JP2011134562A - Separator for nonaqueous secondary battery, and nonaqueous secondary battery - Google Patents
Separator for nonaqueous secondary battery, and nonaqueous secondary battery Download PDFInfo
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- JP2011134562A JP2011134562A JP2009292623A JP2009292623A JP2011134562A JP 2011134562 A JP2011134562 A JP 2011134562A JP 2009292623 A JP2009292623 A JP 2009292623A JP 2009292623 A JP2009292623 A JP 2009292623A JP 2011134562 A JP2011134562 A JP 2011134562A
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- secondary battery
- separator
- aqueous secondary
- polyolefin
- heat
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- 229910052744 lithium Inorganic materials 0.000 claims description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
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- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、非水系二次電池用セパレータ及び非水系二次電池に関わるものであり、特に非水系二次電池等の安全性を向上させる技術に関するものである。 The present invention relates to a separator for a non-aqueous secondary battery and a non-aqueous secondary battery, and particularly relates to a technique for improving the safety of a non-aqueous secondary battery or the like.
正極にコバルト酸リチウムに代表されるリチウム含有遷移金属酸化物、負極にリチウムをドープ・脱ドープ可能な炭素材料を用いたリチウムイオン二次電池を代表とする非水系二次電池は、高エネルギー密度を有するという特徴から携帯電話に代表される携帯電子機器の電源として重要なものであり、これら携帯電子機器の急速な普及に伴いその需要は高まる一方である。 Non-aqueous secondary batteries such as lithium-ion secondary batteries, which use lithium-containing transition metal oxides typified by lithium cobaltate as the positive electrode and carbon materials that can be doped or dedoped with lithium as the negative electrode, have high energy density. It is important as a power source for portable electronic devices typified by mobile phones because of its characteristics, and demand for these portable electronic devices is increasing with the rapid spread of these portable electronic devices.
また、ハイブリッド自動車など、環境対応を意識した自動車が数多く開発されているが、搭載される電源の一つとして、高エネルギー密度を有するリチウムイオン二次電池が大きく注目されている。 In addition, many automobiles that are environmentally conscious, such as hybrid cars, have been developed, but lithium ion secondary batteries having a high energy density have attracted a great deal of attention as one of the power sources to be mounted.
リチウムイオン二次電池の多くは、正極、電解液を含むセパレータ、負極の積層体から構成されている。セパレータは、主たる機能として正極と負極の短絡防止を担っているが、要求特性として、リチウムイオンの移動度、強度、耐久性などがある。 Many lithium ion secondary batteries are composed of a laminate of a positive electrode, a separator containing an electrolytic solution, and a negative electrode. The separator is responsible for preventing a short circuit between the positive electrode and the negative electrode as a main function, but as required characteristics, there are mobility, strength, durability, and the like of lithium ions.
現在、リチウムイオン二次電池セパレータ用途に適するフィルムとして各種のポリオレフィン微多孔膜が数多く提案されている。ポリオレフィン微多孔膜中でもポリエチレン微多孔膜は、上述にある要求特性を満たし、かつ高温時の安全機能として、高温による孔の閉塞から電流を遮断する事による熱暴走防止機能、いわゆるシャットダウン機能を有している事もあり、リチウムイオン二次電池のセパレータとして幅広く使用されている。 At present, various polyolefin microporous membranes have been proposed as films suitable for lithium ion secondary battery separator applications. Among polyolefin microporous membranes, polyethylene microporous membranes meet the above-mentioned required characteristics, and have a function of preventing thermal runaway by shutting off current from hole blockage due to high temperatures, a so-called shutdown function, as a safety function at high temperatures. It is widely used as a separator for lithium ion secondary batteries.
しかしながら、温度上昇により微多孔膜の孔が閉塞されて電流が一旦遮断されても、電池温度が微多孔膜を構成するポリエチレンの融点を超えて、ポリエチレンの耐熱性の限界を超えると、微多孔膜自体が溶融してシャットダウン機能が失われる。その結果、電極間の短絡をきっかけとして電池の熱暴走がおこり、リチウムイオン二次電池を組み込んだ装置の破壊や、発火による事故発生などを招くおそれがある。このため、さらなる安全性確保のために、高温時でもシャットダウン機能を維持できるセパレータが求められている。 However, even if the pores of the microporous membrane are blocked due to the temperature rise and the current is interrupted once, if the battery temperature exceeds the melting point of polyethylene constituting the microporous membrane and exceeds the heat resistance limit of polyethylene, the microporous membrane The membrane itself melts and the shutdown function is lost. As a result, a short circuit between the electrodes causes a thermal runaway of the battery, which may cause destruction of a device incorporating the lithium ion secondary battery or occurrence of an accident due to ignition. For this reason, in order to ensure further safety, there is a demand for a separator that can maintain a shutdown function even at high temperatures.
そこで、特許文献１には、ポリエチレン微多孔膜の表面に、全芳香族ポリアミド等の耐熱性ポリマーからなる耐熱性多孔質層を被覆した非水系二次電池用セパレータが提案されている。また、特許文献２には、耐熱性多孔質層中にアルミナ等の無機微粒子を含ませて、シャットダウン機能に加えて耐熱性の向上を図った構成が示されている。また、特許文献３には、耐熱性多孔質層中に水酸化アルミニウム等の金属水酸化物粒子を含ませて、シャットダウン機能および耐熱性に加えて難燃性の向上を図った構成が示されている。これらの構成はいずれも、シャットダウン機能と耐熱性を両立させた点において、電池の安全性という観点において優れた効果が期待できる。 Thus, Patent Document 1 proposes a separator for a non-aqueous secondary battery in which the surface of a polyethylene microporous membrane is covered with a heat-resistant porous layer made of a heat-resistant polymer such as wholly aromatic polyamide. Patent Document 2 discloses a configuration in which inorganic fine particles such as alumina are included in the heat-resistant porous layer to improve the heat resistance in addition to the shutdown function. Patent Document 3 discloses a structure in which metal hydroxide particles such as aluminum hydroxide are included in the heat-resistant porous layer to improve the flame retardancy in addition to the shutdown function and heat resistance. ing. Any of these configurations can be expected to have an excellent effect in terms of battery safety in terms of both a shutdown function and heat resistance.
しかし、これら非水系二次電池用セパレータはポリオレフィン微多孔膜を耐熱性多孔質層でコーティングするという構造のため、ポリオレフィン微多孔膜の有するシャットダウン機能を抑制する傾向にあり、ポリオレフィン微多孔膜のみからなるセパレータに匹敵するシャットダウン機能を有する非水系二次電池用セパレータが望まれていた。更に、リチウムイオン二次電池は携帯電子機器等に多く使用されている事から、上記に示す高温時の安全確保のほかに、衝撃時における安全性も強く求められている。 However, these non-aqueous secondary battery separators have a structure in which a polyolefin microporous membrane is coated with a heat-resistant porous layer, and therefore there is a tendency to suppress the shutdown function of the polyolefin microporous membrane. Therefore, a separator for a non-aqueous secondary battery having a shutdown function comparable to the separator is desired. Further, since lithium ion secondary batteries are widely used in portable electronic devices and the like, in addition to ensuring safety at high temperatures as described above, safety at impact is also strongly required.
本発明の目的は、シャットダウン特性や耐熱性に加え、優れた機械強度を有する非水系二次電池用セパレータを提供することにある。 The objective of this invention is providing the separator for non-aqueous secondary batteries which has the outstanding mechanical strength in addition to the shutdown characteristic and heat resistance.
本発明者らは、シャットダウン特性や耐熱性に加え、優れた機械強度を有する非水系二次電池用セパレータを提供すべく鋭意検討を重ねた結果、ポリオレフィン微多孔膜が特定の構成をとっている事により可能である事を見出し、本発明に到達した。 As a result of intensive studies to provide a separator for a non-aqueous secondary battery having excellent mechanical strength in addition to shutdown characteristics and heat resistance, the present inventors have taken a specific configuration of the polyolefin microporous membrane. We have found that this is possible, and have reached the present invention.
すなわち、本発明は、ポリオレフィン多孔質基材と、耐熱性樹脂を含んで形成され前記ポリオレフィン多孔質基材の片面又は両面に積層された耐熱性多孔質層と、を備えた非水系二次電池用セパレータであって、前記ポリオレフィン多孔質基材は、ポリエチレンとポリエチレン以外のポリオレフィンとを含むことを特徴とする非水系二次電池用セパレータである。
また、リチウムのドープ・脱ドープにより起電力を得る非水系二次電池であって、前記非水系二次電池用セパレータを用いたことを特徴とする非水系二次電池である。
That is, the present invention provides a non-aqueous secondary battery comprising a polyolefin porous substrate and a heat-resistant porous layer formed by containing a heat-resistant resin and laminated on one or both sides of the polyolefin porous substrate. The non-aqueous secondary battery separator is characterized in that the polyolefin porous substrate contains polyethylene and a polyolefin other than polyethylene.
