uses this separator and has high reliability are provided. be able to.
（実施形態１）
先ず、本発明の非水電解液電池用セパレータ（以下、単に「セパレータ」という。）について説明する。本発明のセパレータは、樹脂多孔質膜と、前記樹脂多孔質膜の表面に配置された耐熱多孔質層とを備えている。即ち、本発明のセパレータは、樹脂多孔質膜の少なくとも片面に耐熱多孔質層を有している。
(Embodiment 1)
First, the non-aqueous electrolyte battery separator of the present invention (hereinafter simply referred to as “separator”) will be described. The separator of this invention is equipped with the resin porous membrane and the heat resistant porous layer arrange | positioned on the surface of the said resin porous membrane. That is, the separator of the present invention has a heat resistant porous layer on at least one surface of the resin porous membrane.
本発明のセパレータにおいて、樹脂多孔質膜は、正極と負極との短絡を防止しつつ、イオンを透過するセパレータ本来の機能を有する層である。 In the separator of the present invention, the resin porous membrane is a layer having an original function of transmitting a separator while preventing a short circuit between the positive electrode and the negative electrode.
詳しくは後述するように、樹脂多孔質膜には、例えば、通常のリチウムイオン二次電池などの非水電解液電池用のセパレータと同様に、ポリオレフィンを主成分とする微多孔膜が使用されるが、このような樹脂多孔質膜は、前述の通り、高温環境下で収縮しやすく、高温下での形状安定性が劣っている。 As will be described in detail later, for example, a microporous membrane mainly composed of polyolefin is used for the resin porous membrane, similarly to a separator for a non-aqueous electrolyte battery such as a normal lithium ion secondary battery. However, as described above, such a porous resin membrane is likely to shrink under a high temperature environment and has poor shape stability under high temperature.
本発明のセパレータは、前記のような高温下での形状安定性に劣る樹脂（樹脂多孔質膜に含まれる樹脂、耐熱多孔質層に含まれる膨潤性微粒子およびバインダーを含めた、セパレータに含まれる全ての樹脂）の比率を、セパレータの構成成分の全体積中（空孔部分を除く全体積中。以下同じ。）５０〜９９．９体積％として、その比率が非常に大きい構成とし、樹脂多孔質膜の少なくとも片面に、特定の膨潤性微粒子と耐熱性微粒子とバインダーとを特定の組成比で含有する薄い耐熱多孔質層を形成することで、全体の厚みの増大を抑えつつ、例えば２００℃といった高温での形状安定性を高めており、これにより、従来にも増して高温下での信頼性および安全性の高い非水電解液電池（本発明の非水電解液電池）の提供を可能としている。 The separator of the present invention is contained in a separator including a resin having poor shape stability at a high temperature as described above (including a resin contained in a resin porous membrane, a swellable fine particle contained in a heat resistant porous layer, and a binder). The ratio of (all resins) is 50 to 99.9% by volume in the total volume of the constituent components of the separator (in the total volume excluding the void portion; the same applies hereinafter), and the ratio is very large. By forming a thin heat-resistant porous layer containing specific swellable fine particles, heat-resistant fine particles, and a binder in a specific composition ratio on at least one surface of the membrane, for example, 200 ° C. while suppressing an increase in the overall thickness It is possible to provide a non-aqueous electrolyte battery (non-aqueous electrolyte battery of the present invention) that is more reliable and safer at high temperatures than ever before. It is said.
本発明のセパレータに係る耐熱多孔質層の含有する膨潤性微粒子は、通常、電池が使用される温度領域（およそ７０℃以下）では、電池の有する非水電解液を吸収しないかまたは吸収量が限られており、従って膨潤の度合いが一定以下であるが、電池内が異常に発熱した際に非水電解液を吸収して大きく膨潤し且つ温度上昇と共に膨潤度が増大するような性質を有する樹脂から形成される。本発明のセパレータを用いた電池は、通常に使用される温度領域においては、膨潤性微粒子に吸収されない流動可能な非水電解液がセパレータの空孔内に存在するため、セパレータ内部のＬｉ（リチウム）イオンの伝導性が高くなり、良好な特性を有する電池となる。しかし、温度上昇に伴って膨潤度が増大する性質が現れる温度以上に加熱された場合には、耐熱多孔質層に含まれる膨潤性微粒子が、電池内の非水電解液を吸収して膨潤し、セパレータの空孔内部に存在する流動可能な非水電解液、およびセパレータと正極との界面の非水電解液が減少するため、正極と非水電解液の熱暴走反応を良好に抑制できる。 The swellable fine particles contained in the heat-resistant porous layer according to the separator of the present invention usually do not absorb or absorb the non-aqueous electrolyte contained in the battery in the temperature range (approximately 70 ° C. or lower) in which the battery is used. Therefore, the degree of swelling is below a certain level, but when the inside of the battery is abnormally heated, it absorbs the non-aqueous electrolyte and swells greatly, and the degree of swelling increases as the temperature rises. Formed from resin. In the battery using the separator of the present invention, in a temperature range that is normally used, a flowable non-aqueous electrolyte that is not absorbed by the swellable fine particles exists in the pores of the separator. ) The ion conductivity is increased, and the battery has good characteristics. However, when heated above the temperature at which the degree of swelling increases as the temperature rises, the swellable fine particles contained in the heat-resistant porous layer absorb the nonaqueous electrolyte in the battery and swell. Since the flowable non-aqueous electrolyte present in the pores of the separator and the non-aqueous electrolyte at the interface between the separator and the positive electrode are reduced, the thermal runaway reaction between the positive electrode and the non-aqueous electrolyte can be satisfactorily suppressed.
膨潤性微粒子において、温度上昇に伴って膨潤度が増大する性質（以下、「熱膨潤性」という。）を示し始める温度は、７０℃以上であることが好ましく、７５℃以上であることがより好ましい。膨潤性微粒子が熱膨潤性を示し始める温度が低すぎると、通常の使用温度域における電池内でのＬｉイオンの伝導性が低くなりすぎて、機器の使用に支障をきたす場合が生じることがある。また、膨潤性微粒子が熱膨潤性を示し始める温度が高すぎると、電池内での正極と非水電解液との熱暴走反応の抑制作用が発現する温度が高くなりすぎて、電池の安全性および信頼性の向上効果が小さくなる虞がある。よって、膨潤性微粒子において、熱膨潤性を示し始める温度は、１５０℃以下であることが好ましく、１４５℃以下であることがより好ましい。 In the swellable fine particles, the temperature at which the degree of swelling increases with increasing temperature (hereinafter referred to as “thermal swellability”) is preferably 70 ° C. or higher, more preferably 75 ° C. or higher. preferable. If the temperature at which the swellable microparticles begin to exhibit thermal swellability is too low, the Li ion conductivity in the battery in the normal operating temperature range may become too low, which may hinder the use of the device. . Also, if the temperature at which the swellable microparticles begin to exhibit thermal swellability is too high, the temperature at which the effect of suppressing the thermal runaway reaction between the positive electrode and the non-aqueous electrolyte in the battery becomes too high, and the battery safety In addition, the reliability improvement effect may be reduced. Therefore, in the swellable fine particles, the temperature at which the thermal swellability starts to be exhibited is preferably 150 ° C. or less, and more preferably 145 ° C. or less.
耐熱多孔質層が含有する膨潤性微粒子としては、２５℃において測定される非水電解液（電池の有する非水電解液）の吸液量が、膨潤性微粒子１ｇあたり、１．５ｍＬ以下であることが好ましく、１ｍＬ以下であることがより好ましい。 As the swellable fine particles contained in the heat-resistant porous layer, the liquid absorption amount of the nonaqueous electrolyte solution (nonaqueous electrolyte solution possessed by the battery) measured at 25 ° C. is 1.5 mL or less per 1 g of the swellable fine particles. Preferably, it is 1 mL or less.
膨潤性微粒子が温度上昇により膨潤するメカニズムについては、詳細は明らかではないが、例えば、膨潤性微粒子の一例として挙げられる架橋ポリメチルメタクリレート（架橋ＰＭＭＡ）では、粒子の主体をなす架橋ＰＭＭＡのガラス転移点（Ｔｇ）が１００℃付近にあるため、１００℃付近になった際に架橋ＰＭＭＡ粒子が柔軟になって、より多くの非水電解液を吸収して膨潤するといったメカニズムが考えられる。よって、膨潤性微粒子のＴｇは、例えば５０℃以上（より好ましくは８０℃以上）１３０℃以下であることが好ましいと考えられる。そして、膨潤性微粒子は、１３０℃において測定される非水電解液（電池の有する非水電解液）の吸液量が、膨潤性微粒子１ｇあたり、２ｍＬ以上であることが好ましい。 Although the details of the mechanism by which the swellable fine particles swell due to temperature rise are not clear, for example, in the case of cross-linked polymethyl methacrylate (cross-linked PMMA), which is an example of the swellable fine particles, the glass transition of the cross-linked PMMA that forms the main component of the particles Since the point (Tg) is in the vicinity of 100 ° C., a mechanism may be considered in which the cross-linked PMMA particles become flexible when the temperature reaches about 100 ° C., and more non-aqueous electrolyte solution is absorbed and swollen. Therefore, it is considered that the Tg of the swellable fine particles is preferably, for example, 50 ° C. or higher (more preferably 80 ° C. or higher) and 130 ° C. or lower. And as for swellable microparticles | fine-particles, it is preferable that the liquid absorption amount of the nonaqueous electrolyte solution (nonaqueous electrolyte solution which a battery has) measured at 130 degreeC is 2 mL or more per g of swellable microparticles | fine-particles.
本明細書でいう「膨潤性微粒子の２５℃における非水電解液の吸収量」は、以下のようにして求められる値である。膨潤性微粒子（水分散体の場合は、それを１日常温で乾燥させたもの）を乳鉢および乳棒を用いて十分に粉砕して粉末とする。この粉末０．３ｇをガラス製容器に入れ、ここに、非水電解液（電池に使用する非水電解液）５ｍＬを加え、前記粉末を非水電解液中に２５℃で２４時間浸漬させる。その後、２５μｍ金属メッシュで濾過して粉末と非水電解液とを分離し、得られた非水電解液（前記粉末に吸収されなかった非水電解液）の量を測定し、前記ガラス製容器に入れた非水電解液の量との差から、膨潤性微粒子の２５℃における非水電解液の吸収量を求める。 The “absorption amount of the non-aqueous electrolyte at 25 ° C. of the swellable fine particles” referred to in the present specification is a value determined as follows. Swellable fine particles (in the case of an aqueous dispersion, those dried for 1 day at room temperature) are sufficiently ground using a mortar and pestle to form a powder. 0.3 g of this powder is put in a glass container, 5 mL of a non-aqueous electrolyte (non-aqueous electrolyte used in a battery) is added thereto, and the powder is immersed in the non-aqueous electrolyte at 25 ° C. for 24 hours. Thereafter, the powder and the non-aqueous electrolyte are separated by filtration through a 25 μm metal mesh, the amount of the obtained non-aqueous electrolyte (the non-aqueous electrolyte not absorbed by the powder) is measured, and the glass container From the difference from the amount of the non-aqueous electrolyte solution put in, the absorption amount of the non-aqueous electrolyte solution at 25 ° C. of the swellable fine particles is obtained.
また、本明細書でいう「膨潤性微粒子の１３０℃における非水電解液の吸収量」は、以下のようにして求められる値である。２５℃での吸収量測定の場合と同様にして得られた膨潤性微粒子の粉末０．３ｇをガラス製容器に入れ、ここに、非水電解液（電池に使用する非水電解液）５ｍＬを加え、前記粉末を非水電解液中に２５℃で２４時間浸漬させる。その後、ガラス製容器内の非水電解液を１３０℃に加熱し、１３０℃に保った状態で２５μｍ金属メッシュで濾過して粉末と非水電解液とを分離し、得られた非水電解液（前記粉末に吸収されなかった非水電解液）の量を測定し、前記ガラス製容器に入れた非水電解液の量との差から、膨潤性微粒子の１３０℃における非水電解液の吸収量を求める。 Further, the “absorption amount of the non-aqueous electrolyte solution at 130 ° C. of the swellable fine particles” referred to in the present specification is a value obtained as follows. In a glass container, 0.3 g of a swellable fine particle powder obtained in the same manner as in the case of measuring the amount of absorption at 25 ° C. is added, and 5 mL of a non-aqueous electrolyte (non-aqueous electrolyte used in a battery) is added here. In addition, the powder is immersed in a non-aqueous electrolyte at 25 ° C. for 24 hours. Thereafter, the non-aqueous electrolyte in the glass container is heated to 130 ° C., and filtered with a 25 μm metal mesh while maintaining the temperature at 130 ° C. to separate the powder from the non-aqueous electrolyte, and the obtained non-aqueous electrolyte The amount of (non-aqueous electrolyte not absorbed by the powder) was measured, and from the difference from the amount of non-aqueous electrolyte placed in the glass container, the absorption of the non-aqueous electrolyte at 130 ° C. of the swellable fine particles Find the amount.
前記の方法による２５℃の吸収量測定および１３０℃の吸収量測定では、濾過に伴う非水電解液のロスや、加熱時の非水電解液溶媒の揮発によるロス（１３０℃の吸収量測定の場合）が生じ得る。よって、前記の各吸収量は、いずれも、予め非水電解液のみについて前記の各操作を行って測定したロス量を用いて補正する。 In the absorption measurement at 25 ° C. and the absorption measurement at 130 ° C. by the above method, the loss of the non-aqueous electrolyte due to filtration and the loss due to the volatilization of the non-aqueous electrolyte solvent during heating (measurement of absorption at 130 ° C. Case) may occur. Therefore, each of the above absorption amounts is corrected using the loss amount measured by performing each of the above operations on only the non-aqueous electrolyte.
また、本明細書でいう膨潤性微粒子のガラス転移点（Ｔｇ）は、日本工業規格（ＪＩＳ）Ｋ ７１２１の規定に準じて、示差走査熱量計（ＤＳＣ）を用いて測定される値である。 The glass transition point (Tg) of the swellable fine particles referred to in the present specification is a value measured using a differential scanning calorimeter (DSC) in accordance with the provisions of Japanese Industrial Standard (JIS) K7121.
膨潤性微粒子を構成する材料は、耐熱性および電気絶縁性を有しており、非水電解液に対して安定であり、更に、電池の作動電圧範囲において酸化還元されにくい電気化学的に安定な材料が好ましく、そのような材料としては、例えば、樹脂架橋体が挙げられる。より具体的には、スチレン樹脂［ポリスチレン（ＰＳ）など］、スチレン・ブタジエンゴム（ＳＢＲ）、アクリル樹脂（ＰＭＭＡなど）、ポリアルキレンオキシド［ポリエチレンオキシド（ＰＥＯ）など］、フッ素樹脂（ＰＶＤＦなど）、およびこれらの誘導体よりなる群から選ばれる少なくとも１種の樹脂の架橋体；尿素樹脂；ポリウレタン；などが例示できる。膨潤性微粒子には、前記例示の樹脂を１種単独で用いてもよく、２種以上を併用してもよい。また、膨潤性微粒子は、必要に応じて、樹脂に添加される公知の各種添加剤、例えば、酸化防止剤などを含有していても構わない。 The material constituting the swellable fine particles has heat resistance and electrical insulation, is stable to non-aqueous electrolyte, and is electrochemically stable that is not easily oxidized and reduced in the operating voltage range of the battery. A material is preferable, and examples of such a material include a crosslinked resin. More specifically, styrene resin [polystyrene (PS), etc.], styrene-butadiene rubber (SBR), acrylic resin (PMMA, etc.), polyalkylene oxide [polyethylene oxide (PEO), etc.], fluororesin (PVDF, etc.), And a crosslinked product of at least one resin selected from the group consisting of these and derivatives thereof; urea resin; polyurethane; and the like. In the swellable fine particles, the above-exemplified resins may be used alone or in combination of two or more. Further, the swellable fine particles may contain various known additives added to the resin, for example, an antioxidant, if necessary.
前記膨潤性微粒子の構成材料の中でも、スチレン樹脂架橋体、アクリル樹脂架橋体およびフッ素樹脂架橋体が好ましく、架橋ＰＭＭＡが特に好ましい。 Among the constituent materials of the swellable fine particles, crosslinked styrene resin, crosslinked acrylic resin, and crosslinked fluororesin are preferable, and crosslinked PMMA is particularly preferable.
膨潤性微粒子の平均粒子径は、０．０５μｍ以上であることが好ましく、０．１μｍ以上であることがより好ましく、０．２μｍ以上であることが更に好ましく、また、３μｍ以下であることが好ましく、２μｍ以下であることがより好ましい。詳しくは後述するが、耐熱多孔質層は、その構成成分を媒体に分散または溶解させた耐熱多孔質層形成用組成物を用いて形成することが好ましい。その場合、膨潤性微粒子の平均粒子径が小さすぎると、その表面積が大きくなって膨潤性微粒子同士が凝集しやすくなり、耐熱多孔質層形成用組成物の媒体に良好に分散させにくくなる虞がある。また、膨潤性微粒子の平均粒子径が大きすぎると、耐熱多孔質層中のリチウムイオンの運動をセパレータの全面で均一にし難くなり、電池の充放電時のリチウムイオンの移動障壁となる虞がある。 The average particle size of the swellable fine particles is preferably 0.05 μm or more, more preferably 0.1 μm or more, further preferably 0.2 μm or more, and preferably 3 μm or less. More preferably, it is 2 μm or less. As will be described in detail later, the heat-resistant porous layer is preferably formed using a heat-resistant porous layer forming composition in which the constituent components are dispersed or dissolved in a medium. In that case, if the average particle diameter of the swellable fine particles is too small, the surface area becomes large and the swellable fine particles are likely to aggregate with each other, which may make it difficult to disperse well in the medium of the heat-resistant porous layer forming composition. is there. In addition, if the average particle size of the swellable fine particles is too large, it is difficult to make the movement of lithium ions in the heat resistant porous layer uniform over the entire surface of the separator, which may cause a lithium ion migration barrier during battery charge / discharge. .
本明細書でいう微粒子（膨潤性微粒子および後記の耐熱性微粒子）の平均粒子径は、例えば、レーザー散乱粒度分布計（例えば、ＨＯＲＩＢＡ社製「ＬＡ−９２０」）を用い、微粒子を溶解したり、微粒子が膨潤したりしない媒体に、微粒子を分散させて測定した体積基準の積算分率における５０％での粒径（Ｄ５０）として規定することができる。 The average particle size of the fine particles (swellable fine particles and heat-resistant fine particles described later) referred to in the present specification is obtained by, for example, dissolving the fine particles using a laser scattering particle size distribution meter (for example, “LA-920” manufactured by HORIBA). The particle size (D50) at 50% of the volume-based integrated fraction measured by dispersing the fine particles in a medium in which the fine particles do not swell can be defined.
耐熱多孔質層は、前記の膨潤性微粒子とともに耐熱性微粒子を含有するが、本明細書でいう耐熱性微粒子における「耐熱性」とは、少なくとも２００℃において変形などの形状変化が目視で確認されないことを意味している。また、耐熱性微粒子の有する耐熱温度は、３００℃以上であることが好ましい。本明細書でいう耐熱性微粒子の有する「耐熱温度」とは、その温度において変形などの形状変化が目視で確認されない温度を意味している。 The heat-resistant porous layer contains heat-resistant fine particles together with the above-mentioned swellable fine particles, but “heat resistance” in the heat-resistant fine particles referred to in the present specification does not visually confirm a shape change such as deformation at least at 200 ° C. It means that. Further, the heat resistant temperature of the heat resistant fine particles is preferably 300 ° C. or higher. The “heat-resistant temperature” of the heat-resistant fine particles referred to in the present specification means a temperature at which no shape change such as deformation is visually confirmed.
耐熱性微粒子としては、電気絶縁性を有しており、電気化学的に安定で、更に後述する非水電解液や、耐熱多孔質層形成用組成物に用いる媒体に安定であり、高温状態で非水電解液に溶解しないものであれば、特に制限はない。 The heat-resistant fine particles have electrical insulating properties, are electrochemically stable, and are stable to a medium used for a non-aqueous electrolyte and a heat-resistant porous layer forming composition, which will be described later. There is no particular limitation as long as it does not dissolve in the non-aqueous electrolyte.
このような耐熱性微粒子の具体例としては、例えば、酸化鉄、ＳｉＯ2（シリカ）、Ａｌ2Ｏ3（アルミナ）、ＴｉＯ2、ＢａＴｉＯ3、ＺｒＯ2などの酸化物微粒子；窒化アルミニウム、窒化ケイ素などの窒化物微粒子；フッ化カルシウム、フッ化バリウム、硫酸バリウムなどの難溶性のイオン結晶微粒子；シリコン、ダイヤモンドなどの共有結合性結晶微粒子；タルク、モンモリロナイトなどの粘土微粒子；ベーマイト、ゼオライト、アパタイト、カオリン、ムライト、スピネル、オリビン、セリサイト、ベントナイトなどの鉱物資源由来物質またはそれらの人造物；などの無機微粒子が挙げられる。また、金属微粒子；ＳｎＯ2、スズ−インジウム酸化物（ＩＴＯ）などの酸化物微粒子；カーボンブラック、グラファイトなどの炭素質微粒子；などの導電性微粒子の表面を、電気絶縁性を有する材料（例えば、前記の電気絶縁性の耐熱性微粒子を構成する材料など）で表面処理することで、電気絶縁性を持たせた微粒子であってもよい。耐熱性微粒子には、これらを１種単独で用いてもよく、２種以上を併用してもよい。耐熱性微粒子としては、シリカ、アルミナ、ベーマイトがより好ましく、ベーマイトが特に好ましい。 Specific examples of such heat-resistant fine particles include, for example, oxide fine particles such as iron oxide, SiO 2 (silica), Al 2 O 3 (alumina), TiO 2 , BaTiO 3 , ZrO 2 ; aluminum nitride, silicon nitride Nitride fine particles such as: Calcium fluoride, barium fluoride, barium sulfate and other poorly soluble ionic crystal fine particles; silicon, diamond and other covalently bonded crystal fine particles; talc, montmorillonite and other clay fine particles; boehmite, zeolite, apatite, Inorganic fine particles such as kaolin, mullite, spinel, olivine, sericite, bentonite and other mineral resource-derived substances or artificial products thereof. Further, the surface of the conductive fine particles such as metal fine particles; oxide fine particles such as SnO 2 and tin-indium oxide (ITO); carbonaceous fine particles such as carbon black and graphite; It may be fine particles that have been made electrically insulating by surface treatment with the above-mentioned materials constituting the electrically insulating heat-resistant fine particles. These heat resistant fine particles may be used alone or in combination of two or more. As the heat-resistant fine particles, silica, alumina, and boehmite are more preferable, and boehmite is particularly preferable.
耐熱性微粒子の形状については特に制限はなく、球状、粒子状、板状など、いずれの形状であってもよい。 The shape of the heat-resistant fine particle is not particularly limited, and may be any shape such as a spherical shape, a particle shape, or a plate shape.
耐熱性微粒子の平均粒子径（一次粒子の平均粒子径）は、０．０５μｍ以上であることが好ましく、０．１μｍ以上であることがより好ましく、０．２μｍ以上であることが更に好ましく、また、３μｍ以下であることが好ましく、２μｍ以下であることがより好ましい。耐熱性微粒子の平均粒子径が小さすぎると、その表面積が大きくなって耐熱性微粒子同士が凝集しやすくなり、耐熱多孔質層形成用組成物の媒体に良好に分散させにくくなる虞がある。また、耐熱性微粒子の平均粒子径が大きすぎると、耐熱多孔質層中のリチウムイオンの運動をセパレータの全面で均一にし難くなり、電池の充放電時のリチウムイオンの移動障壁となる虞がある。 The average particle size of the heat-resistant fine particles (average particle size of primary particles) is preferably 0.05 μm or more, more preferably 0.1 μm or more, still more preferably 0.2 μm or more, It is preferably 3 μm or less, and more preferably 2 μm or less. If the average particle diameter of the heat-resistant fine particles is too small, the surface area becomes large and the heat-resistant fine particles are likely to aggregate with each other, which may make it difficult to disperse them well in the medium of the heat-resistant porous layer forming composition. In addition, if the average particle size of the heat-resistant fine particles is too large, it is difficult to make the movement of lithium ions in the heat-resistant porous layer uniform across the entire surface of the separator, which may cause a lithium ion migration barrier during battery charge / discharge. .
本発明のセパレータに係る耐熱多孔質層は、膨潤性微粒子や耐熱性微粒子といった微粒子同士の密着性を高めたり、耐熱多孔質層と樹脂多孔質膜との密着性を高めたりするために、バインダーを含有している。 The heat-resistant porous layer according to the separator of the present invention is a binder for increasing the adhesion between fine particles such as swellable fine particles and heat-resistant fine particles, and improving the adhesion between the heat-resistant porous layer and the resin porous membrane. Contains.
バインダーには、Ｎ−ビニルアセトアミド系ポリマーを使用する。Ｎ−ビニルアセトアミド系ポリマーを用いた場合には、耐熱多孔質層を構成する耐熱性微粒子や膨潤性微粒子が密に充填されるために耐熱多孔質層の強度が増すことから、耐熱多孔質層を薄くしたり、また、耐熱多孔質層中のバインダー量を特に少なくしたりしても、セパレータの耐熱性（高温下での形状安定性）を高く維持することができる。また、耐熱多孔質層を、耐熱多孔質層形成用組成物を用いて形成する場合、Ｎ−ビニルアセトアミド系ポリマーは前記組成物中において増粘剤として機能し、前記組成物中での耐熱性微粒子や膨潤性微粒子の沈降抑制に寄与し得る。このため、Ｎ−ビニルアセトアミド系ポリマーの使用によって、より均質で表面平滑性に優れ、電池内において内部抵抗の斑の原因となり難い耐熱多孔質層を形成できるようになる。 For the binder, an N-vinylacetamide-based polymer is used. When an N-vinylacetamide-based polymer is used, the heat-resistant porous layer increases in strength because the heat-resistant fine particles and the swellable fine particles constituting the heat-resistant porous layer are densely packed. Even if the thickness of the separator is reduced or the amount of the binder in the heat resistant porous layer is particularly reduced, the heat resistance (shape stability at high temperature) of the separator can be maintained high. In addition, when the heat-resistant porous layer is formed using the heat-resistant porous layer forming composition, the N-vinylacetamide-based polymer functions as a thickener in the composition, and the heat resistance in the composition This can contribute to the suppression of sedimentation of fine particles and swellable fine particles. For this reason, the use of the N-vinylacetamide-based polymer makes it possible to form a heat-resistant porous layer that is more homogeneous and excellent in surface smoothness and is less likely to cause internal resistance spots in the battery.