Moreover, it is a non-aqueous secondary battery which obtains an electromotive force by doping and dedoping of lithium, wherein the non-aqueous secondary battery separator is used.
本発明では、シャットダウン特性や耐熱性に加え、優れた機械強度を有する非水系二次電池用セパレータを提供することができる。本発明の非水系二次電池用セパレータによれば、非水系二次電池の安全性を向上させることができる。 In the present invention, a separator for a non-aqueous secondary battery having excellent mechanical strength in addition to shutdown characteristics and heat resistance can be provided. According to the separator for a non-aqueous secondary battery of the present invention, the safety of the non-aqueous secondary battery can be improved.
以下に、本発明の実施の形態について順次説明する。なお、これらの説明及び実施例は本発明を例示するものであり、本発明の範囲を制限するものではない。 Hereinafter, embodiments of the present invention will be sequentially described. In addition, these description and Examples illustrate this invention, and do not restrict | limit the scope of the present invention.
［非水系二次電池用セパレータ］
本発明の非水系二次電池用セパレータは、ポリオレフィン多孔質基材と、耐熱性樹脂を含んで形成され前記ポリオレフィン多孔質基材の片面又は両面に積層された耐熱性多孔質層と、を備えた非水系二次電池用セパレータであって、前記ポリオレフィン多孔質基材は、ポリエチレンとポリエチレン以外のポリオレフィン（以下、他のポリオレフィンと適宜称す）とを含むことを特徴とする。
[Separator for non-aqueous secondary battery]
A separator for a non-aqueous secondary battery according to the present invention includes a polyolefin porous substrate, and a heat resistant porous layer formed by including a heat resistant resin and laminated on one or both surfaces of the polyolefin porous substrate. Further, the separator for a non-aqueous secondary battery is characterized in that the polyolefin porous substrate contains polyethylene and a polyolefin other than polyethylene (hereinafter referred to as other polyolefin as appropriate).
このような本発明の非水系二次電池用セパレータによれば、基材となるポリオレフィン多孔質基材がポリエチレンと他のポリオレフィンを含む事により、シャットダウン特性及び機械強度が得られる共に、耐熱性多孔質層によりシャットダウン温度以上の温度においても、ポリオレフィン多孔質基材が保持されるため高温時の安全性を確保できる。従って、本発明のセパレータによれば、安全性に優れた非水系二次電池を得ることができる。 According to such a separator for a non-aqueous secondary battery of the present invention, the polyolefin porous substrate as a substrate contains polyethylene and other polyolefins, so that shutdown characteristics and mechanical strength can be obtained, and heat resistant porous The polyolefin porous substrate is retained even at a temperature equal to or higher than the shutdown temperature by the porous layer, so that safety at a high temperature can be ensured. Therefore, according to the separator of the present invention, a non-aqueous secondary battery excellent in safety can be obtained.
本発明のポリオレフィン多孔質基材はポリエチレンと他のポリオレフィンとを含む。シャットダウン特性はポリエチレンが主に担っており、機械強度は他のポリオレフィンが主に担っている。よって、本発明において、他のポリオレフィンとしては、ポリエチレンよりも機械強度の高いポリオレフィンであれば特に限定されるものではなく、具体的にはポリプロピレン、ポリメチルペンテン、またはこれらの１種以上の組合わせ等を挙げることができる。中でも、ポリエチレンの融点と比較的近い融点を有するポリプロピレンを用いることが、製造法の観点から好ましい。 The polyolefin porous substrate of the present invention contains polyethylene and other polyolefins. The shutdown characteristic is mainly borne by polyethylene, and the mechanical strength is mainly borne by other polyolefins. Therefore, in the present invention, the other polyolefin is not particularly limited as long as it is a polyolefin having higher mechanical strength than polyethylene, and specifically, polypropylene, polymethylpentene, or a combination of one or more of these. Etc. can be mentioned. Among these, it is preferable from the viewpoint of the production method to use polypropylene having a melting point relatively close to that of polyethylene.
また、他のポリオレフィンの多くの臨界表面張力は、ポリエチレンの臨界表面張力より低いものが多い。本発明では、耐熱性多孔質層は、耐熱性樹脂を含むスラリーをポリオレフィン多孔質層の上に塗工する事で形成する。耐熱性樹脂を溶解させる溶媒としては、ジメチルアセトアミド、Ｎ，Ｎ−メチルピロリドンなどが用いられる。このようなスラリーは、濡れ性の関係から、ポリオレフィン多孔質基材におけるポリエチレン部分上には塗布できるが、ポリプロピレン等の他のポリオレフィン部分上に塗布するのは困難である。本発明ではポリエチレンと他のポリオレフィンは混合して用いるため、ポリエチレンと他のポリオレフィンはミクロなレベルで混合しており、耐熱性多孔質層は、ポリプロピレン等の他のポリオレフィンを避ける形で形成されるため、耐熱性多孔質層と本発明のポリオレフィン多孔質基材の接着力は、耐熱性多孔質層とポリエチレンのみからなる多孔質基材を複合する場合よりも低下する。結果、本発明によれば、耐熱性多孔質層によるポリエチレンの流動性の阻害が抑制され、優れたシャットダウン特性を有することになる。 Also, many of the critical surface tensions of other polyolefins are often lower than the critical surface tension of polyethylene. In the present invention, the heat resistant porous layer is formed by applying a slurry containing a heat resistant resin on the polyolefin porous layer. As a solvent for dissolving the heat-resistant resin, dimethylacetamide, N, N-methylpyrrolidone, or the like is used. Such a slurry can be applied on the polyethylene portion of the polyolefin porous substrate because of wettability, but is difficult to apply on other polyolefin portions such as polypropylene. In the present invention, polyethylene and other polyolefins are used in combination, so polyethylene and other polyolefins are mixed at a micro level, and the heat-resistant porous layer is formed so as to avoid other polyolefins such as polypropylene. Therefore, the adhesive force between the heat-resistant porous layer and the polyolefin porous substrate of the present invention is lower than when the heat-resistant porous layer and a porous substrate made only of polyethylene are combined. As a result, according to the present invention, inhibition of the fluidity of polyethylene by the heat-resistant porous layer is suppressed, and excellent shutdown characteristics are obtained.
本発明の非水系二次電池用セパレータは、全体の膜厚が３０μｍ以下であることが好ましい。セパレータが３０μｍを超える場合、非水系二次電池のエネルギー密度が低下する傾向があり、好ましくない。 The separator for a non-aqueous secondary battery of the present invention preferably has a total film thickness of 30 μm or less. When a separator exceeds 30 micrometers, there exists a tendency for the energy density of a non-aqueous secondary battery to fall, and it is unpreferable.
本発明の非水系二次電池用セパレータの空孔率は３０〜７０％であることが好ましい。更に好ましくは、４０％〜６０％である。空孔率が３０％を下回る場合、透過性が低下しリチウムイオンの移動度が低下する場合があるため、好ましくない。一方、空孔率が７０％を越える場合、力学強度が不十分となりハンドリング性が低下する場合があるため、好ましくない。 The porosity of the nonaqueous secondary battery separator of the present invention is preferably 30 to 70%. More preferably, it is 40% to 60%. When the porosity is less than 30%, the permeability may decrease and the mobility of lithium ions may decrease, which is not preferable. On the other hand, when the porosity exceeds 70%, the mechanical strength is insufficient and the handling property may be deteriorated.
本発明の非水系二次電池用セパレータのガーレ値（ＪＩＳ・Ｐ８１１７）は１００〜５００ｓｅｃ／１００ｃｃであることが好ましい。ガーレ値がこの範囲にある時、セパレータの機械強度と膜抵抗のバランスがとれたものとなる。１００ｓｅｃ／１００ｃｃ未満の場合、該セパレータの機械強度が低下する傾向にあり好ましくない。５００ｓｅｃ／１００ｃｃを超える場合、該非水系二次電池用セパレータの膜抵抗が低下する傾向にあり、好ましくない。 The Gurley value (JIS P8117) of the separator for a non-aqueous secondary battery of the present invention is preferably 100 to 500 sec / 100 cc. When the Gurley value is in this range, the separator mechanical strength and the membrane resistance are balanced. If it is less than 100 sec / 100 cc, the mechanical strength of the separator tends to decrease, which is not preferable. When it exceeds 500 sec / 100 cc, the membrane resistance of the separator for non-aqueous secondary batteries tends to decrease, which is not preferable.
本発明の非水系二次電池用セパレータの膜抵抗は１．５〜１０ｏｈｍ・ｃｍ２であることが好ましい。非水系二次電池用セパレータの膜抵抗は非水系二次電池の負荷特性に影響するため、小さい方が好ましい。 The membrane resistance of the non-aqueous secondary battery separator of the present invention is preferably 1.5 to 10 ohm · cm 2 . Since the membrane resistance of the non-aqueous secondary battery separator affects the load characteristics of the non-aqueous secondary battery, a smaller one is preferable.
本発明の非水系二次電池用セパレータの突刺強度は４５０〜１０００ｇであることが好ましい。突刺強度が４５０ｇ未満の場合、電池使用時の激しい衝撃等により、セパレータに破膜、ピンホール等が発生し、非水系二次電池が短絡する可能性があり好ましくない。４５０ｇを超えているという事は、非水系二次電池用セパレータとして充分な強度を有する事を意味し、耐衝撃性が高い事を示す。 The puncture strength of the nonaqueous secondary battery separator of the present invention is preferably 450 to 1000 g. When the puncture strength is less than 450 g, the separator may cause a film breakage, a pinhole, or the like due to a severe impact during use of the battery, and the nonaqueous secondary battery may be short-circuited. When it exceeds 450 g, it means having sufficient strength as a separator for a non-aqueous secondary battery, and indicates that the impact resistance is high.
本発明の非水系二次電池用セパレータの引張強度は１０Ｎ以上であることが好ましい。１０Ｎ未満の場合、非水系二次電池を作成する時にセパレータを捲回する際に、セパレータが破損する可能性が高くなる。１０Ｎ以上という事は、非水系二次電池用電池セパレータとして充分な強度を有する事を意味し、製造する際や、加工する際のハンドリング性が高い事を示す。 The tensile strength of the nonaqueous secondary battery separator of the present invention is preferably 10 N or more. If it is less than 10N, the separator is likely to be damaged when the separator is wound when a non-aqueous secondary battery is produced. 10N or more means that it has sufficient strength as a battery separator for non-aqueous secondary batteries, and indicates that it is easy to handle and process.
本発明の非水系二次電池用セパレータのシャットダウン温度は１３０〜１５５℃であることが好ましい。シャットダウン温度は、抵抗値が１０３ｏｈｍ・ｃｍ２となった温度を差す。シャットダウン温度が１３０℃未満の場合、同時にポリオレフィン多孔質基材が完全溶融し短絡現象が発生するメルトダウンと呼ばれる現象が低温で発生する事になり、安全上好ましくない。また、シャットダウン温度が１５５℃より大きい場合、高温時の十分な安全機能が期待できず好ましくない。好ましくは１３５〜１５０℃である。なお、本発明の非水系二次電池用セパレータのシャットダウン温度と、これに用いた多孔質基材単独でのシャットダウン温度との差は、０〜５℃であることが好ましい。 The shutdown temperature of the separator for a non-aqueous secondary battery of the present invention is preferably 130 to 155 ° C. The shutdown temperature is the temperature at which the resistance value is 10 3 ohm · cm 2 . When the shutdown temperature is less than 130 ° C., a phenomenon called meltdown, in which the polyolefin porous base material is completely melted and a short-circuit phenomenon occurs at the same time, is not preferable for safety. Moreover, when the shutdown temperature is higher than 155 ° C., a sufficient safety function at a high temperature cannot be expected, which is not preferable. Preferably it is 135-150 degreeC. In addition, it is preferable that the difference of the shutdown temperature of the separator for non-aqueous secondary batteries of this invention and the shutdown temperature of the porous base material used for this is 0-5 degreeC.
本発明の非水系二次電池用セパレータの１０５℃における熱収縮率は０．５〜１０％であることが好ましい。熱収縮率がこの範囲にある時、非水系二次電池用セパレータの形状安定性とシャットダウン特性のバランスがとれたものとなる。１０％以上の場合、高温時の形状安定性が悪くなり、好ましくない。好ましくは０．５〜５％である。 The thermal contraction rate at 105 ° C. of the separator for a non-aqueous secondary battery of the present invention is preferably 0.5 to 10%. When the heat shrinkage rate is within this range, the shape stability and shutdown characteristics of the non-aqueous secondary battery separator are balanced. When it is 10% or more, the shape stability at high temperature is deteriorated, which is not preferable. Preferably it is 0.5 to 5%.
［ポリオレフィン多孔質基材］
本発明のポリオレフィン多孔質基材において、多孔質基材としては、微多孔膜状、不織布状、紙状、その他三次元ネットーワーク状の多孔質構造を有した基材を挙げることができるが、より優れたシャットダウン特性が得られ、かつ、耐熱性多孔質層の塗工性が良好になる点で、微多孔膜であることが好ましい。ここで、微多孔膜とは、内部に多数の微細孔を有し、これら微細孔が連結された構造となっており、一方の面から他方の面へと気体あるいは液体が通過可能となった膜を言う。
[Polyolefin porous substrate]
In the polyolefin porous substrate of the present invention, examples of the porous substrate include a substrate having a microporous membrane shape, a nonwoven fabric shape, a paper shape, and other three-dimensional network-like porous structures, A microporous membrane is preferred in that superior shutdown characteristics are obtained and the coating property of the heat-resistant porous layer is improved. Here, the microporous membrane has a structure in which a large number of micropores are connected and these micropores are connected, and gas or liquid can pass from one surface to the other. Say the membrane.
本発明で用いられるポリオレフィン多孔質基材の原料としては、ポリエチレン、および、ポリエチレン以外のポリオレフィンを用いる必要がある。ポリオレフィン多孔質基材は、９０重量％以上がポリエチレンおよび他のポリオレフィンからなるものであればよく、１０重量％以下の、電池特性に影響を与えない他の成分を含んでいても構わない。ポリエチレンとしては、高密度ポリエチレンや、高密度ポリエチレンと超高分子量ポリエチレンの混合物が、強度および耐熱性等の観点から好ましい。他のポリオレフィンとしては、上述したようにポリエチレンよりも機械強度の高いポリオレフィンであれば特に限定されるものではないが、具体的にはポリプロピレン、ポリメチルペンテン、またはこれらの１種以上の組合わせ等を挙げることができる。中でも、ポリエチレンの融点と比較的近い融点を有するポリプロピレンを用いることが製造法の観点から好ましい。ポリプロピレンとしては、ポリプロピレンの重量平均分子量（Mw）は１万〜４００万が好ましく、３０万〜３００万がより好ましい。 As a raw material for the polyolefin porous substrate used in the present invention, it is necessary to use polyethylene and polyolefins other than polyethylene. The polyolefin porous substrate may be composed of 90% by weight or more of polyethylene and other polyolefins, and may contain 10% by weight or less of other components that do not affect battery characteristics. As the polyethylene, high-density polyethylene or a mixture of high-density polyethylene and ultrahigh molecular weight polyethylene is preferable from the viewpoints of strength and heat resistance. The other polyolefin is not particularly limited as long as it is a polyolefin having higher mechanical strength than polyethylene as described above. Specifically, polypropylene, polymethylpentene, or a combination of one or more of these, etc. Can be mentioned. Among these, it is preferable from the viewpoint of the production method to use polypropylene having a melting point relatively close to that of polyethylene. As polypropylene, the weight average molecular weight (Mw) of polypropylene is preferably 10,000 to 4,000,000, more preferably 300,000 to 3,000,000.
本発明において、ポリオレフィン多孔質基材に含まれるポリエチレンと他のポリオレフィンの比に特に限定はないが、ポリエチレンが６０〜９５重量％含まれることが好ましい。ポリエチレンの添加率が６０重量％未満の場合、シャットダウン特性が低下することになり、好ましくない。逆にポリエチレンの添加率が９５重量％を超える場合、機械強度が低下することになり、好ましくない。 In the present invention, the ratio of polyethylene and other polyolefin contained in the polyolefin porous substrate is not particularly limited, but it is preferable that 60 to 95% by weight of polyethylene is contained. When the addition ratio of polyethylene is less than 60% by weight, the shutdown characteristics are deteriorated, which is not preferable. On the contrary, when the addition rate of polyethylene exceeds 95% by weight, the mechanical strength is lowered, which is not preferable.