前記のＮ−ビニルアセトアミド系ポリマーには、Ｎ−ビニルアセトアミドの単独重合体（ポリＮ−ビニルアセトアミド）と、Ｎ−ビニルアセトアミドの共重合体とが含まれる。
Ｎ−ビニルアセトアミドの共重合体としては、例えば、Ｎ−ビニルアセトアミドとＮ−ビニルアセトアミド以外のエチレン性不飽和モノマーとの共重合体が挙げられる。
The N-vinylacetamide-based polymer includes a homopolymer of N-vinylacetamide (poly N-vinylacetamide) and a copolymer of N-vinylacetamide.
Examples of the copolymer of N-vinylacetamide include a copolymer of N-vinylacetamide and an ethylenically unsaturated monomer other than N-vinylacetamide.
Ｎ−ビニルアセトアミドの共重合体の形成に用い得るエチレン性不飽和モノマー（Ｎ−ビニルアセトアミド以外のエチレン性不飽和モノマー）としては、例えば、アクリル酸、メタクリル酸、メチルアクリレート、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、オクチルアクリレート、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、ブチルメタクリレート、オクチルメタクリレート、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、アクリロニトリル、メタクリロニトリル、酢酸ビニル、アクリルアミド、メタクリルアミド、Ｎ−メチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−ビニルホルムアミド、Ｎ−メチル，Ｎ−ビニルホルムアミド、Ｎ−ビニルピロリドン、Ｎ−ビニル−２−カプロラクタム、マレイン酸、イタコン酸、２−アクリルアミド−２−メチル−プロパンスルホン酸、２−アクリルアミドエタンスルホン酸、２−メタクリルアミドエタンスルホン酸、３−メタクリルアミドプロパンスルホン酸、アクリル酸メチルスルホン酸、メタクリル酸メチルスルホン酸、アクリル酸−２−エチルスルホン酸、メタクリル酸−２−エチルスルホン酸、アクリル酸−３−プロピルスルホン酸、メタクリル酸−３−プロピルスルホン酸、アクリル酸−２−メチル−３−プロピルスルホン酸、メタクリル酸−２−メチル−３−プロピルスルホン酸、アクリル酸−１，１’−ジメチル−２−エチルスルホン酸、メタクリル酸−１，１’−ジメチル−２−エチルスルホン酸またはそれらの塩、メチルビニルケトン、エチルビニルケトン、メチルビニルエーテル、エチルビニルエーテル、含フッ素エチレン、スチレンまたはその誘導体、ビニルアリルベンゼンなどが挙げられ、これらのうちの１種のみを使用してもよく、２種以上を併用してもよい。 Examples of ethylenically unsaturated monomers (ethylenically unsaturated monomers other than N-vinylacetamide) that can be used to form a copolymer of N-vinylacetamide include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, and propyl acrylate. , Butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, acrylamide , Methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-isopropylacrylic N-vinylformamide, N-methyl, N-vinylformamide, N-vinylpyrrolidone, N-vinyl-2-caprolactam, maleic acid, itaconic acid, 2-acrylamido-2-methyl-propanesulfonic acid, 2-acrylamide Ethanesulfonic acid, 2-methacrylamide amidoethanesulfonic acid, 3-methacrylamidopropanesulfonic acid, methyl acrylate sulfonic acid, methyl methacrylate sulfonic acid, acrylic acid-2-ethylsulfonic acid, methacrylic acid-2-ethylsulfonic acid, Acrylic acid-3-propylsulfonic acid, methacrylic acid-3-propylsulfonic acid, acrylic acid-2-methyl-3-propylsulfonic acid, methacrylic acid-2-methyl-3-propylsulfonic acid, acrylic acid-1,1 '-Dimethyl-2-ethylsulfonic acid, Examples include chloroic acid-1,1′-dimethyl-2-ethylsulfonic acid or salts thereof, methyl vinyl ketone, ethyl vinyl ketone, methyl vinyl ether, ethyl vinyl ether, fluorine-containing ethylene, styrene or derivatives thereof, and vinyl allylbenzene. Only one of these may be used, or two or more may be used in combination.
Ｎ−ビニルアセトアミドと、Ｎ−ビニルアセトアミド以外のエチレン性不飽和モノマーとの共重合体における共重合比（質量割合）は、後者のエチレン性不飽和モノマーが２〜５０質量％であることが好ましい。 The copolymerization ratio (mass ratio) of the copolymer of N-vinylacetamide and an ethylenically unsaturated monomer other than N-vinylacetamide is preferably 2 to 50% by mass of the latter ethylenically unsaturated monomer. .
Ｎ−ビニルアセトアミド系ポリマーの分子量は、ゲルパーミエーションクロマトグラフィーを用いて測定される数平均分子量（ポリスチレン換算値）で、１０００以上であることが好ましく、４０００以上であることがより好ましく、また、１００００００以下であることが好ましく、７０００００以下であることがより好ましく、５０００００以下であることが更に好ましい。 The molecular weight of the N-vinylacetamide polymer is a number average molecular weight (polystyrene conversion value) measured using gel permeation chromatography, preferably 1000 or more, more preferably 4000 or more, It is preferably 1000000 or less, more preferably 700000 or less, and further preferably 500000 or less.
また、バインダーには、Ｎ−ビニルアセトアミド系ポリマーとともに、他のバインダーを使用することもできる。このような他のバインダーとしては、例えば、エチレン−酢酸ビニル共重合体、アクリレート共重合体、ビニルアルコール系ポリマー、ビニルエーテル系ポリマー、ビニルピロリドン系ポリマーなどが挙げられる。 In addition to the N-vinylacetamide polymer, other binders can be used as the binder. Examples of such other binders include ethylene-vinyl acetate copolymers, acrylate copolymers, vinyl alcohol polymers, vinyl ether polymers, vinyl pyrrolidone polymers, and the like.
耐熱多孔質層においては、高温下におけるセパレータの形状安定性を高める観点から、膨潤性微粒子、耐熱性微粒子およびバインダーの組成比を以下のようにする。先ず、膨潤性微粒子と耐熱性微粒子との体積比率を、１０：９０〜９５：５、好ましくは４５：５５〜７０：３０とする。また、膨潤性微粒子と耐熱性微粒子との合計量を１００質量部としたとき、Ｎ−ビニルアセトアミド系ポリマーの含有量を、０．１質量部以上、好ましくは０．１５質量部以上、より好ましくは０．２質量部以上とし、また、１５質量部以下とすることが好ましく、５質量部以下とすることがより好ましく、３質量部以下とすることが更に好ましく、１質量部以下とすることが特に好ましい。 In the heat-resistant porous layer, the composition ratio of the swellable fine particles, the heat-resistant fine particles and the binder is set as follows from the viewpoint of enhancing the shape stability of the separator at a high temperature. First, the volume ratio of swellable fine particles to heat-resistant fine particles is set to 10:90 to 95: 5, preferably 45:55 to 70:30. Further, when the total amount of the swellable fine particles and the heat-resistant fine particles is 100 parts by mass, the content of the N-vinylacetamide polymer is 0.1 parts by mass or more, preferably 0.15 parts by mass or more, more preferably Is 0.2 parts by mass or more, preferably 15 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and 1 part by mass or less. Is particularly preferred.
また、膨潤性微粒子と耐熱性微粒子との合計量１００質量部に対して、Ｎ−ビニルアセトアミド系ポリマーの含有量が前記の値となるように耐熱多孔質層形成用組成物を調製することで、これらの微粒子をＮ−ビニルアセトアミド系ポリマーによって良好に被覆して、組成物中での微粒子の沈降をより良好に抑制し、より均質で表面平滑性に優れた耐熱多孔質層を形成できる。 Moreover, by preparing the composition for forming a heat resistant porous layer so that the content of the N-vinylacetamide-based polymer becomes the above value with respect to 100 parts by mass of the total amount of the swellable fine particles and the heat resistant fine particles. These fine particles can be satisfactorily coated with an N-vinylacetamide-based polymer, so that the precipitation of the fine particles in the composition can be better suppressed, and a heat-resistant porous layer having more uniform and excellent surface smoothness can be formed.
また、耐熱多孔質層における空孔量を適度に維持し、例えば、電池の負荷特性を高める観点からは、膨潤性微粒子と耐熱性微粒子との合計量を１００質量部としたとき、バインダーの含有量（Ｎ−ビニルアセトアミド系ポリマーを含むバインダーの総量）を、１５質量部以下とすることが好ましく、５質量部以下とすることがより好ましく、３質量部以下とすることが更に好ましく、１質量部以下とすることが特に好ましい。また、上記バインダーの含有量は、０．１質量部以上、好ましくは０．１５質量部以上、より好ましくは０．２質量部以上とする。 In addition, the amount of pores in the heat-resistant porous layer is appropriately maintained. For example, from the viewpoint of improving the load characteristics of the battery, when the total amount of the swellable fine particles and the heat-resistant fine particles is 100 parts by mass, The amount (total amount of binder containing N-vinylacetamide-based polymer) is preferably 15 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less. It is particularly preferable that the amount is not more than parts. The binder content is 0.1 parts by mass or more, preferably 0.15 parts by mass or more, more preferably 0.2 parts by mass or more.
耐熱多孔質層における膨潤性微粒子の含有量は、耐熱多孔質層の構成成分の全体積（空孔部分の体積を除く全体積。以下同じ。）中、１０体積％以上であることが好ましく、４５体積％以上であることがより好ましい。耐熱多孔質層中の膨潤性微粒子の含有量を前記のようにすることで、電池発熱時の熱暴走反応を良好に抑制することができる。 The content of the swellable fine particles in the heat-resistant porous layer is preferably 10% by volume or more in the total volume of the constituent components of the heat-resistant porous layer (the total volume excluding the volume of the void portion; the same applies hereinafter), More preferably, it is 45 volume% or more. By setting the content of the swellable fine particles in the heat-resistant porous layer as described above, the thermal runaway reaction during battery heat generation can be satisfactorily suppressed.
ただし、耐熱多孔質層中に膨潤性微粒子を過度に含有させると、電池の信頼性および安全性の向上が期待できるものの、電池が使用される温度領域での非水電解液の吸収量が増えたり、膨潤性微粒子の凝集によって耐熱多孔質層の表面の平滑性が低下し、内部抵抗がセパレータの位置ごとに変動したりして、電池の負荷特性が低下する虞がある。このような観点から、耐熱多孔質層における膨潤性微粒子の含有量は、例えば、耐熱多孔質層の構成成分の全体積中、９５体積％以下であることが好ましく、７０体積％以下であることがより好ましい。 However, excessively containing swellable fine particles in the heat-resistant porous layer can be expected to improve the reliability and safety of the battery, but the amount of nonaqueous electrolyte absorbed in the temperature range where the battery is used increases. In addition, the smoothness of the surface of the heat-resistant porous layer may be reduced due to aggregation of the swellable fine particles, and the internal resistance may vary depending on the position of the separator, which may reduce the load characteristics of the battery. From such a viewpoint, the content of the swellable fine particles in the heat resistant porous layer is, for example, preferably 95% by volume or less, and 70% by volume or less in the total volume of the constituent components of the heat resistant porous layer. Is more preferable.
また、耐熱多孔質層における耐熱性微粒子の含有量は、高温時におけるセパレータの形状安定性をより良好に高め、電池内が高温になった際の熱収縮を良好に抑制するとともに、耐熱多孔質層内での膨潤性微粒子の凝集を抑えて、耐熱多孔質層の表面平滑性を高める観点から、耐熱多孔質層の構成成分の全体積中、５体積％以上であることが好ましく、３０体積％以上であることがより好ましい。 In addition, the content of the heat-resistant fine particles in the heat-resistant porous layer enhances the shape stability of the separator at high temperatures, suppresses heat shrinkage when the inside of the battery becomes high temperature, and heat-resistant porous From the viewpoint of suppressing the aggregation of the swellable fine particles in the layer and enhancing the surface smoothness of the heat resistant porous layer, the total volume of the constituent components of the heat resistant porous layer is preferably 5% by volume or more, and 30 volumes. % Or more is more preferable.
本発明のセパレータは、耐熱多孔質層を樹脂多孔質膜の片面にのみ有していてもよく、両面に有していてもよいが、例えば、セパレータの生産性を高める観点からは、樹脂多孔質膜の片面にのみ耐熱多孔質層を有していることが好ましい。 The separator of the present invention may have a heat-resistant porous layer only on one side of the resin porous membrane or on both sides. For example, from the viewpoint of increasing the productivity of the separator, It is preferable to have a heat-resistant porous layer only on one side of the membrane.
耐熱多孔質層の厚み（樹脂多孔質膜の両面に耐熱多孔質層が形成されている場合は、両耐熱多孔質層の合計厚み。耐熱多孔質層の厚みについて、以下同じ。）は、セパレータの熱収縮を抑制する耐熱多孔質層の作用を十分に確保する観点から、２μｍ以上であり、３μｍ以上であることが好ましい。また、耐熱多孔質層をこのような厚みとすることで、電池内に導電性の異物が混入した場合における内部短絡による発熱などを良好に防止することもできる。ただし、耐熱多孔質層の厚みが厚すぎると、セパレータの全厚みが大きくなってしまい、電池の負荷特性の低下が引き起こされたり、電池容量の向上が困難となったりする虞がある。よって、耐熱多孔質層の厚みは、１０μｍ以下であり、５μｍ以下であることが好ましい。本発明のセパレータでは、このような薄い耐熱多孔質層を１層形成するだけで、例えば２００℃といった高温での形状安定性を高めることができる。 The thickness of the heat resistant porous layer (when heat resistant porous layers are formed on both sides of the resin porous membrane, the total thickness of both heat resistant porous layers. The same applies to the thickness of the heat resistant porous layer). From the viewpoint of sufficiently ensuring the action of the heat-resistant porous layer that suppresses thermal shrinkage of the film, it is 2 μm or more, and preferably 3 μm or more. In addition, by setting the heat-resistant porous layer to such a thickness, heat generation due to an internal short circuit when conductive foreign matter is mixed in the battery can be well prevented. However, if the thickness of the heat-resistant porous layer is too thick, the total thickness of the separator increases, which may cause a reduction in battery load characteristics or make it difficult to improve battery capacity. Therefore, the thickness of the heat resistant porous layer is 10 μm or less, and preferably 5 μm or less. In the separator of the present invention, the shape stability at a high temperature of, for example, 200 ° C. can be enhanced only by forming one thin heat-resistant porous layer.