本発明に用いるポリオレフィン多孔質基材の膜厚は、５〜２５μｍであることが好ましい。５μｍを下回る場合、力学強度が不十分となりハンドリング性が低下する場合があるため、好ましくない。２５μｍを超える場合、非水系二次電池のエネルギー密度が低下し、十分な負荷特性を達成するのが困難になる場合があるため、好ましくない。 The film thickness of the polyolefin porous substrate used in the present invention is preferably 5 to 25 μm. When the thickness is less than 5 μm, the mechanical strength is insufficient and the handling property may be lowered. When it exceeds 25 μm, the energy density of the non-aqueous secondary battery decreases, and it may be difficult to achieve sufficient load characteristics, which is not preferable.
本発明のポリオレフィン多孔質基材の空孔率は３０〜６０％であることが好ましい。更に好ましくは、４０％〜６０％である。空孔率が３０％を下回る場合、透過性が低下しリチウムイオンの移動度が低下する場合があるため、好ましくない。一方、空孔率が６０％を越える場合、力学強度が不十分となりハンドリング性が低下する場合があるため、好ましくない。 The porosity of the polyolefin porous substrate of the present invention is preferably 30 to 60%. More preferably, it is 40% to 60%. When the porosity is less than 30%, the permeability may decrease and the mobility of lithium ions may decrease, which is not preferable. On the other hand, when the porosity exceeds 60%, the mechanical strength is insufficient and the handling property may be deteriorated.
本発明のポリオレフィン多孔質基材のガーレ値（ＪＩＳ・Ｐ８１１７）は５０〜５００ｓｅｃ／１００ｃｃであることが好ましい。ガーレ値がこの範囲にある時、セパレータの機械強度と膜抵抗のバランスがとれたものとなる。５０ｓｅｃ／１００ｃｃ未満の場合、該セパレータの機械強度が低下する傾向にあり好ましくない。５００ｓｅｃ／１００ｃｃを超える場合、ポリオレフィン多孔質基材の膜抵抗が低下する傾向にあり、好ましくない。 The Gurley value (JIS P8117) of the polyolefin porous substrate of the present invention is preferably 50 to 500 sec / 100 cc. When the Gurley value is in this range, the separator mechanical strength and the membrane resistance are balanced. If it is less than 50 sec / 100 cc, the mechanical strength of the separator tends to decrease, which is not preferable. When it exceeds 500 sec / 100 cc, the membrane resistance of the polyolefin porous substrate tends to decrease, which is not preferable.
本発明のポリオレフィン多孔質基材の膜抵抗は０．５〜５ｏｈｍ・ｃｍ２であることが好ましい。ポリオレフィン多孔質基材の膜抵抗は、これを加工して得た非水系二次電池用セパレータ及び非水系二次電池の負荷特性に影響するため、小さい方が好ましい。 The membrane resistance of the polyolefin porous substrate of the present invention is preferably 0.5 to 5 ohm · cm 2 . Since the membrane resistance of the polyolefin porous substrate affects the load characteristics of the non-aqueous secondary battery separator and the non-aqueous secondary battery obtained by processing the polyolefin porous substrate, a smaller one is preferable.
本発明のポリオレフィン多孔質基材の突刺強度は４００ｇ以上であることが好ましい。４００ｇを下回る場合、これを使用した非水系二次電池用セパレータが十分な突刺強度を有する事が困難になり、電池使用時の激しい衝撃等により、セパレータに破膜、ピンホール等が発生し、非水系二次電池が短絡する可能性があり好ましくない。４００ｇを超えているという事は、これを用いた非水系二次電池用セパレータが充分な強度を有する事を意味し、耐衝撃性が高い事を示す。 The piercing strength of the polyolefin porous substrate of the present invention is preferably 400 g or more. If it is less than 400 g, it becomes difficult for the separator for non-aqueous secondary batteries using this to have sufficient piercing strength, resulting in severe film impact, pinholes, etc. due to severe impact during battery use, The non-aqueous secondary battery may be short-circuited, which is not preferable. That it exceeds 400 g means that the separator for non-aqueous secondary batteries using this has sufficient intensity | strength, and shows that impact resistance is high.
本発明のポリオレフィン多孔質基材の引張強度は１０Ｎ以上であることが好ましい。１０Ｎを下回る場合、非水系二次電池を作成する時にセパレータを捲回する際に、セパレータが破損する可能性が高くなる。１０Ｎ以上という事は、電池用セパレータとして充分な強度を有する事を意味し、製造する際や、加工する際のハンドリング性が高い事を示す。 The polyolefin porous substrate of the present invention preferably has a tensile strength of 10N or more. When less than 10N, when winding a separator when producing a non-aqueous secondary battery, possibility that a separator will be damaged becomes high. 10N or more means that the battery has sufficient strength as a battery separator, and indicates that the handleability is high when manufacturing and processing.
本発明のポリオレフィン多孔質基材の１０５℃における熱収縮率は５〜２５％以下であることが好ましい。熱収縮率がこの範囲にある時、ポリオレフィン多孔質基材を加工して得た非水系二次電池用セパレータの形状安定性とシャットダウン特性のバランスがとれたものとなる。熱収縮率が５％未満の場合、ポリオレフィンの流動性が悪い事を意味し、シャットダウン特性が低下し、好ましくない。熱収縮率が２５％を越える場合、高温時の形状安定性が悪くなり、好ましくない。 The heat shrinkage rate at 105 ° C. of the polyolefin porous substrate of the present invention is preferably 5 to 25% or less. When the heat shrinkage is in this range, the shape stability and shutdown characteristics of the separator for a non-aqueous secondary battery obtained by processing a polyolefin porous substrate are balanced. When the heat shrinkage rate is less than 5%, it means that the polyolefin has poor fluidity, and the shutdown characteristics are lowered, which is not preferable. When the thermal shrinkage rate exceeds 25%, the shape stability at high temperature is deteriorated, which is not preferable.
［ポリオレフィン多孔質基材の製造法］
以下本発明で用いられるポリオレフィン多孔質基材のうち、ポリオレフィン微多孔膜の好ましい製造法について述べる。
本発明のポリオレフィン微多孔膜の製造法に、特に制限は無いが、具体的には下記（１）〜（６）の工程を経て製造できる。
[Polyolefin porous substrate manufacturing method]
Hereinafter, among the polyolefin porous substrates used in the present invention, a preferred method for producing a polyolefin microporous membrane will be described.
Although there is no restriction | limiting in particular in the manufacturing method of the polyolefin microporous film of this invention, Specifically, it can manufacture through the process of following (1)-(6).
（１）ポリオレフィン溶液の調整
ポリオレフィンをパラフィン、流動パラフィン、パラフィン油、鉱油、ひまし油、テトラリン、エチレングリコール、グリセリン、デカリン、トルエン、キシレン、ジエチルトリアミン、エチルジアミン、ジメチルスルホキシド、ヘキサン等の溶剤に溶解させた溶液を調整する。この時、溶剤を混合して溶液を作成しても構わない。ポリオレフィン溶液の濃度は１〜３５重量％が好ましく、より好ましくは１０〜３０重量％である。ポリオレフィン溶液の濃度が１重量％未満では、冷却ゲル化して得られるゲル状成形物が溶媒で高度に膨潤されるため変形し易く、取扱いに支障をきたす場合がある。一方、３５重量％を越えると押し出しの際の圧力が高くなるため吐出量が低くなり生産性が上げられない場合がある。また、押し出し工程での配向が進み、延伸性や均一性が確保できなくなる場合がある。
(1) Preparation of polyolefin solution Polyolefin is dissolved in a solvent such as paraffin, liquid paraffin, paraffin oil, mineral oil, castor oil, tetralin, ethylene glycol, glycerin, decalin, toluene, xylene, diethyltriamine, ethyldiamine, dimethylsulfoxide, hexane, etc. Adjust the solution. At this time, a solution may be prepared by mixing solvents. The concentration of the polyolefin solution is preferably 1 to 35% by weight, more preferably 10 to 30% by weight. When the concentration of the polyolefin solution is less than 1% by weight, the gel-like molded product obtained by cooling and gelation is highly swollen with a solvent, so that it is easily deformed, which may hinder handling. On the other hand, if it exceeds 35% by weight, the pressure at the time of extrusion becomes high, so the discharge amount becomes low and the productivity may not be increased. Moreover, the orientation in the extrusion process proceeds, and stretchability and uniformity may not be ensured.
（２）ポリオレフィン溶液の押出
調整した溶液もしくは融液を一軸押出機、もしくは二軸押出機で混練し、融点以上かつ融点＋６０℃以下の温度でＴダイもしくはＩダイで押し出す。好ましくは二軸押出機を用いる。そして、押し出した溶液をチルロールまたは冷却浴に通過させて、ゲル状のベーステープを形成する。この際、ゲル化温度以下に急冷しゲル化することが好ましい。
(2) Extrusion of polyolefin solution The adjusted solution or melt is kneaded with a single screw extruder or a twin screw extruder, and extruded with a T die or an I die at a temperature not lower than the melting point and not higher than the melting point + 60 ° C. A twin screw extruder is preferably used. Then, the extruded solution is passed through a chill roll or a cooling bath to form a gel-like base tape. At this time, it is preferable to rapidly cool below the gelation temperature to cause gelation.