本発明のセパレータに係る樹脂多孔質膜は、融解温度、すなわち、ＪＩＳ Ｋ ７１２１の規定に準じて、示差走査熱量計（ＤＳＣ）を用いて測定される融解温度が、８０℃以上１８０℃以下のポリオレフィンを主成分とする樹脂多孔質膜である。樹脂多孔質膜を構成するポリオレフィンとしては、低密度ポリエチレン、高密度ポリエチレン、超高分子量ポリエチレンなどのポリエチレン（ＰＥ）；ポリプロピレン（ＰＰ）；などが挙げられ、これらのうちの１種のみを用いてもよく、２種以上を併用してもよい。２種以上のポリオレフィンを用いた樹脂多孔質膜としては、例えば、ＰＥ層の両面にＰＰ層を形成した３層構造のポリオレフィン製樹脂多孔質膜が挙げられる。セパレータが、このようなポリオレフィンで構成された樹脂多孔質膜を有していることで、８０〜１８０℃でポリオレフィンが軟化してセパレータの空孔が閉塞される、いわゆるシャットダウン特性を確保することができる。樹脂多孔質膜を構成するポリオレフィンの融解温度は、１５０℃以下であることがより好ましい。 The resin porous membrane according to the separator of the present invention has a melting temperature, that is, a melting temperature measured using a differential scanning calorimeter (DSC) of 80 ° C. or higher and 180 ° C. or lower in accordance with JIS K 7121. It is a resin porous membrane mainly composed of polyolefin. Examples of the polyolefin constituting the resin porous membrane include polyethylene (PE) such as low density polyethylene, high density polyethylene, and ultrahigh molecular weight polyethylene; polypropylene (PP); and the like, and only one of these is used. Or two or more of them may be used in combination. Examples of the resin porous membrane using two or more kinds of polyolefin include a polyolefin porous resin membrane having a three-layer structure in which PP layers are formed on both sides of the PE layer. Since the separator has a porous resin membrane composed of such a polyolefin, the so-called shutdown characteristic can be secured in which the polyolefin softens at 80 to 180 ° C. and the pores of the separator are blocked. it can. The melting temperature of the polyolefin constituting the resin porous membrane is more preferably 150 ° C. or lower.
樹脂多孔質膜としては、例えば、従来から知られている溶剤抽出法や、乾式または湿式延伸法などにより形成された孔を多数有するイオン透過性の多孔質膜（電池のセパレータとして汎用されている微多孔膜）を用いることができる。 As the resin porous membrane, for example, an ion-permeable porous membrane having a large number of pores formed by a conventionally known solvent extraction method, dry type or wet drawing method (used widely as a battery separator) A microporous membrane) can be used.
樹脂多孔質膜における「ポリオレフィンが主成分」とは、樹脂多孔質膜を構成する成分の全体積のうち、ポリオレフィンが５０体積％以上であることを意味するが、樹脂多孔質膜においては、シャットダウン特性をより良好に確保する観点から、主成分となるポリオレフィンが、樹脂多孔質膜を構成する成分の全体積のうち、７０体積％以上であることが好ましく、８０体積％以上であることが更に好ましい（ポリオレフィンが１００体積％であってもよい。）。 “Polyolefin is the main component” in the porous resin membrane means that the polyolefin is 50% by volume or more of the total volume of the components constituting the porous resin membrane. From the viewpoint of ensuring better characteristics, the polyolefin as the main component is preferably 70% by volume or more, more preferably 80% by volume or more, of the total volume of the components constituting the resin porous membrane. Preferred (100% by volume of polyolefin may be used).
また、耐熱多孔質層の空孔率は４０〜７０％であることが好ましく、且つ樹脂多孔質膜に含まれるポリオレフィンの体積は、耐熱多孔質層の空孔体積の５０％以上であることが好ましい。これにより、シャットダウンが生じた際に、軟化または溶融したポリオレフィンが耐熱多孔質層の空孔を充分に閉塞して、イオン伝導を遮断することができる。 The porosity of the heat resistant porous layer is preferably 40 to 70%, and the volume of the polyolefin contained in the resin porous membrane is 50% or more of the pore volume of the heat resistant porous layer. preferable. Thereby, when shutdown occurs, the softened or melted polyolefin sufficiently closes the pores of the heat-resistant porous layer, and can block ionic conduction.
樹脂多孔質膜の厚み（セパレータが樹脂多孔質膜を複数有する場合には、その合計厚み。樹脂多孔質膜の厚みについて、以下同じ。）は、電池のシャットダウン特性を良好に確保する観点から、９μｍ以上であることが好ましく、１２μｍ以上であることがより好ましい。また、セパレータの全厚みを小さくして、電池の容量や出力密度をより向上させる観点から、樹脂多孔質膜の厚みは、３５μｍ以下であることが好ましく、２１μｍ以下であることがより好ましい。 The thickness of the resin porous membrane (when the separator has a plurality of resin porous membranes, the total thickness. The same applies to the thickness of the resin porous membrane), from the viewpoint of ensuring good battery shutdown characteristics. It is preferably 9 μm or more, and more preferably 12 μm or more. In addition, from the viewpoint of reducing the total thickness of the separator and further improving the capacity and output density of the battery, the thickness of the resin porous membrane is preferably 35 μm or less, and more preferably 21 μm or less.
また、本発明のセパレータにおいては、シャットダウン特性および弾性を良好に確保する観点から、セパレータの構成成分の全体積中、樹脂（樹脂多孔質膜に含まれる樹脂、耐熱多孔質層に含まれる膨潤性微粒子およびバインダーを含めた、セパレータに含まれる全ての樹脂。セパレータ中の樹脂の比率に関して、以下同じ。）が、５０体積％以上であり、８０体積％以上であることが好ましい。ただし、セパレータ中における樹脂の比率が大きすぎると、耐熱多孔質層に含まれる耐熱性微粒子の割合が小さくなって、高温下におけるセパレータの形状安定性が低下するため、セパレータの構成成分の全体積中における全ての樹脂の比率は、９９．９体積％以下であり、９８体積％以下であることが好ましい。 Further, in the separator of the present invention, from the viewpoint of ensuring good shutdown characteristics and elasticity, the resin (resin contained in the resin porous membrane, swellability contained in the heat resistant porous layer) is included in the total volume of the constituent components of the separator. All resins contained in the separator including the fine particles and the binder (the same applies hereinafter with respect to the ratio of the resin in the separator)) is preferably 50% by volume or more and preferably 80% by volume or more. However, if the ratio of the resin in the separator is too large, the ratio of the heat-resistant fine particles contained in the heat-resistant porous layer is reduced, and the shape stability of the separator at high temperatures is reduced. The ratio of all the resins in the inside is 99.9% by volume or less, and preferably 98% by volume or less.
セパレータの全厚みは、十分な強度を確保する観点から、１２μｍ以上であることが好ましく、２１μｍ以上であることがより好ましい。ただし、セパレータが厚すぎると、電池の高出力化の効果が小さくなる虞があることから、セパレータの全厚みは、４５μｍ以下であることが好ましく、３５μｍ以下であることがより好ましい。 The total thickness of the separator is preferably 12 μm or more, and more preferably 21 μm or more, from the viewpoint of securing sufficient strength. However, if the separator is too thick, the effect of increasing the output of the battery may be reduced. Therefore, the total thickness of the separator is preferably 45 μm or less, and more preferably 35 μm or less.
セパレータの空孔率としては、非水電解液の保液量を確保してイオン透過性を良好にするために、乾燥した状態で、３０％以上であることが好ましく、４０％以上であることがより好ましい。一方、セパレータ強度の確保と内部短絡の防止の観点から、セパレータの空孔率は、乾燥した状態で、７０％以下であることが好ましく、６０％以下であることがより好ましい。セパレータの空孔率：Ｐ（％）は、セパレータの厚み、面積あたりの質量、構成成分の密度から、下記式（１）を用いて各成分ｉについての総和を求めることにより計算できる。 The porosity of the separator is preferably 30% or more and 40% or more in a dried state in order to ensure the amount of nonaqueous electrolyte retained and to improve ion permeability. Is more preferable. On the other hand, from the viewpoint of ensuring the strength of the separator and preventing internal short circuit, the porosity of the separator is preferably 70% or less, more preferably 60% or less, in a dry state. The porosity of the separator: P (%) can be calculated by obtaining the sum for each component i from the thickness of the separator, the mass per area, and the density of the constituent components using the following formula (1).
Ｐ＝｛１−（ｍ／ｔ）／（Σａi・ρi）｝×１００ （１）
ここで、前記式（１）中、ａi：全体の質量を１としたときの成分ｉの比率、ρi：成分ｉの密度（ｇ／ｃｍ3）、ｍ：セパレータの単位面積あたりの質量（ｇ／ｃｍ2）、ｔ：セパレータの厚み（ｃｍ）である。
P = {1- (m / t) / (Σa i · ρ i )} × 100 (1)
Here, in the formula (1), a i : the ratio of component i when the total mass is 1, ρ i : density of component i (g / cm 3 ), m: mass per unit area of the separator (G / cm 2 ), t: thickness of separator (cm).
更に、前記式（１）において、ｍを樹脂多孔質膜の単位面積あたりの質量（ｇ／ｃｍ2）とし、ｔを樹脂多孔質膜の厚み（ｃｍ）とすることで、前記式（１）を用いて樹脂多孔質膜の空孔率：Ｐ（％）を求めることもできる。この方法により求められる樹脂多孔質膜の空孔率は、３０〜７０％であることが好ましい。 Further, in the above formula (1), m is the mass per unit area (g / cm 2 ) of the resin porous membrane, and t is the thickness (cm) of the resin porous membrane, whereby the formula (1) Can also be used to determine the porosity of the resin porous membrane: P (%). It is preferable that the porosity of the resin porous membrane calculated | required by this method is 30 to 70%.
また、前記式（１）において、ｍを耐熱多孔質層の単位面積あたりの質量（ｇ／ｃｍ2）とし、ｔを耐熱多孔質層の厚み（ｃｍ）とすることで、前記式（１）を用いて耐熱多孔質層の空孔率：Ｐ（％）を求めることもできる。この方法により求められる耐熱多孔質層の空孔率は、３０〜７５％であることが好ましい。 In the formula (1), m is the mass per unit area (g / cm 2 ) of the heat resistant porous layer, and t is the thickness (cm) of the heat resistant porous layer. Can also be used to determine the porosity of the heat-resistant porous layer: P (%). It is preferable that the porosity of the heat resistant porous layer calculated | required by this method is 30 to 75%.
本発明のセパレータの熱収縮率は、２００℃の温度雰囲気下に静置したときの熱収縮率が５％以下であることが好ましく、０％であることが特に好ましい。セパレータの熱収縮率が大きすぎると、導電性異物が混入することによる内部短絡の発生時に、セパレータの熱収縮による内部短絡の拡大を抑制する効果が小さくなる虞がある。セパレータの前記熱収縮率は、セパレータを、これまで説明してきた構成とすることで確保することができる。 The thermal contraction rate of the separator of the present invention is preferably 5% or less, particularly preferably 0% when left in a 200 ° C. temperature atmosphere. If the thermal contraction rate of the separator is too large, the effect of suppressing the expansion of the internal short circuit due to the thermal contraction of the separator may be reduced when an internal short circuit occurs due to the mixing of conductive foreign substances. The thermal contraction rate of the separator can be ensured by configuring the separator as described above.
本明細書でいう「２００℃の温度雰囲気下に静置したときのセパレータの熱収縮率」は、具体的には、後述する実施例で用いた方法により測定する。 The “thermal contraction rate of the separator when left in a 200 ° C. temperature atmosphere” as used herein is specifically measured by the method used in the examples described later.
本発明のセパレータは、例えば、耐熱多孔質層を構成する膨潤性微粒子、耐熱性微粒子およびバインダーなどを、水や有機溶媒といった媒体に分散させてスラリー状やペースト状の耐熱多孔質層形成用組成物（バインダーは、媒体に溶解していてもよい。）を調製し、これを樹脂多孔質膜の表面に塗布し、乾燥する方法により製造することができる。 The separator of the present invention is, for example, a composition for forming a heat-resistant porous layer in the form of a slurry or paste by dispersing swellable fine particles, heat-resistant fine particles and a binder constituting the heat-resistant porous layer in a medium such as water or an organic solvent. It can be manufactured by preparing a product (the binder may be dissolved in a medium), applying it to the surface of the porous resin membrane, and drying it.
耐熱多孔質層形成用組成物を塗布するにあたっては、例えば、これらの組成物を公知の塗工装置により塗布する方法が採用できる。耐熱多孔質層形成用組成物を塗布する際に使用できる塗工装置としては、例えば、グラビアコーター、ナイフコーター、リバースロールコーター、ダイコーターなどが挙げられる。 In applying the heat-resistant porous layer forming composition, for example, a method of applying these compositions with a known coating apparatus can be employed. Examples of the coating apparatus that can be used when applying the heat-resistant porous layer forming composition include a gravure coater, a knife coater, a reverse roll coater, and a die coater.
耐熱多孔質層形成用組成物に用いられる媒体は、耐熱性微粒子や膨潤性微粒子などを均一に分散でき、また、バインダーを均一に溶解または分散できるものであればよいが、例えば、トルエンなどの芳香族炭化水素、テトラヒドロフランなどのフラン類、メチルエチルケトン、メチルイソブチルケトンなどのケトン類など、一般的な有機溶媒が好適に用いられる。これらの媒体に、界面張力を制御する目的で、アルコール（エチレングリコール、プロピレングリコールなど）、または、モノメチルアセテートなどの各種プロピレンオキサイド系グリコールエーテルなどを適宜添加してもよい。また、バインダーが水溶性である場合、エマルジョンとして使用する場合などでは、前記の通り水を媒体としてもよく、この際にもアルコール類（メチルアルコール、エチルアルコール、イソプロピルアルコール、エチレングリコールなど）を適宜加えて界面張力を制御することもできる。 The medium used in the heat-resistant porous layer forming composition may be any medium that can uniformly disperse heat-resistant fine particles and swellable fine particles, and can uniformly dissolve or disperse the binder. Common organic solvents such as aromatic hydrocarbons, furans such as tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are preferably used. In order to control the interfacial tension, alcohols (ethylene glycol, propylene glycol, etc.) or various propylene oxide glycol ethers such as monomethyl acetate may be appropriately added to these media. When the binder is water-soluble or used as an emulsion, water may be used as described above, and alcohols (such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and ethylene glycol) may be used as appropriate. In addition, the interfacial tension can be controlled.
耐熱多孔質層形成用組成物は、その固形分含量を、例えば１０〜８０質量％とすることが好ましい。 The heat-resistant porous layer forming composition preferably has a solid content of, for example, 10 to 80% by mass.
樹脂多孔質膜には、耐熱多孔質層との接着性を高めるために、表面改質を行うことができる。ポリオレフィンが主成分の樹脂多孔質膜は表面の接着性が一般に高くないため、表面改質が有効であることが多い。 The resin porous membrane can be subjected to surface modification in order to enhance the adhesion with the heat resistant porous layer. Surface modification is often effective because resin porous membranes composed mainly of polyolefins generally do not have high surface adhesion.
樹脂多孔質膜の表面改質方法としては、例えば、コロナ放電処理、プラズマ放電処理、紫外線照射処理などが挙げられる。環境問題への対応の観点から、例えば耐熱多孔質層形成用組成物の媒体には水を用いることがより望ましく、このことからも、表面改質によって、樹脂多孔質膜の表面の親水性を高めておくことは非常に好ましい。 Examples of the method for modifying the surface of the resin porous membrane include corona discharge treatment, plasma discharge treatment, and ultraviolet irradiation treatment. From the viewpoint of responding to environmental problems, for example, it is more desirable to use water as the medium for the heat-resistant porous layer forming composition. From this, the hydrophilicity of the surface of the resin porous membrane can be improved by surface modification. It is very preferable to raise it.
（実施形態２）
次に、本発明の非水電解液電池について説明する。本発明の非水電解液電池は、正極、負極、セパレータおよび非水電解液を備えており、前記セパレータが実施形態１で説明した本発明のセパレータであればよく、その他の構成および構造については特に制限はなく、従来から知られている非水電解液電池で採用されている各種構成および構造を適用することができる。
(Embodiment 2)
Next, the nonaqueous electrolyte battery of the present invention will be described. The non-aqueous electrolyte battery of the present invention includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, and the separator may be the separator of the present invention described in the first embodiment. There is no particular limitation, and various configurations and structures employed in conventionally known nonaqueous electrolyte batteries can be applied.
本発明の非水電解液電池には、一次電池と二次電池とが含まれるが、以下には、特に主要な態様である二次電池（リチウムイオン二次電池）の構成について詳細に説明する。 The non-aqueous electrolyte battery of the present invention includes a primary battery and a secondary battery. The configuration of a secondary battery (lithium ion secondary battery) which is a particularly main aspect will be described in detail below. .
非水電解質電池の形態としては、スチール缶やアルミニウム缶などを外装缶として使用した筒形（角筒形や円筒形など）などが挙げられる。また、金属を蒸着したラミネートフィルムを外装体としたソフトパッケージ電池とすることもできる。 Examples of the form of the nonaqueous electrolyte battery include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can, an aluminum can, or the like as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
本発明の非水電解液電池の正極としては、従来から知られている非水電解液二次電池に用いられている正極であれば特に制限はない。例えば、活物質として、Ｌｉ1+xＭＯ2（−０．１＜ｘ＜０．１、Ｍ：Ｃｏ、Ｎｉ、Ｍｎなど）で表されるリチウム含有遷移金属酸化物；ＬｉＭｎ2Ｏ4などのリチウムマンガン酸化物；ＬｉＭｎ2Ｏ4のＭｎの一部を他元素で置換したＬｉＭｎxＭ(1-x)Ｏ2；オリビン型ＬｉＭＰＯ4（Ｍ：Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ）；ＬｉＭｎ0.5Ｎｉ0.5Ｏ2；Ｌｉ(1+a)ＭｎxＮｉyＣｏ(1-x-y)Ｏ2(−０．１＜ａ＜０．１、０＜ｘ＜０．５、０＜ｙ＜０．５)；などを適用することが可能であり、これらの正極活物質に公知の導電助剤（カーボンブラックなどの炭素材料など）やポリフッ化ビニリデン（ＰＶＤＦ）などのバインダーなどを適宜添加した正極合剤を、集電体を芯材として成形体に仕上げたものなどを用いることができる。 The positive electrode of the nonaqueous electrolyte battery of the present invention is not particularly limited as long as it is a positive electrode used in a conventionally known nonaqueous electrolyte secondary battery. For example, as an active material, a lithium-containing transition metal oxide represented by Li 1 + x MO 2 (−0.1 <x <0.1, M: Co, Ni, Mn, etc.); LiMn 2 O 4, etc. LiMn manganese oxide; LiMn x M (1-x) O 2 in which part of Mn of LiMn 2 O 4 is substituted with another element; olivine type LiMPO 4 (M: Co, Ni, Mn, Fe); LiMn 0.5 Ni 0.5 O 2 ; Li (1 + a) Mn x Ni y Co (1-xy) O 2 (−0.1 <a <0.1, 0 <x <0.5, 0 <y <0.5) A positive electrode mixture in which a known conductive additive (carbon material such as carbon black) or a binder such as polyvinylidene fluoride (PVDF) is appropriately added to these positive electrode active materials. In addition, a product obtained by finishing a molded body using a current collector as a core material can be used.
正極の集電体としては、アルミニウムなどの金属の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、厚みが１０〜３０μｍのアルミニウム箔が好適に用いられる。 As the current collector of the positive electrode, a metal foil such as aluminum, a punching metal, a net, an expanded metal, or the like can be used. Usually, an aluminum foil having a thickness of 10 to 30 μm is preferably used.
正極側のリード部は、通常、正極作製時に、集電体の一部に正極合剤層を形成せずに集電体の露出部を残し、そこをリード部とすることによって設けられる。ただし、リード部は必ずしも当初から集電体と一体化されたものであることは要求されず、集電体にアルミニウム製の箔などを後から接続することによって設けてもよい。 The lead portion on the positive electrode side is normally provided by leaving the exposed portion of the current collector without forming the positive electrode mixture layer on a part of the current collector and forming the lead portion at the time of producing the positive electrode. However, the lead portion is not necessarily integrated with the current collector from the beginning, and may be provided by connecting an aluminum foil or the like to the current collector later.
本発明の非水電解液電池の負極としては、従来から知られている非水電解液二次電池に用いられている負極であれば特に制限はない。例えば、活物質として、黒鉛、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物の焼成体、メソカーボンマイクロビーズ（ＭＣＭＢ）、炭素繊維などの、リチウムを吸蔵、放出可能な炭素系材料の１種または２種以上の混合物が用いられる。また、Ｓｉ、Ｓｎ、Ｇｅ、Ｂｉ、Ｓｂ、Ｉｎなどの元素およびその合金、リチウム含有窒化物またはリチウム含有酸化物などのリチウム金属に近い低電圧で充放電できる化合物、もしくはリチウム金属やリチウム／アルミニウム合金も負極活物質として用いることができる。これらの負極活物質に導電助剤（カーボンブラックなどの炭素材料など）やＰＶＤＦなどのバインダーなどを適宜添加した負極合剤を、集電体を芯材として成形体に仕上げたものが用いられる他、上記の各種合金やリチウム金属の箔を単独で用いてもよく、また、上記の各種合金やリチウム金属を集電体上に積層して用いてもよい。 The negative electrode of the nonaqueous electrolyte battery of the present invention is not particularly limited as long as it is a negative electrode used in a conventionally known nonaqueous electrolyte secondary battery. For example, carbon that can occlude and release lithium, such as graphite, pyrolytic carbons, cokes, glassy carbons, fired organic polymer compounds, mesocarbon microbeads (MCMB), and carbon fibers as active materials One type or a mixture of two or more types of system materials is used. Further, elements such as Si, Sn, Ge, Bi, Sb, In and alloys thereof, compounds that can be charged and discharged at a low voltage close to lithium metal such as lithium-containing nitrides or lithium-containing oxides, or lithium metal or lithium / aluminum An alloy can also be used as the negative electrode active material. In addition to these negative electrode active materials, a negative electrode mixture prepared by appropriately adding a conductive additive (carbon material such as carbon black) or a binder such as PVDF to a molded body using a current collector as a core is used. The above various alloys and lithium metal foils may be used alone, or the above various alloys and lithium metal may be laminated on a current collector.
負極に集電体を用いる場合には、集電体としては、銅製やニッケル製の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、銅箔が用いられる。この負極集電体は、高エネルギー密度の電池を得るために負極全体の厚みを薄くする場合、厚みの上限は４０μｍであることが好ましく、また、下限は５μｍであることが望ましい。 When a current collector is used for the negative electrode, a copper or nickel foil, a punching metal, a net, an expanded metal, or the like can be used as the current collector, but a copper foil is usually used. In the negative electrode current collector, when the thickness of the entire negative electrode is reduced in order to obtain a battery having a high energy density, the upper limit of the thickness is preferably 40 μm, and the lower limit is preferably 5 μm.
負極側のリード部も、正極側のリード部と同様に、通常、負極作製時に、集電体の一部に負極剤層（負極活物質を有する層）を形成せずに集電体の露出部を残し、そこをリード部とすることによって設けられる。ただし、この負極側のリード部は必ずしも当初から集電体と一体化されたものであることは要求されず、集電体に銅製の箔などを後から接続することによって設けてもよい。 Similarly to the lead portion on the positive electrode side, the negative electrode lead portion is usually exposed to the current collector without forming a negative electrode agent layer (a layer having a negative electrode active material) on a part of the current collector during negative electrode fabrication. It is provided by leaving a part and using it as a lead part. However, the lead portion on the negative electrode side is not necessarily integrated with the current collector from the beginning, and may be provided by connecting a copper foil or the like to the current collector later.
電極は、前記の正極と前記の負極とを、本発明のセパレータを介して積層した積層電極体や、更にこれを巻回した巻回電極体の形態で用いることができる。正極と負極とを本発明のセパレータを介して積層する場合、本発明のセパレータの耐熱多孔質層側を正極と接触させることが好ましい。これにより、電池が発熱した際に、耐熱多孔質層に含まれる膨潤性微粒子が非水電解液を吸収して、正極の界面の非水電解液が減少するため、正極と非水電解液との熱暴走反応を良好に抑制できる。 The electrode can be used in the form of a laminated electrode body in which the positive electrode and the negative electrode are laminated via the separator of the present invention, or a wound electrode body in which this is wound. When laminating the positive electrode and the negative electrode via the separator of the present invention, it is preferable to contact the heat-resistant porous layer side of the separator of the present invention with the positive electrode. Thus, when the battery generates heat, the swellable fine particles contained in the heat-resistant porous layer absorb the non-aqueous electrolyte, and the non-aqueous electrolyte at the interface of the positive electrode decreases. The thermal runaway reaction can be suppressed well.
耐熱多孔質層の非水電解液には、例えば、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、プロピオン酸メチル、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、γ−ブチロラクトン、エチレングリコールサルファイト、１，２−ジメトキシエタン、１，３−ジオキソラン、テトラヒドロフラン、２−メチル−テトラヒドロフラン、ジエチルエーテルなどの１種のみからなる有機溶媒、または２種以上の混合溶媒に、例えば、ＬｉＣｌＯ4、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＣＦ3ＣＯ2、Ｌｉ2Ｃ2Ｆ4（ＳＯ3）2、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、ＬｉＣnＦ2n+1ＳＯ3（２≦ｎ≦７）、ＬｉＮ（ＲfＯＳＯ2）2〔ここで、Ｒfはフルオロアルキル基を示す。〕などのリチウム塩から選ばれる少なくとも１種を溶解させることによって調製したものが使用される。このリチウム塩の非水電解液中の濃度としては、０．５〜１．５ｍｏｌ／Ｌとすることが好ましく、０．９〜１．２５ｍｏｌ／Ｌとすることがより好ましい。 Examples of the nonaqueous electrolytic solution for the heat resistant porous layer include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propionate, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, ethylene glycol sulfite, 1,2- An organic solvent composed of only one kind such as dimethoxyethane, 1,3-dioxolane, tetrahydrofuran, 2-methyl-tetrahydrofuran, diethyl ether, or a mixed solvent of two or more kinds, for example, LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (2 ≦ n ≦ 7), LiN (R f OS 2) 2 [wherein, R f represents a fluoroalkyl group. And the like prepared by dissolving at least one selected from lithium salts such as The concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.5 to 1.5 mol / L, and more preferably 0.9 to 1.25 mol / L.