（３）ゲル状組成物の乾燥
延伸温度で揮発する溶剤を使用する場合、ゲル状組成物を乾燥する。
(3) Drying of gel-like composition When using the solvent which volatilizes at extending | stretching temperature, a gel-like composition is dried.
（４）ゲル状組成物の延伸
ゲル状組成物を延伸する。ここで、延伸処理の前に弛緩処理を行っても良い。延伸処理は、ゲル状成形物を加熱し、通常のテンター法、ロール法、圧延法もしくはこれらの方法の組合せによって所定の倍率で２軸延伸する。２軸延伸は、同時または逐次のどちらであってもよい。また縦多段延伸や３、４段延伸とすることもできる。
延伸温度は、９０℃〜ポリオレフィンの融点未満であることが好ましく、さらに好ましくは１００〜１２０℃である。加熱温度が融点を越える場合は、ポリオレフィンのベーステープ部分が溶解するために延伸できない。又、加熱温度が９０℃未満の場合は、ベーステープ積層組成物の軟化が不十分で延伸において破膜し易く高倍率の延伸が困難となる場合がある。
延伸後、必要に応じて熱固定を行い、熱寸法安定性を持たせる。
(4) Stretching of the gel composition The gel composition is stretched. Here, a relaxation treatment may be performed before the stretching treatment. In the stretching treatment, the gel-like molded product is heated and biaxially stretched at a predetermined magnification by a normal tenter method, roll method, rolling method, or a combination of these methods. Biaxial stretching may be simultaneous or sequential. Moreover, it can also be set as longitudinal multistage extending | stretching, 3 or 4 steps | stretching.
The stretching temperature is preferably 90 ° C. to less than the melting point of the polyolefin, more preferably 100 to 120 ° C. If the heating temperature exceeds the melting point, the base tape portion of the polyolefin dissolves and cannot be stretched. Moreover, when heating temperature is less than 90 degreeC, the softening of a base tape laminated composition is inadequate, and it may be easy to break at the time of extending | stretching, and it may become difficult to extend | stretch at high magnification.
After stretching, heat setting is performed as necessary to provide thermal dimensional stability.
（５）溶剤の抽出・除去
延伸後のベーステープ積層組成物を抽出溶剤に浸漬して、溶媒を抽出する。抽出溶剤としてはペンタン、ヘキサン、ヘプタン、シクロヘキサン、デカリン、テトラリンなどの炭化水素、塩化メチレン、四塩化炭素、メチレンクロライドなどの塩素化炭化水素、三フッ化エタンなどのフッ化炭化水素、ジエチルエーテル、ジオキサン等のエーテル類など易揮発性のものを用いることができる。これらの溶剤はポリオレフィン組成物の溶解に用いた溶媒に応じて適宜選択し、単独もしくは混合して用いることができる。溶媒の抽出は、微多孔膜中の溶媒を１重量％未満に迄除去する。
(5) Extraction and removal of solvent The base tape laminated composition after stretching is immersed in an extraction solvent to extract the solvent. Extraction solvents include hydrocarbons such as pentane, hexane, heptane, cyclohexane, decalin and tetralin, chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride and methylene chloride, fluorinated hydrocarbons such as ethane trifluoride, diethyl ether, Easily volatile substances such as ethers such as dioxane can be used. These solvents are appropriately selected according to the solvent used for dissolving the polyolefin composition, and can be used alone or in combination. Solvent extraction removes the solvent in the microporous membrane to less than 1% by weight.
（６）微多孔膜のアニール
微多孔膜をアニールにより熱セットする。アニールは８０〜１５０℃で実施する。
(6) Annealing of microporous film The microporous film is heat-set by annealing. Annealing is performed at 80 to 150 ° C.
［耐熱性多孔質層］
本発明において、耐熱性多孔質層とは、微多孔膜状の層を意味する。ここで、微多孔膜状の層とは、内部に多数の微細孔を有し、これら微細孔が連結された構造となっており、一方の面から他方の面へと気体あるいは液体が通過可能となった層のことを言う。
[Heat-resistant porous layer]
In the present invention, the heat resistant porous layer means a microporous film-like layer. Here, the microporous film-like layer has a large number of micropores inside, and has a structure in which these micropores are connected. Gas or liquid can pass from one surface to the other. It says the layer that became.
本発明で用いられる耐熱性樹脂は、融点２００℃以上のポリマーあるいは融点を有しないが分解温度が２００℃以上のポリマーが適当であり、好ましくは、全芳香族ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルスルホン、ポリスルホン、ポリケトン、ポリエーテルケトンおよびポリエーテルイミドからなる群から選ばれる少なくとも１種の樹脂である。特に、耐久性の観点から全芳香族ポリアミドが好適であり、多孔質層を形成しやすく耐酸化還元性に優れるという観点から、メタ型全芳香族ポリアミドであるポリメタフェニレンイソフタルアミドがさらに好適である。 As the heat-resistant resin used in the present invention, a polymer having a melting point of 200 ° C. or higher or a polymer having no melting point but a decomposition temperature of 200 ° C. or higher is suitable, and preferably a wholly aromatic polyamide, polyimide, polyamideimide, polyether It is at least one resin selected from the group consisting of sulfone, polysulfone, polyketone, polyetherketone and polyetherimide. In particular, wholly aromatic polyamides are preferable from the viewpoint of durability, and polymetaphenylene isophthalamide, which is a meta-type wholly aromatic polyamide, is more preferable from the viewpoint of easy formation of a porous layer and excellent redox resistance. is there.
本発明において、耐熱性多孔質層はポリオレフィン多孔質基材の両面または片面に形成すればよいが、ハンドリング性、耐久性および熱収縮の抑制効果の観点から、基材の表裏両面に形成した方が好ましい。 In the present invention, the heat-resistant porous layer may be formed on both surfaces or one surface of the polyolefin porous substrate, but from the viewpoints of handling properties, durability, and the effect of suppressing heat shrinkage, it is formed on both surfaces of the substrate. Is preferred.
本発明において、耐熱性多孔質層の厚みについては、耐熱性多孔質層が基材の両面に形成されている場合は、耐熱性多孔質層の厚みの合計が３μｍ以上１２μｍ以下であることが好ましく、耐熱性多孔質層が基材の片面にのみ形成されている場合は耐熱性多孔質層の厚みが３μｍ以上１２μｍ以下であることが好ましい。耐熱性多孔質層の空孔率は６０〜９０％の範囲が好適である。 In the present invention, regarding the thickness of the heat resistant porous layer, when the heat resistant porous layer is formed on both surfaces of the substrate, the total thickness of the heat resistant porous layer may be 3 μm or more and 12 μm or less. Preferably, when the heat resistant porous layer is formed only on one side of the substrate, the thickness of the heat resistant porous layer is preferably 3 μm or more and 12 μm or less. The porosity of the heat resistant porous layer is preferably in the range of 60 to 90%.
［無機フィラー］
本発明において、耐熱性多孔質層には無機フィラーが含まれていることが好ましい。この場合、耐熱性多孔質層中の無機フィラーは、耐熱性樹脂に捕捉された状態で存在している。
[Inorganic filler]
In the present invention, the heat resistant porous layer preferably contains an inorganic filler. In this case, the inorganic filler in the heat resistant porous layer is present in a state of being captured by the heat resistant resin.
本発明における無機フィラーとしては、特に限定はないが、具体的にはアルミナ、チタニア、シリカ、ジルコニアなどの金属酸化物、炭酸カルシウムなどの金属炭酸塩、リン酸カルシウムなどの金属リン酸塩、水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物などが好適に用いられる。このような無機フィラーは、不純物の溶出や耐久性の観点から結晶性の高いものが好ましい。 The inorganic filler in the present invention is not particularly limited, but specifically, metal oxides such as alumina, titania, silica, zirconia, metal carbonates such as calcium carbonate, metal phosphates such as calcium phosphate, aluminum hydroxide A metal hydroxide such as magnesium hydroxide is preferably used. Such an inorganic filler is preferably highly crystalline from the viewpoints of impurity elution and durability.
中でも、無機フィラーとしては、２００〜４００℃において吸熱反応を生じるものであるものが好ましい。この様な特性を有する無機フィラーとして、特に限定されないが、金属水酸化物、硼素塩化合物または粘土鉱物等からなる無機フィラーであって、２００〜４００℃において吸熱反応を生じるものが挙げられる。具体的には、例えば、水酸化アルミニウムや水酸化マグネシウム、アルミン酸カルシウム、ドーソナイト、硼酸亜鉛等が挙げられ、これらは単独若しくは２種以上を組合せて用いることができる。また、これらの難燃性の無機フィラーには、アルミナやジルコニア、シリカ、マグネシア、チタニア等の金属酸化物、金属窒化物、金属炭化物、金属炭酸塩などの他の無機フィラーを適宜混合して用いることもできる。 Especially, as an inorganic filler, what produces an endothermic reaction in 200-400 degreeC is preferable. Although it does not specifically limit as an inorganic filler which has such a characteristic, It is an inorganic filler which consists of a metal hydroxide, a boron salt compound, or a clay mineral, Comprising: What produces an endothermic reaction in 200-400 degreeC is mentioned. Specific examples include aluminum hydroxide, magnesium hydroxide, calcium aluminate, dosonite, zinc borate and the like, and these can be used alone or in combination of two or more. In addition, these flame retardant inorganic fillers are appropriately mixed with other inorganic fillers such as metal oxides such as alumina, zirconia, silica, magnesia, and titania, metal nitrides, metal carbides, and metal carbonates. You can also.
ここで、非水系二次電池では、正極の分解に伴う発熱が最も危険と考えられており、この分解は３００℃近傍で起こる。このため、吸熱反応の発生温度が２００℃〜４００℃の範囲であれば、非水系二次電池の発熱を防ぐ上で有効である。なお、２００℃以上においては、負極はほぼ活性を失っているので、金属水酸化物から発生した水と反応して発熱を引き起こすことはなく安全である。また、無機フィラーの吸熱反応温度が４００℃を超える場合、非水系二次電池の発熱を好適に防止できないおそれがあるため好ましくない。例えば、水酸化アルミニウムやドーソナイト、アルミン酸カルシウムは２００〜３００℃の範囲において脱水反応が起こり、また、水酸化マグネシウムや硼酸亜鉛は３００〜４００℃の範囲において脱水反応が起こるため、これらの無機フィラーのうち少なくともいずれか一種を用いることが好ましい。 Here, in the non-aqueous secondary battery, heat generation accompanying the decomposition of the positive electrode is considered to be the most dangerous, and this decomposition occurs in the vicinity of 300 ° C. For this reason, if the generation | occurrence | production temperature of endothermic reaction is the range of 200 to 400 degreeC, it is effective in preventing the heat_generation | fever of a non-aqueous secondary battery. It should be noted that at 200 ° C. or higher, since the negative electrode almost loses its activity, it does not react with water generated from the metal hydroxide to cause heat generation and is safe. Moreover, when the endothermic reaction temperature of an inorganic filler exceeds 400 degreeC, since there exists a possibility that the heat_generation | fever of a non-aqueous secondary battery cannot be prevented suitably, it is unpreferable. For example, aluminum hydroxide, dawsonite, and calcium aluminate undergo a dehydration reaction in the range of 200 to 300 ° C, and magnesium hydroxide and zinc borate undergo a dehydration reaction in the range of 300 to 400 ° C. It is preferable to use at least one of them.
特に本発明では、無機フィラーは金属水酸化物からなることが好ましい。金属水酸化物は、加熱により大きな吸熱を伴う脱水反応が起こるため、水の放出と吸熱の双方による難燃性の向上効果が得られる。水の放出は、可燃性の電解液を希釈して、電池そのものも難燃化する上で有効である。また、金属水酸化物はアルミナ等のような金属酸化物と比較して軟らかい材料であるため、セパレータに含まれる無機フィラーによって製造時の各工程で使用する部品が磨耗してしまうといったハンドリング上の問題が発生しない。また、耐熱性多孔質層に水酸化アルミニウムや水酸化マグネシウム等の金属水酸化物を添加した場合は、帯電した電荷の減衰が速くなるため、帯電を低いレベルに保つことが可能となり、ハンドリング性が改善される。さらに、水酸化アルミニウムや水酸化マグネシウムはフッ酸を吸着・共沈させる機能があるため、電解液中のフッ酸濃度を低いレベルに維持することが可能であり、非水系二次電池の耐久性を改善することが可能となる。よって、無機フィラーは金属水酸化物であることが好ましく、中でも水酸化アルミニウムまたは水酸化マグネシウムであることが好ましい。 In particular, in the present invention, the inorganic filler is preferably made of a metal hydroxide. Since the metal hydroxide undergoes a dehydration reaction accompanied by a large endotherm by heating, an effect of improving flame retardancy due to both the release of water and endotherm can be obtained. The release of water is effective in diluting the flammable electrolyte and making the battery itself incombustible. In addition, since metal hydroxide is a softer material than metal oxides such as alumina, the parts used in each process at the time of manufacturing are worn by the inorganic filler contained in the separator. There is no problem. In addition, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is added to the heat-resistant porous layer, the charged charge decays quickly, so that the charge can be kept at a low level and handling properties are improved. Is improved. Furthermore, aluminum hydroxide and magnesium hydroxide have the function of adsorbing and co-precipitating hydrofluoric acid, so it is possible to maintain the hydrofluoric acid concentration in the electrolyte at a low level, and the durability of non-aqueous secondary batteries Can be improved. Therefore, the inorganic filler is preferably a metal hydroxide, and particularly preferably aluminum hydroxide or magnesium hydroxide.
本発明において、無機フィラーの平均粒子径は０．１〜２μｍの範囲が好ましい。無機フィラーの平均粒子径が２μｍを超えると、耐熱性多孔質層の高温時の耐短絡性が低下するため好ましくない。さらに、耐熱性多孔質層を適切な厚みで成形する上で支障をきたすといった不具合もある。また、無機フィラーの平均粒子径が０．１μｍ未満であると、塗膜強度が低下し粉落ちの課題が生じるだけでなく、このように小さいものを用いることはコスト上の観点から実質的に困難である。 In the present invention, the average particle size of the inorganic filler is preferably in the range of 0.1 to 2 μm. When the average particle diameter of the inorganic filler exceeds 2 μm, the short circuit resistance at high temperature of the heat resistant porous layer is lowered, which is not preferable. Further, there is a problem that it hinders the formation of the heat-resistant porous layer with an appropriate thickness. In addition, when the average particle size of the inorganic filler is less than 0.1 μm, not only does the coating film strength decrease and the problem of powder falling occurs, but using such a small one is substantially from the viewpoint of cost. Have difficulty.
本発明において、耐熱性多孔質層における無機フィラーの含有量は５０〜９５重量％であることが好ましい。無機フィラーの含有量が５０重量％未満であると、無機フィラーによる耐熱性向上の効果が十分に得られない場合があるため好ましくない。また、無機フィラーの含有量が９５重量％を超えると、耐熱性多孔質層が緻密化されすぎてイオン透過性が低下したり、耐熱性多孔質層が脆くなってハンドリング性が低下する場合があるため好ましくない。 In this invention, it is preferable that content of the inorganic filler in a heat resistant porous layer is 50 to 95 weight%. If the content of the inorganic filler is less than 50% by weight, the effect of improving heat resistance by the inorganic filler may not be sufficiently obtained, which is not preferable. On the other hand, if the content of the inorganic filler exceeds 95% by weight, the heat-resistant porous layer may be excessively densified and ion permeability may be reduced, or the heat-resistant porous layer may become brittle and handling properties may be reduced. This is not preferable.
［耐熱性多孔質層の製造法］
本発明において、非水系二次電池用セパレータの製造法は、上述した構成の本発明のセパレータが製造できれば特に限定されないが、例えば下記（１）〜（５）の工程を経て製造することが可能である。
[Method for producing heat-resistant porous layer]
In the present invention, the method for producing a separator for a non-aqueous secondary battery is not particularly limited as long as the separator of the present invention having the above-described configuration can be produced. For example, it can be produced through the following steps (1) to (5). It is.