続いて、本発明のリチウムイオン二次電池の一例を図面に基づき説明する。図１は、本発明のリチウムイオン二次電池の一例を示す断面図である。図１において、本発明のリチウム二次電池は、上記で説明した正極活物質を含む正極合剤層を有する正極１と、負極活物質を含む負極合剤層を有する負極２と、本発明のセパレータ３と、非水電解液４とを備えている。正極１と負極２とはセパレータ３を介して渦巻状に巻回され、巻回構造の電極体として非水電解液４と共に円筒形の電池缶５内に収容されている。
Then, an example of the lithium ion secondary battery of this invention is demonstrated based on drawing. FIG. 1 is a cross-sectional view showing an example of the lithium ion secondary battery of the present invention. In FIG. 1, a lithium secondary battery of the present invention includes a
ただし、図１においては、煩雑化を避けるため、正極１や負極２の作製にあたり使用した集電体である金属箔などは図示していない。また、セパレータ３は、その切断面を示すが、断面を示すハッチングは付していない。
However, in FIG. 1, in order to avoid complication, the metal foil which is a current collector used for manufacturing the
電池缶５は、例えば鉄製で表面にニッケルメッキが施されていて、その底部には上記巻回構造の電極体の挿入に先立って、例えばポリプロピレンからなる絶縁体６が配置されている。封口板７は、例えばアルミニウム製で円板状をしていて、その中央部に薄肉部７ａが設けられ、且つ薄肉部７ａの周囲に電池内圧を防爆弁９に作用させるための圧力導入口７ｂとしての孔が設けられている。そして、薄肉部７ａの上面に防爆弁９の突出部９ａが溶接され、溶接部分１１を構成している。封口板７に設けた薄肉部７ａや防爆弁９の突出部９ａなどは、図面上での理解がしやすいように、切断面のみを図示しており、切断面後方の輪郭線は図示を省略している。また、封口板７の薄肉部７ａと防爆弁９の突出部９ａとの溶接部分１１も、図面上での理解が容易なように、実際よりは誇張した状態に図示している。
The battery can 5 is made of, for example, iron and nickel-plated on the surface, and an insulator 6 made of, for example, polypropylene is disposed at the bottom of the battery can 5 prior to the insertion of the electrode body having the winding structure. The sealing
端子板８は、例えば圧延鋼製で表面にニッケルメッキが施され、周縁部が鍔状になった帽子状をしており、端子板８にはガス排出口８ａが設けられている。防爆弁９は、例えばアルミニウム製で円板状をしており、その中央部には発電要素側（図１では、下側）に先端部を有する突出部９ａが設けられ、且つ薄肉部９ｂが設けられ、突出部９ａの下面が、上記のように、封口板７の薄肉部７ａの上面に溶接され、溶接部分１１を形成している。絶縁パッキング１０は、例えばポリプロピレン製で環状をしており、封口板７の周縁部の上部に配置され、その上部に防爆弁９が配置していて、封口板７と防爆弁９とを絶縁するとともに、両者の間から電解液が漏れないように両者の間隙を封止している。環状ガスケット１２は、例えばポリプロピレンで形成されている。リード体１３は、例えばアルミニウムで形成され、封口板７と正極１とを接続している。巻回構造の電極体の上部には絶縁体１４が配置され、負極２と電池缶５の底部とは、例えばニッケル製のリード体１５で接続されている。
The
図１の電池においては、封口板７の薄肉部７ａと防爆弁９の突出部９ａとが溶接部分１１で接触し、防爆弁９の周縁部と端子板８の周縁部とが接触し、正極１と封口板７とは正極側のリード体１３で接続されているので、通常の状態では、正極１と端子板８とは、リード体１３、封口板７、防爆弁９およびそれらの溶接部分１１によって電気的接続が得られ、電路として正常に機能する。
In the battery of FIG. 1, the thin-
そして、電池が高温に曝されたり、過充電によって発熱するなど、電池に異常事態が起こり、電池内部にガスが発生して電池の内圧が上昇した場合には、その内圧上昇により、防爆弁９の中央部が内圧方向（図１では、上側の方向）に変形する。それに伴って溶接部分１１で一体化されてなる封口板７の薄肉部７ａに剪断力が働いて該薄肉部７ａが破断するか、または防爆弁９の突出部９ａと封口板７の薄肉部７ａとの溶接部分１１が剥離した後、この防爆弁９に設けられている薄肉部９ｂが開裂してガスを端子板８のガス排出口８ａから電池外部に排出させて電池の破裂を防止することができるように設計されている。
When an abnormal situation occurs in the battery, such as the battery is exposed to high temperature or generates heat due to overcharge, and gas is generated inside the battery and the internal pressure of the battery increases, the explosion-proof valve 9 The center part of the is deformed in the internal pressure direction (the upper direction in FIG. 1). Along with this, a shearing force is applied to the
本発明の非水電解液電池は、自動車用途や電動工具、各種電子機器の電源用途などを始めとして、従来から知られている非水電解液電池（非水電解液一次電池、非水電解液二次電池）が用いられている各種用途と同じ用途にも適用することができる。 The non-aqueous electrolyte battery of the present invention is a conventionally known non-aqueous electrolyte battery (non-aqueous electrolyte primary battery, non-aqueous electrolyte solution, including automobile applications, power tools, and power supply applications for various electronic devices). The present invention can also be applied to the same uses as various uses in which secondary batteries are used.
以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は本発明を制限するものではない。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.
（実施例１）
＜セパレータの作製＞
水６００ｇ中に、耐熱性微粒子である多面体形状のベーマイト合成品（アスペクト比１．４、Ｄ５０＝０．６３μｍ）５００ｇと、バインダーであるポリＮ−ビニルアセトアミド（耐熱性微粒子と、後述する膨潤性微粒子との合計１００質量部に対して５質量部となる量）とを、スリーワンモーターを用いて１時間攪拌して分散させ、更に膨潤性微粒子である架橋ＰＭＭＡ微粒子の水分散体（Ｄ５０＝０．５μｍ、Ｔｇ＝１０５℃、固形分比率４０質量％）を、架橋ＰＭＭＡ微粒子とベーマイト合成品との比率が体積比で５０：５０になるように加え、均一に分散させて耐熱多孔質層形成用組成物を調製した。
Example 1
<Preparation of separator>
In 600 g of water, 500 g of a polyhedral boehmite synthetic product (aspect ratio 1.4, D50 = 0.63 μm) as heat-resistant fine particles, and poly N-vinylacetamide (heat-resistant fine particles and swelling properties described later) as a
前記の架橋ＰＭＭＡ微粒子は、前述の方法により測定される２５℃および１３０℃における非水電解液（後述する電池に使用する非水電解液）の吸収量が、それぞれ、架橋ＰＭＭＡ微粒子１ｇあたり、０．７ｍＬおよび２．０ｍＬであった。 The cross-linked PMMA fine particles have an absorption amount of non-aqueous electrolyte (non-aqueous electrolyte used in a battery described later) at 25 ° C. and 130 ° C. measured by the above-described method of 0 per 1 g of cross-linked PMMA fine particles. 0.7 mL and 2.0 mL.
セパレータ用の樹脂多孔質膜として、厚みが１６μｍ、空孔率が４０％で、ＰＥ層の両面にＰＰ層を有する三層構造のＰＰ／ＰＥ／ＰＰ製微多孔膜を用意し（ＰＰの融解温度１５５℃、ＰＥの融解温度１３５℃）、その両面にコロナ放電処理を施した。そして、ＰＰ／ＰＥ／ＰＰ製微多孔膜の片面に耐熱多孔質層形成用組成物を、ダイコーターを用いて、乾燥後の厚みが４．０μｍになるように均一に塗布し、乾燥して耐熱多孔質層を形成し、セパレータを得た。 As a porous resin membrane for a separator, a three-layer PP / PE / PP microporous membrane having a thickness of 16 μm and a porosity of 40% and having a PP layer on both sides of the PE layer is prepared (melting of PP The temperature was 155 ° C., the melting temperature of PE was 135 ° C.), and both surfaces were subjected to corona discharge treatment. Then, the heat-resistant porous layer forming composition is uniformly applied to one side of the microporous membrane made of PP / PE / PP using a die coater so that the thickness after drying becomes 4.0 μm, and dried. A heat resistant porous layer was formed to obtain a separator.
前記のセパレータに係る耐熱多孔質層では、ベーマイトの比重を３ｇ／ｃｍ3、架橋ＰＭＭＡの比重を１ｇ／ｃｍ3、バインダーの比重を１ｇ／ｃｍ3として算出した膨潤性微粒子の体積比率が４５体積％、耐熱性微粒子の体積比率が４５体積％であった。また、前記の各比重に加えて、ＰＥの比重を１ｇ／ｃｍ3、ＰＰの比重を１ｇ／ｃｍ3として算出したセパレータ全体中の樹脂（樹脂多孔質膜に係るポリオレフィン、並びに耐熱多孔質層に係る膨潤性微粒子およびバインダー）の体積比率は８７体積％であった。 In the heat-resistant porous layer according to the separator, the volume ratio of the swellable fine particles calculated by setting the specific gravity of boehmite to 3 g / cm 3 , the specific gravity of crosslinked PMMA to 1 g / cm 3 , and the specific gravity of the binder to 1 g / cm 3 is 45 volumes. %, And the volume ratio of the heat-resistant fine particles was 45% by volume. In addition to the specific gravity described above, the resin in the whole separator was calculated with a specific gravity of PE of 1 g / cm 3 and a specific gravity of PP of 1 g / cm 3 (in the polyolefin related to the resin porous membrane and the heat resistant porous layer). The volume ratio of the swellable fine particles and the binder) was 87% by volume.
＜正極の作製＞
正極活物質であるＬｉＮｉ0.6Ｍｎ0.2Ｃｏ0.2Ｏ2：８６．２質量部と、導電助剤である黒鉛：９．０質量部およびアセチレンブラック：１．８質量部とを混合し、ここに、３質量部のＰＶＤＦ（バインダー）を含むＮ−メチル−２−ピロリドン（ＮＭＰ）溶液を加え、よく混練して正極合剤含有スラリーを調製した。次に、正極集電体となる厚みが２０μｍのアルミニウム箔の両面に、乾燥後の正極合剤層の質量が、正極集電体の片面あたり１１．６ｍｇ／ｃｍ2となる量で前記のスラリーを均一に塗布し、その後８０℃で乾燥し、更にロールプレス機で圧縮成形して正極を得た。正極合剤含有スラリーをアルミニウム箔に塗布する際には、アルミニウム箔の一部が露出するようにした。前記正極の正極合剤層の厚みは、集電体（アルミニウム箔）の片面あたり、２６μｍであった。
<Preparation of positive electrode>
LiNi 0.6 Mn 0.2 Co 0.2 O 2 as positive electrode active material: 86.2 parts by mass, graphite as a conductive additive: 9.0 parts by mass, and acetylene black: 1.8 parts by mass, An N-methyl-2-pyrrolidone (NMP) solution containing 3 parts by mass of PVDF (binder) was added and kneaded well to prepare a positive electrode mixture-containing slurry. Next, the slurry is added in such an amount that the mass of the positive electrode mixture layer after drying is 11.6 mg / cm 2 on one side of the positive electrode current collector on both surfaces of an aluminum foil having a thickness of 20 μm to be the positive electrode current collector. Was applied uniformly, then dried at 80 ° C., and further compression molded with a roll press to obtain a positive electrode. When applying the positive electrode mixture-containing slurry to the aluminum foil, a part of the aluminum foil was exposed. The thickness of the positive electrode mixture layer of the positive electrode was 26 μm per one side of the current collector (aluminum foil).
前記の正極を、正極合剤層の大きさが８００ｍｍ×４８ｍｍで、且つアルミニウム箔の露出部を含むように裁断し、更に、電流を取り出すためのアルミニウム製リード片を、アルミニウム箔の露出部に溶接した。 The positive electrode is cut so that the size of the positive electrode mixture layer is 800 mm × 48 mm and includes the exposed portion of the aluminum foil, and an aluminum lead piece for taking out an electric current is formed on the exposed portion of the aluminum foil. Welded.
＜負極の作製＞
負極活物質である天然黒鉛：９０質量部と、導電助剤であるアセチレンブラック：４．７質量部とを混合し、ここに、５．３質量部のＰＶＤＦ（バインダー）を含むＮＭＰ溶液を加え、よく混練して負極合剤含有スラリーを調製した。次に、負極集電体となる厚みが２０μｍの圧延銅箔の両面に、乾燥後の負極合剤層の質量が、負極集電体の片面あたり５．０ｍｇ／ｃｍ2となる量で前記のスラリーを均一に塗布し、その後８０℃で乾燥し、更にロールプレス機で圧縮成形して負極を得た。なお、負極合剤含有スラリーを圧延銅箔に塗布する際には、圧延銅箔の一部が露出するようにした。前記負極の負極合剤層の厚みは、集電体（圧延銅箔）の片面あたり、２１μｍであった。
<Production of negative electrode>
Natural graphite as a negative electrode active material: 90 parts by mass and acetylene black as a conductive auxiliary agent: 4.7 parts by mass are mixed, and an NMP solution containing 5.3 parts by mass of PVDF (binder) is added thereto. The mixture was well kneaded to prepare a negative electrode mixture-containing slurry. Next, the weight of the negative electrode mixture layer after drying on both sides of a rolled copper foil having a thickness of 20 μm to be a negative electrode current collector is 5.0 mg / cm 2 per side of the negative electrode current collector in the amount described above. The slurry was uniformly applied, then dried at 80 ° C., and further compression molded with a roll press to obtain a negative electrode. When applying the negative electrode mixture-containing slurry to the rolled copper foil, a part of the rolled copper foil was exposed. The thickness of the negative electrode mixture layer of the negative electrode was 21 μm per one side of the current collector (rolled copper foil).