（１）塗工用スラリーの作製
耐熱性樹脂を溶剤に溶かし、塗工用スラリーを作製する。溶剤は耐熱性樹脂を溶解するものであればよく、特に限定は無いが、具体的には極性溶剤が好ましく、例えばＮ−メチルピロリドン、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシドなどが挙げられる。また、当該溶剤はこれらの極性溶剤に加えて耐熱性樹脂に対して貧溶剤となる溶剤も加えることができる。このような貧溶剤を適用することでミクロ相分離構造が誘発され、耐熱性多孔質層を形成する上で多孔化が容易となる。貧溶剤としては、アルコールの類が好適であり、特にグリコールのような多価アルコールが好適である。塗工用スラリー中の耐熱性樹脂の濃度は４〜９重量％が好ましい。また必要に応じ、これに無機フィラーを分散させて塗工用スラリーとする。塗工用スラリー中に無機フィラーを分散させるに当たって、無機フィラーの分散性が好ましくないときは、無機フィラーをシランカップリング剤などで表面処理し、分散性を改善する手法も適用可能である。
(1) Preparation of coating slurry A heat-resistant resin is dissolved in a solvent to prepare a coating slurry. The solvent is not particularly limited as long as it dissolves the heat-resistant resin, but specifically, a polar solvent is preferable, and examples thereof include N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethylsulfoxide. Moreover, the said solvent can add the solvent used as a poor solvent with respect to heat resistant resin in addition to these polar solvents. By applying such a poor solvent, a microphase separation structure is induced and the formation of a heat-resistant porous layer is facilitated. As the poor solvent, alcohols are preferable, and polyhydric alcohols such as glycol are particularly preferable. The concentration of the heat resistant resin in the coating slurry is preferably 4 to 9% by weight. Moreover, an inorganic filler is disperse | distributed to this as needed, and it is set as the slurry for coating. In dispersing the inorganic filler in the coating slurry, when the dispersibility of the inorganic filler is not preferable, a method of improving the dispersibility by surface-treating the inorganic filler with a silane coupling agent or the like is also applicable.
（２）スラリーの塗工
スラリーをポリオレフィン多孔質基材の少なくとも一方の表面に塗工する。ポリオレフィン多孔質基材の両面に耐熱性多孔質層を形成する場合は、基材の両面に同時に塗工することが、工程の短縮という観点で好ましい。塗工用スラリーを塗工する方法としては、ナイフコーター法、グラビアコーター法、スクリーン印刷法、マイヤーバー法、ダイコーター法、リバースロールコーター法、インクジェット法、スプレー法、ロールコーター法などが挙げられる。この中でも、塗膜を均一に形成するという観点において、リバースロールコーター法が好適である。基材の両面に同時に塗工する場合は、例えば、基材を一対のマイヤーバーの間に通すことで基材の両面に過剰な塗工用スラリーを塗布し、これを一対のリバースロールコーターの間に通して過剰なスラリーを掻き落すことで精密計量するという方法が挙げられる。
(2) Coating of slurry The slurry is coated on at least one surface of the polyolefin porous substrate. When forming a heat resistant porous layer on both surfaces of a polyolefin porous substrate, it is preferable from a viewpoint of shortening of a process to apply simultaneously on both surfaces of a substrate. Examples of the method for coating the slurry for coating include a knife coater method, a gravure coater method, a screen printing method, a Meyer bar method, a die coater method, a reverse roll coater method, an ink jet method, a spray method, and a roll coater method. . Among these, the reverse roll coater method is preferable from the viewpoint of uniformly forming a coating film. When applying simultaneously to both sides of the base material, for example, by passing the base material between a pair of Meyer bars, an excess coating slurry is applied to both sides of the base material, and this is applied to a pair of reverse roll coaters. There is a method of precise measurement by scraping off excess slurry in between.
（３）スラリーの凝固
スラリーが塗工された基材を、前記耐熱性樹脂を凝固させることが可能な凝固液で処理する。これにより、耐熱性樹脂を凝固させて、耐熱性樹脂からなる耐熱性多孔質層あるいは、耐熱性樹脂に無機フィラーが結着された耐熱性多孔質層を形成する。凝固液で処理する方法としては、塗工用スラリーを塗工した基材に対して凝固液をスプレーで吹き付ける方法や、当該基材を凝固液の入った浴（凝固浴）中に浸漬する方法などが挙げられる。ここで、凝固浴を設置する場合は、塗工装置の下方に設置することが好ましい。凝固液としては、当該耐熱性樹脂を凝固できるものであれば特に限定されないが、水、または、スラリーに用いた溶剤に水を適当量混合させたものが好ましい。ここで、水の混合量は凝固液に対して４０〜８０重量％が好適である。水の量が４０重量％より少ないと、耐熱性樹脂を凝固するのに必要な時間が長くなったり、凝固が不十分になったりという問題が生じる。また、水の量が８０重量％より多いと、溶剤回収においてコスト高となったり、凝固液と接触する表面の凝固が速くなりすぎて表面が十分に多孔化されなかったりという問題が生じる。
(3) Solidification of slurry The base material on which the slurry is applied is treated with a coagulating liquid capable of coagulating the heat-resistant resin. Thereby, the heat resistant resin is solidified to form a heat resistant porous layer made of the heat resistant resin or a heat resistant porous layer in which the inorganic filler is bound to the heat resistant resin. As a method of treating with the coagulating liquid, a method of spraying the coagulating liquid on the substrate coated with the coating slurry, or a method of immersing the substrate in a bath (coagulating bath) containing the coagulating liquid. Etc. Here, when installing a coagulation bath, it is preferable to install it below the coating apparatus. The coagulation liquid is not particularly limited as long as it can coagulate the heat-resistant resin, but water or a solution obtained by mixing an appropriate amount of water with the solvent used in the slurry is preferable. Here, the mixing amount of water is preferably 40 to 80% by weight with respect to the coagulation liquid. When the amount of water is less than 40% by weight, there arises a problem that the time required for solidifying the heat-resistant resin becomes long or the solidification becomes insufficient. On the other hand, when the amount of water is more than 80% by weight, there arises a problem that the cost for solvent recovery becomes high, or the surface that comes into contact with the coagulation liquid is solidified too quickly and the surface is not sufficiently porous.
（４）凝固液の除去
凝固液を水洗することによって除去する。
(4) Removal of coagulating liquid The coagulating liquid is removed by washing with water.
（５）乾燥
シートから水を乾燥して除去する。乾燥方法は特に限定は無いが、乾燥温度は５０〜８０℃が好適であり、高い乾燥温度を適用する場合は熱収縮による寸法変化が起こらないようにするためにロールに接触させるような方法を適用することが好ましい。
(5) Drying Dry and remove water from the sheet. Although there is no particular limitation on the drying method, the drying temperature is preferably 50 to 80 ° C. When a high drying temperature is applied, a method of contacting with a roll to prevent dimensional change due to heat shrinkage. It is preferable to apply.
［非水系二次電池］
本発明の非水系二次電池は、リチウムのドープ・脱ドープにより起電力を得る非水系二次電池であって、上述した構成の非水系二次電池用セパレータを用いたことを特徴とする。非水系二次電池は、負極と正極がセパレータを介して対向している電池要素に電解液が含浸され、これが外装に封入された構造となっている。
[Non-aqueous secondary battery]
The non-aqueous secondary battery of the present invention is a non-aqueous secondary battery that obtains an electromotive force by doping or dedoping lithium, and is characterized by using the separator for a non-aqueous secondary battery having the above-described configuration. The non-aqueous secondary battery has a structure in which a battery element in which a negative electrode and a positive electrode face each other with a separator interposed therebetween is impregnated with an electrolytic solution, and this is enclosed in an exterior.
負極は、負極活物質、導電助剤およびバインダーからなる負極合剤が、集電体上に成形された構造となっている。負極活物質としては、リチウムを電気化学的にドープすることが可能な材料が挙げられ、例えば炭素材料、シリコン、アルミニウム、スズ、ウッド合金などが挙げられる。導電助剤は、アセチレンブラック、ケッチェンブラックといった炭素材料が挙げられる。バインダーは有機高分子からなり、例えばポリフッ化ビニリデン、カルボキシメチルセルロースなどが挙げられる。集電体には銅箔、ステンレス箔、ニッケル箔などを用いることが可能である。 The negative electrode has a structure in which a negative electrode mixture composed of a negative electrode active material, a conductive additive and a binder is formed on a current collector. Examples of the negative electrode active material include materials capable of electrochemically doping lithium, and examples thereof include carbon materials, silicon, aluminum, tin, and wood alloys. Examples of the conductive assistant include carbon materials such as acetylene black and ketjen black. The binder is made of an organic polymer, and examples thereof include polyvinylidene fluoride and carboxymethyl cellulose. As the current collector, a copper foil, a stainless steel foil, a nickel foil, or the like can be used.