前記の負極を、負極合剤層の大きさが８５０ｍｍ×５２ｍｍで、且つ圧延銅箔の露出部を含むように裁断し、更に、電流を取り出すためのニッケル製リード片を、圧延銅箔の露出部に溶接した。 The negative electrode is cut so that the size of the negative electrode mixture layer is 850 mm × 52 mm and includes the exposed portion of the rolled copper foil, and a nickel lead piece for taking out the current is exposed to the rolled copper foil. Welded to the part.
＜電池の組み立て＞
前記の正極と前記の負極とを、前記のセパレータを、その耐熱多孔質層が正極と対向するように介在させつつ重ね合わせ、渦巻状に巻回して巻回電極体とした。この巻回電極体を、アルミニウム合金製の円筒形の外装体（外装缶）に挿入し、非水電解液（エチレンカーボネートとジメチルカーボネートとメチルエチルカーボネートとを２：４：４の体積比で混合した溶媒に、ＬｉＰＦ6を１ｍｏｌ／Ｌの濃度で溶解させた溶液）を外装体内に注入した後に、外装体の開口部を熱融着して、長さ６５ｍｍ、直径１８ｍｍの円筒形の巻回電極体を内部に有する非水電解液二次電池（リチウムイオン二次電池）を作製した。得られた電池の定格容量は１１５０ｍＡｈであった。以降の各実施例および比較例の電池も、定格容量は全て１１５０ｍＡｈとした。
<Battery assembly>
The positive electrode and the negative electrode were overlapped with the separator interposed so that the heat-resistant porous layer faced the positive electrode, and wound into a spiral shape to obtain a wound electrode body. This wound electrode body is inserted into a cylindrical outer casing (outer can) made of an aluminum alloy, and a non-aqueous electrolyte (ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate are mixed at a volume ratio of 2: 4: 4). A solution in which LiPF 6 is dissolved at a concentration of 1 mol / L) is injected into the exterior body, and the opening of the exterior body is heat-sealed to form a cylindrical winding having a length of 65 mm and a diameter of 18 mm. A non-aqueous electrolyte secondary battery (lithium ion secondary battery) having an electrode body therein was produced. The obtained battery had a rated capacity of 1150 mAh. The batteries of the following examples and comparative examples all have a rated capacity of 1150 mAh.
（実施例２）
架橋ＰＭＭＡ微粒子とベーマイト合成品との比率が、体積比で３０：７０となるようにした以外は実施例１と同様にして耐熱多孔質層形成用組成物を調製し、この耐熱多孔質層形成用組成物を用いた以外は、実施例１と同様にしてセパレータを作製した。このセパレータに係る耐熱多孔質層では、実施例１のセパレータと同様にして算出した膨潤性微粒子の体積比率が２７体積％、耐熱性微粒子の体積比率が６３体積％であり、実施例１と同様にして算出したセパレータ全体中の樹脂の体積比率は８２体積％であった。
(Example 2)
A composition for forming a heat resistant porous layer was prepared in the same manner as in Example 1 except that the ratio of the crosslinked PMMA fine particles to the boehmite synthesized product was 30:70 by volume. A separator was prepared in the same manner as in Example 1 except that the composition for use was used. In the heat-resistant porous layer according to this separator, the volume ratio of swellable fine particles calculated in the same manner as in the separator of Example 1 is 27% by volume, and the volume ratio of heat-resistant fine particles is 63% by volume. The volume ratio of the resin in the whole separator calculated as described above was 82% by volume.
そして、このセパレータを用いた以外は、実施例１と同様にして非水電解液二次電池を作製した。 And the nonaqueous electrolyte secondary battery was produced like Example 1 except having used this separator.
（実施例３）
架橋ＰＭＭＡ微粒子とベーマイト合成品との比率が、体積比で７０：３０となるようにした以外は実施例１と同様にして耐熱多孔質層形成用組成物を調製し、この耐熱多孔質層形成用組成物を用いた以外は、実施例１と同様にしてセパレータを作製した。このセパレータに係る耐熱多孔質層では、実施例１のセパレータと同様にして算出した膨潤性微粒子の体積比率が６５体積％、耐熱性微粒子の体積比率が２８体積％であり、実施例１と同様にして算出したセパレータ全体中の樹脂の体積比率は９２体積％であった。
(Example 3)
A composition for forming a heat resistant porous layer was prepared in the same manner as in Example 1 except that the ratio of the crosslinked PMMA fine particles to the boehmite synthesized product was 70:30 in volume ratio. A separator was prepared in the same manner as in Example 1 except that the composition for use was used. In the heat resistant porous layer according to this separator, the volume ratio of the swellable fine particles calculated in the same manner as in the separator of Example 1 is 65% by volume, and the volume ratio of the heat resistant fine particles is 28% by volume. The volume ratio of the resin in the whole separator calculated as described above was 92% by volume.
そして、このセパレータを用いた以外は、実施例１と同様にして非水電解液二次電池を作製した。 And the nonaqueous electrolyte secondary battery was produced like Example 1 except having used this separator.
（実施例４）
Ｎ−ビニルアセトアミド系ポリマーの量を、膨潤性微粒子と耐熱性微粒子との合計１００質量部に対して１質量部となる量に変更した以外は、実施例１と同様にして耐熱多孔質層形成用組成物を調製し、この耐熱多孔質層形成用組成物を用いた以外は、実施例１と同様にしてセパレータを作製した。このセパレータに係る耐熱多孔質層では、実施例１のセパレータと同様にして算出した膨潤性微粒子の体積比率が４９体積％、耐熱性微粒子の体積比率が４９体積％であり、実施例１と同様にして算出したセパレータ全体中の樹脂の体積比率は８６体積％であった。
Example 4
Formation of heat-resistant porous layer in the same manner as in Example 1 except that the amount of the N-vinylacetamide-based polymer was changed to 1 part by mass with respect to 100 parts by mass in total of the swellable fine particles and heat-resistant fine particles. A separator was prepared in the same manner as in Example 1 except that the composition for heat treatment was prepared and this heat-resistant porous layer forming composition was used. In the heat resistant porous layer according to this separator, the volume ratio of swellable fine particles calculated in the same manner as in the separator of Example 1 was 49% by volume, and the volume ratio of heat resistant fine particles was 49% by volume. The volume ratio of the resin in the whole separator calculated as described above was 86% by volume.
そして、このセパレータを用いた以外は、実施例１と同様にして非水電解液二次電池を作製した。 And the nonaqueous electrolyte secondary battery was produced like Example 1 except having used this separator.
（実施例５）
Ｎ−ビニルアセトアミド系ポリマーの量を、膨潤性微粒子と耐熱性微粒子との合計１００質量部に対して１５質量部となる量に変更した以外は、実施例１と同様にして耐熱多孔質層形成用組成物を調製し、この耐熱多孔質層形成用組成物を用いた以外は、実施例１と同様にしてセパレータを作製した。このセパレータに係る耐熱多孔質層では、実施例１のセパレータと同様にして算出した膨潤性微粒子の体積比率が３８体積％、耐熱性微粒子の体積比率が３８体積％であり、実施例１と同様にして算出したセパレータ全体中の樹脂の体積比率は８９体積％であった。
(Example 5)
The heat resistant porous layer was formed in the same manner as in Example 1 except that the amount of the N-vinylacetamide-based polymer was changed to 15 parts by mass with respect to 100 parts by mass in total of the swellable fine particles and the heat resistant fine particles. A separator was prepared in the same manner as in Example 1 except that the composition for heat treatment was prepared and this heat-resistant porous layer forming composition was used. In the heat-resistant porous layer according to this separator, the volume ratio of swellable fine particles calculated in the same manner as in the separator of Example 1 was 38% by volume, and the volume ratio of heat-resistant fine particles was 38% by volume. The volume ratio of the resin in the whole separator calculated as described above was 89% by volume.
そして、このセパレータを用いた以外は、実施例１と同様にして非水電解液二次電池を作製した。 And the nonaqueous electrolyte secondary battery was produced like Example 1 except having used this separator.
（比較例１）
ＰＥ製の微多孔膜（厚み２０μｍ、空孔率４０％）を、耐熱多孔質層を形成することなくセパレータに用いた以外は、実施例１と同様にして非水電解液二次電池を作製した。
(Comparative Example 1)
A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that a PE microporous film (thickness 20 μm, porosity 40%) was used as a separator without forming a heat-resistant porous layer. did.
（比較例２）
膨潤性微粒子である架橋ＰＭＭＡ微粒子を使用せず、バインダーをＮ−ビニルアセトアミド系ポリマーに代えてアクリレート共重合体（モノマー成分としてブチルアクリレートを主成分とするアクリル酸−ブチルアクリレート共重合体)とし、そのバインダーの量を耐熱性微粒子１００質量部に対して５質量部とした以外は、実施例１と同様にして耐熱多孔質層形成用組成物を調製し、この耐熱多孔質層形成用組成物を用いた以外は、実施例１と同様にしてセパレータを作製した。このセパレータに係る耐熱多孔質層では、実施例１のセパレータと同様にして算出した耐熱性微粒子の体積比率が８７体積％であり、実施例１と同様にして算出したセパレータ全体中の樹脂の体積比率は７４体積％であった。
(Comparative Example 2)
Without using crosslinked PMMA fine particles which are swellable fine particles, an acrylate copolymer (acrylic acid-butyl acrylate copolymer containing butyl acrylate as a main component as a monomer component) instead of an N-vinylacetamide polymer binder as a binder, A composition for forming a heat resistant porous layer was prepared in the same manner as in Example 1 except that the amount of the binder was changed to 5 parts by weight with respect to 100 parts by weight of the heat resistant fine particles, and this heat resistant porous layer forming composition was prepared. A separator was produced in the same manner as in Example 1 except that was used. In the heat-resistant porous layer according to this separator, the volume ratio of the heat-resistant fine particles calculated in the same manner as in the separator of Example 1 is 87% by volume, and the volume of the resin in the whole separator calculated in the same manner as in Example 1 The ratio was 74% by volume.
そして、このセパレータを用いた以外は、実施例１と同様にして非水電解液二次電池を作製した。 And the nonaqueous electrolyte secondary battery was produced like Example 1 except having used this separator.
（比較例３）
耐熱性微粒子を用いず、実施例１で用いたものと同じ架橋ＰＭＭＡ微粒子の水分散体１０００ｇに、実施例１で用いたものと同じバインダーを、膨潤性微粒子１００質量部に対して５質量部の量で加え、スリーワンモーターを用いて１時間攪拌して分散させ、耐熱多孔質層形成用組成物を調製した。
(Comparative Example 3)
Without using the heat-resistant fine particles, the same binder as used in Example 1 is added to 1000 g of the aqueous dispersion of the same crosslinked PMMA fine particles as used in Example 1, and 5 parts by mass with respect to 100 parts by mass of the swellable fine particles. The mixture was stirred and dispersed for 1 hour using a three-one motor to prepare a heat-resistant porous layer forming composition.
前記の耐熱多孔質層形成用組成物を用いた以外は、実施例１と同様にしてセパレータを作製した。このセパレータに係る耐熱多孔質層では、実施例１のセパレータと同様にして算出した膨潤性微粒子の体積比率が９５体積％であり、実施例１と同様にして算出したセパレータ全体中の樹脂の体積比率は１００体積％であった。 A separator was prepared in the same manner as in Example 1 except that the heat-resistant porous layer forming composition was used. In the heat-resistant porous layer according to this separator, the volume ratio of the swellable fine particles calculated in the same manner as in the separator of Example 1 is 95% by volume, and the volume of the resin in the whole separator calculated in the same manner as in Example 1 The ratio was 100% by volume.
そして、このセパレータを用いた以外は、実施例１と同様にして非水電解液二次電池を作製した。 And the nonaqueous electrolyte secondary battery was produced like Example 1 except having used this separator.
（比較例４）
Ｎ−ビニルアセトアミド系ポリマーの量を、膨潤性微粒子と耐熱性微粒子との合計１００質量部に対して０．０５質量部となる量に変更した以外は、実施例１と同様にして耐熱多孔質層形成用組成物を調製し、この耐熱多孔質層形成用組成物を用いた以外は、実施例１と同様にしてセパレータを作製した。このセパレータに係る耐熱多孔質層では、実施例１のセパレータと同様にして算出した膨潤性微粒子の体積比率が４９．９５体積％、耐熱性微粒子の体積比率が４９．９５体積％であり、実施例１と同様にして算出したセパレータ全体中の樹脂の体積比率は８５体積％であった。
(Comparative Example 4)
The heat resistant porous material was the same as in Example 1 except that the amount of the N-vinylacetamide-based polymer was changed to an amount of 0.05 parts by mass with respect to 100 parts by mass in total of the swellable fine particles and the heat resistant fine particles. A separator was prepared in the same manner as in Example 1 except that a layer forming composition was prepared and this heat resistant porous layer forming composition was used. In the heat resistant porous layer according to this separator, the volume ratio of the swellable fine particles calculated in the same manner as in the separator of Example 1 was 49.95% by volume, and the volume ratio of the heat resistant fine particles was 49.95% by volume. The volume ratio of the resin in the whole separator calculated in the same manner as in Example 1 was 85% by volume.
そして、このセパレータを用いた以外は、実施例１と同様にして非水電解液二次電池を作製した。 And the nonaqueous electrolyte secondary battery was produced like Example 1 except having used this separator.
次に、実施例１〜５および比較例１〜４の電池、並びに、これらの電池に用いたセパレータについて、以下の各評価を行った。 Next, the following evaluation was performed about the battery of Examples 1-5 and Comparative Examples 1-4, and the separator used for these batteries.
＜セパレータの熱収縮率の測定＞
セパレータを縦５ｃｍ、横１０ｃｍの長方形に切り取り、黒インクで縦方向に平行に３ｃｍ、横方向に平行に３ｃｍの十字線を描いた。セパレータを長方形に切り取るにあたっては、その縦方向が、セパレータを構成する樹脂多孔質膜の機械方向（ＭＤ）となるようにし、前記十字線は、その交点が、セパレータ片の中心となるようにした。その後、セパレータ片を、内部を２００℃に設定した恒温槽内に吊るした。そして、１時間後にセパレータ片を恒温槽から取り出して室温まで冷却した後、十字線のうちのより短い方の長さｄ（ｍｍ）を計測し、下記式によって熱収縮率（％）を算出した。
<Measurement of heat shrinkage of separator>
The separator was cut into a rectangular shape with a length of 5 cm and a width of 10 cm, and a cross line of 3 cm parallel to the vertical direction and 3 cm parallel to the horizontal direction was drawn with black ink. When the separator is cut into a rectangle, the longitudinal direction is set to the machine direction (MD) of the porous resin membrane constituting the separator, and the cross line is set so that the intersection is the center of the separator piece. . Thereafter, the separator piece was suspended in a thermostatic chamber whose interior was set to 200 ° C. And after taking out a separator piece from a thermostat after 1 hour and cooling to room temperature, length d (mm) of the shorter one of a crosshair was measured, and heat contraction rate (%) was computed by the following formula. .
熱収縮率＝１００×（３０−ｄ）／３０ Thermal contraction rate = 100 × (30−d) / 30
＜負荷特性の測定＞
各電池について、定格容量（１１５０ｍＡｈ）に対して電流値１／２Ｃ（５７５ｍＡ）で４．２Ｖまで充電した後、所定電流値で３．０Ｖまで放電して、各電流値での放電容量を測定した。放電電流値は１／２Ｃと１０Ｃとした。そして、１／２Ｃでの放電容量に対する１０Ｃでの放電容量の比を百分率で表して、容量維持率を求めた。この容量維持率が大きいほど、電池の負荷特性が良好であるといえる。
<Measurement of load characteristics>
For each battery, after charging to 4.2 V at a current value of 1/2 C (575 mA) with respect to the rated capacity (1150 mAh), discharging to 3.0 V at a predetermined current value, and measuring the discharge capacity at each current value did. The discharge current values were 1 / 2C and 10C. The ratio of the discharge capacity at 10C to the discharge capacity at 1 / 2C was expressed as a percentage to obtain the capacity maintenance ratio. It can be said that the larger the capacity retention rate, the better the load characteristics of the battery.
＜内部短絡試験＞
定格容量まで定電流−定電圧充電〔定電流：１／３Ｃ（３８３．３ｍＡ）、定電圧：４．２Ｖ、充電終止時間：４．５時間〕した各電池の、中央側面の近傍に熱電対をテープでとめ、更に厚み６ｍｍのグラスウールを巻きつけ、直径３０ｍｍの円筒形のアルミニウムラミネートフィルムで外装し、電池を断熱状態にした。また、試験時の電池の電圧および表面温度をモニタリングした。そして、２０℃で、充電状態の電池の中央から、直径３ｍｍのステンレス製の釘を１ｍｍ／ｓｅｃの速度で突き刺した。そして、短絡による電圧降下が観測された時点で釘の降下を停止して保持し、その後の電池表面の温度上昇を確認した。そして、釘の停止から１０秒以内に電池表面が２００℃まで上昇した場合を「温度上昇している（温度上昇）」と評価し、これに該当しない場合を「温度上昇を抑制できている（温度上昇抑制）」と評価した。
<Internal short circuit test>
A thermocouple in the vicinity of the central side of each battery that has been charged with constant current to constant voltage up to the rated capacity [constant current: 1/3 C (383.3 mA), constant voltage: 4.2 V, charge end time: 4.5 hours]. Was wrapped with a glass wool with a thickness of 6 mm, and covered with a cylindrical aluminum laminate film with a diameter of 30 mm to heat-insulate the battery. In addition, the battery voltage and surface temperature during the test were monitored. Then, a stainless steel nail having a diameter of 3 mm was pierced at a speed of 1 mm / sec from the center of the charged battery at 20 ° C. Then, when a voltage drop due to a short circuit was observed, the descent of the nail was stopped and held, and the subsequent temperature rise on the battery surface was confirmed. Then, when the battery surface rises to 200 ° C. within 10 seconds from the stop of the nail, it is evaluated as “temperature rise (temperature rise)”, and when it does not fall under this, “temperature rise can be suppressed ( Temperature rise suppression) ”.
実施例１〜５および比較例１〜４の電池に用いたセパレータの構成を表１に示し、前記の各評価結果を表２に示す。 The structure of the separator used for the battery of Examples 1-5 and Comparative Examples 1-4 is shown in Table 1, and each said evaluation result is shown in Table 2.
表１における耐熱多孔質層の「バインダーの量」は、膨潤性微粒子と耐熱性微粒子との合計１００質量部に対する量（質量部）を意味しており、「セパレータ全体中の樹脂の比率」は、セパレータの構成成分の全体積中における全ての樹脂の体積比率を示している。 The “amount of binder” of the heat-resistant porous layer in Table 1 means the amount (part by mass) relative to 100 parts by mass of the swellable fine particles and the heat-resistant fine particles, and “the ratio of the resin in the whole separator” is The volume ratio of all the resin in the whole volume of the component of a separator is shown.
表２に示す通り、適正な体積比率で膨潤性微粒子と耐熱性微粒子とを含有し、且つ適正な量でＮ−ビニルアセトアミド系ポリマーを含有している耐熱多孔質層を備えた実施例１〜５のセパレータは、耐熱多孔質層を薄くしてセパレータ全体の厚みの増大を抑制しつつ、２００℃におけるセパレータ全体の熱収縮を良好に抑制できている。そして、これらのセパレータを用いた実施例１〜５の非水電解液二次電池は、内部短絡試験時の温度上昇が抑えられており、異常過熱した際にも熱暴走が生じ難い信頼性および安全性に優れたものであることが確認できる。 As shown in Table 2, Examples 1 to 1 comprising a heat-resistant porous layer containing swellable fine particles and heat-resistant fine particles in an appropriate volume ratio and containing an N-vinylacetamide-based polymer in an appropriate amount. In the separator No. 5, the heat shrinkage of the entire separator at 200 ° C. can be satisfactorily suppressed while the heat resistant porous layer is thinned to suppress an increase in the thickness of the entire separator. And the non-aqueous electrolyte secondary battery of Examples 1-5 using these separators has suppressed the temperature rise at the time of an internal short circuit test, and the reliability which is hard to produce thermal runaway even when abnormally overheating, and It can be confirmed that it is excellent in safety.
これに対し、耐熱多孔質層を形成していない比較例１のセパレータ、膨潤性微粒子を含有していない耐熱多孔質層を形成した比較例２のセパレータ、耐熱性微粒子を含有していない耐熱多孔質層を形成した比較例３のセパレータ、およびＮ−ビニルアセトアミド系ポリマーの量が少ない耐熱多孔質層を形成した比較例４のセパレータは、いずれも２００℃での熱収縮率が大きく、これらを用いた比較例１〜４の電池は、内部短絡試験時における信頼性が劣っている。 In contrast, the separator of Comparative Example 1 in which no heat-resistant porous layer was formed, the separator of Comparative Example 2 in which a heat-resistant porous layer not containing swellable fine particles was formed, and the heat-resistant porous material containing no heat-resistant fine particles Both the separator of Comparative Example 3 in which the porous layer was formed and the separator of Comparative Example 4 in which the heat-resistant porous layer with a small amount of N-vinylacetamide polymer was formed had a large heat shrinkage rate at 200 ° C. The batteries of Comparative Examples 1 to 4 used have poor reliability during the internal short circuit test.
また、耐熱多孔質層におけるバインダー量を好適値としたセパレータを用いた実施例１〜４の電池は、耐熱多孔質層におけるバインダー量が多いセパレータを用いた実施例５の電池に比べて、負荷特性が良好である。 In addition, the batteries of Examples 1 to 4 using the separator with the binder amount in the heat resistant porous layer being a suitable value are more loaded than the battery of Example 5 using the separator having a large amount of binder in the heat resistant porous layer. Good characteristics.
本発明は、その趣旨を逸脱しない範囲で、上記以外の形態としても実施が可能である。本出願に開示された実施形態は一例であって、これらに限定はされない。本発明の範囲は、上述の明細書の記載よりも、添付されている請求の範囲の記載を優先して解釈され、請求の範囲と均等の範囲内での全ての変更は、請求の範囲に含まれるものである。 The present invention can be implemented in other forms than the above without departing from the spirit of the present invention. The embodiments disclosed in the present application are merely examples, and the present invention is not limited thereto. The scope of the present invention is construed in preference to the description of the appended claims rather than the description of the above specification, and all modifications within the scope equivalent to the claims are construed in the scope of the claims. It is included.
１ 正極
２ 負極
３ セパレータ
４ 非水電解液
５ 電池缶
６ 絶縁体
７ 封口板
７ａ 薄肉部
７ｂ 圧力導入口
８ 端子板
８ａ ガス排出口
９ 防爆弁
９ａ 突出部
９ｂ 薄肉部
１０ 絶縁パッキング
１１ 溶接部分
１２ 環状ガスケット
１３ リード体
１４ 絶縁体
１５ リード体
DESCRIPTION OF
Claims (8)
前記樹脂多孔質膜は、融解温度が８０〜１８０℃のポリオレフィンを主成分とする樹脂から形成され、
前記耐熱多孔質層は、加熱により非水電解液を吸収して膨潤する膨潤性微粒子と、耐熱性微粒子と、バインダーとを含み、
前記膨潤性微粒子と前記耐熱性微粒子との体積比率が、３０：７０〜７０：３０であり、
前記バインダーは、Ｎ−ビニルアセトアミド系ポリマーを含み、
前記膨潤性微粒子と前記耐熱性微粒子の合計量を１００質量部としたとき、前記Ｎ−ビニルアセトアミド系ポリマーの含有量が、０．１質量部以上であり、
前記セパレータの構成成分の全体積中における全ての樹脂の比率が、５０〜９９．９体積％であり、
前記耐熱多孔質層の厚みが、２〜１０μｍであることを特徴とする非水電解液電池用セパレータ。 A separator for a nonaqueous electrolyte battery comprising a resin porous membrane and a heat-resistant porous layer disposed on the surface of the resin porous membrane,
The resin porous membrane is formed from a resin whose main component is a polyolefin having a melting temperature of 80 to 180 ° C.,
The heat-resistant porous layer includes swellable fine particles that swell by absorbing a non-aqueous electrolyte by heating, heat-resistant fine particles, and a binder,
The volume ratio of the swellable fine particles and the heat-resistant fine particles is 30:70 to 70:30 ,
The binder includes an N-vinylacetamide-based polymer,
When the total amount of the swellable fine particles and the heat-resistant fine particles is 100 parts by mass, the content of the N-vinylacetamide polymer is 0.1 parts by mass or more,
The ratio of all the resins in the total volume of the constituent components of the separator is 50 to 99.9% by volume,
A separator for a non-aqueous electrolyte battery, wherein the heat-resistant porous layer has a thickness of 2 to 10 µm.
前記アクリル樹脂架橋体のガラス転移点が、５０〜１３０℃である請求項１に記載の非水電解液電池用セパレータ。 The swellable fine particles are formed from a crosslinked acrylic resin,
The separator for a nonaqueous electrolyte battery according to claim 1, wherein the acrylic resin crosslinked body has a glass transition point of 50 to 130 ° C.
前記セパレータが、請求項１〜７のいずれかに記載の非水電解液電池用セパレータであることを特徴とする非水電解液電池。 Including positive electrode, negative electrode, separator and non-aqueous electrolyte,
The said separator is a separator for nonaqueous electrolyte batteries in any one of Claims 1-7, The nonaqueous electrolyte battery characterized by the above-mentioned.
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| KR102656529B1 (en) * | 2012-08-07 | 2024-04-12 | 셀가드 엘엘씨 | Improved separator membranes for lithium ion batteries and related methods |
| JP6008199B2 (en) * | 2013-04-16 | 2016-10-19 | トヨタ自動車株式会社 | Lithium ion secondary battery |
| WO2021206431A1 (en) * | 2020-04-06 | 2021-10-14 | 주식회사 엘지에너지솔루션 | Separator for electrochemical element and method for manufacturing same |
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| KR100947072B1 (en) * | 2008-03-27 | 2010-04-01 | 삼성에스디아이 주식회사 | Electrode Assembly and Secondary Battery having the Same |
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