正極は、正極活物質、導電助剤およびバインダーからなる正極合剤が、集電体上に成形された構造となっている。正極活物質としては、リチウム含有遷移金属酸化物等が挙げられ、具体的にはＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ０．５Ｎｉ０．５Ｏ２、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２、ＬｉＭｎ２Ｏ４、ＬｉＦｅＰＯ４等が挙げられる。導電助剤はアセチレンブラック、ケッチェンブラックといった炭素材料が挙げられる。バインダーは有機高分子からなり、例えばポリフッ化ビニリデンなどが挙げられる。集電体にはアルミ箔、ステンレス箔、チタン箔などを用いることが可能である。 The positive electrode has a structure in which a positive electrode mixture composed of a positive electrode active material, a conductive additive and a binder is formed on a current collector. Examples of the positive electrode active material include lithium-containing transition metal oxides. Specifically, LiCoO 2 , LiNiO 2 , LiMn 0.5 Ni 0.5 O 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2, LiMn 2 O 4, LiFePO 4 , and the like. Examples of the conductive assistant include carbon materials such as acetylene black and ketjen black. The binder is made of an organic polymer, and examples thereof include polyvinylidene fluoride. As the current collector, aluminum foil, stainless steel foil, titanium foil, or the like can be used.
電解液は、リチウム塩を非水系溶媒に溶解した構成である。リチウム塩としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４などが挙げられる。非水系溶媒としては、プロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、γ−ブチロラクトン、ビニレンカーボネートなどが挙げられ、これらは単独で用いても混合して用いてもよい。 The electrolytic solution has a structure in which a lithium salt is dissolved in a non-aqueous solvent. Examples of the lithium salt include LiPF 6 , LiBF 4 , LiClO 4 and the like. Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, vinylene carbonate, and the like. These may be used alone or in combination.
外装材は、金属缶またはアルミラミネートパック等が挙げられる。電池の形状は角型、円筒型、コイン型などがあるが、本発明のセパレータはいずれの形状においても好適に適用することが可能である。 Examples of the exterior material include a metal can or an aluminum laminate pack. The shape of the battery includes a square shape, a cylindrical shape, a coin shape, and the like, but the separator of the present invention can be suitably applied to any shape.
以下に実施例を示すが、本発明はこれらに制限されるものではない。
［測定方法］
なお、本実施例における各値は、以下の方法に従って求めた。
Examples are shown below, but the present invention is not limited thereto.
[Measuring method]
In addition, each value in a present Example was calculated | required according to the following method.
（１）ポリオレフィン微多孔膜及び非水系二次電池用セパレータの膜厚は、接触式の膜厚計（ミツトヨ社製）にて２０点測定し、これを平均することで求めた。ここで接触端子は底面が直径０．５ｃｍの円柱状のものを用いた。 (1) The film thickness of the polyolefin microporous membrane and the separator for a non-aqueous secondary battery was determined by measuring 20 points with a contact-type film thickness meter (manufactured by Mitutoyo Corporation) and averaging them. Here, the contact terminal used was a cylindrical one having a bottom surface of 0.5 cm in diameter.
（２）ポリオレフィン微多孔膜及び非水系二次電池用セパレータの目付は、サンプルを１０ｃｍ×１０ｃｍに切り出し重量を測定する。この重量を面積で割ることで１ｍ２当たりの重量である目付を求めた。 (2) The basis weight of the polyolefin microporous membrane and the separator for a non-aqueous secondary battery is obtained by cutting a sample into 10 cm × 10 cm and measuring the weight. By dividing this weight by the area, the basis weight which is the weight per 1 m 2 was obtained.
（３）ポリオレフィン微多孔膜及び非水系二次電池用セパレータの空孔率は、
ε＝｛１−Ｗｓ／（ｄｓ・ｔ）｝×１００ から求めた。
ここで、ε：空隙率（％）、Ｗｓ：目付（ｇ／ｍ２）、ｄｓ：真密度（ｇ／ｃｍ３）、ｔ：膜厚（μｍ）である。
(3) The porosity of the polyolefin microporous membrane and the non-aqueous secondary battery separator is
It calculated | required from (epsilon) = {1-Ws / (ds * t)} * 100.
Here, ε: porosity (%), Ws: basis weight (g / m 2 ), ds: true density (g / cm 3 ), and t: film thickness (μm).
（４）ポリオレフィン微多孔膜及び非水系二次電池用セパレータのガーレ値はＪＩＳ Ｐ８１１７に従って求めた。 (4) The Gurley values of the polyolefin microporous membrane and the non-aqueous secondary battery separator were determined according to JIS P8117.
（５）ポリオレフィン微多孔膜及び非水系二次電池用セパレータの膜抵抗は、以下の方法で求めた。
サンプルを２．６ｃｍ×２．０ｃｍのサイズに切り出す。非イオン性界面活性剤（花王社製エマルゲン２１０Ｐ）を３重量％溶解したメタノール溶液（メタノール：和光純薬社製）に切り出したサンプルを浸漬し、風乾する。厚さ２０μｍのアルミ箔を２．０ｃｍ×１．４ｃｍに切り出しリードタブを付ける。このアルミ箔を２枚用意して、アルミ箔間に切り出したサンプルをアルミ箔が短絡しないように挟む。サンプルに電解液である１ＭのＬｉＢＦ４ プロピレンカーボネート／エチレンカーボネート（１／１重量比）を含浸させる。これをアルミラミネートパック中にタブがアルミパックの外に出るようにして減圧封入する。このようなセルをアルミ箔中にセパレータが１枚、２枚、３枚となるようにそれぞれ作製する。該セルを２０℃の恒温槽中に入れ、交流インピーダンス法で振幅１０ｍＶ、周波数１００ｋＨｚにて該セルの抵抗を測定する。測定されたセルの抵抗値をセパレータの枚数に対してプロットし、このプロットを線形近似し傾きを求める。この傾きに電極面積である２．０ｃｍ×１．４ｃｍを乗じてセパレータ１枚当たりの膜抵抗（ｏｈｍ・ｃｍ２）を求めた。
(5) The membrane resistance of the polyolefin microporous membrane and the non-aqueous secondary battery separator was determined by the following method.
Cut the sample to a size of 2.6 cm × 2.0 cm. A sample cut out in a methanol solution (methanol: manufactured by Wako Pure Chemical Industries, Ltd.) in which 3% by weight of a nonionic surfactant (Emalgen 210P manufactured by Kao Corporation) is dissolved is immersed and air-dried. A 20 μm thick aluminum foil is cut into 2.0 cm × 1.4 cm and a lead tab is attached. Two aluminum foils are prepared, and a sample cut between the aluminum foils is sandwiched so that the aluminum foils are not short-circuited. The sample is impregnated with 1M LiBF 4 propylene carbonate / ethylene carbonate (1/1 weight ratio) as an electrolyte. This is sealed under reduced pressure in an aluminum laminate pack so that the tab comes out of the aluminum pack. Such cells are prepared so that there are one, two, and three separators in the aluminum foil, respectively. The cell is placed in a constant temperature bath at 20 ° C., and the resistance of the cell is measured by an AC impedance method at an amplitude of 10 mV and a frequency of 100 kHz. The measured resistance value of the cell is plotted against the number of separators, and the plot is linearly approximated to obtain the slope. The film resistance (ohm · cm 2 ) per separator was determined by multiplying the inclination by 2.0 cm × 1.4 cm which is the electrode area.
（６）ポリオレフィン微多孔膜及び非水系二次電池用セパレータの突刺強度は、ハンディー圧縮試験器（カトーテック社製、ＫＥＳ−Ｇ５）を用いて、針先端の曲率半径０．５ｍｍ、突刺速度２ｍｍ／ｓｅｃの条件で突刺試験を行い、最大突刺荷重を突刺強度とした。ここでサンプルはΦ１１．３ｍｍの穴があいた金枠（試料ホルダー）にシリコンゴム製のパッキンも一緒に挟み固定した。 (6) The puncture strength of the polyolefin microporous membrane and the non-aqueous secondary battery separator was measured using a handy compression tester (KES-G5, manufactured by Kato Tech Co., Ltd.) with a radius of curvature of the needle tip of 0.5 mm and a puncture speed of 2 mm The puncture test was conducted under the conditions of / sec, and the maximum puncture load was defined as the puncture strength. Here, the sample was fixed by sandwiching a silicon rubber packing in a metal frame (sample holder) having a hole of Φ11.3 mm.
（７）ポリオレフィン微多孔膜及び非水系二次電池用セパレータの引張強度は、１０×１００ｍｍに調整したサンプルを引張試験機（Ａ＆Ｄ社製、ＲＴＣ−１２２５Ａ）を用い、ロードセル荷重５ｋｇｆ、チャック間距離５０ｍｍの条件で測定した。 (7) Tensile strength of polyolefin microporous membrane and non-aqueous secondary battery separator was adjusted to 10 × 100 mm using a tensile tester (A & D, RTC-1225A), load cell load 5 kgf, distance between chucks Measurement was performed under the condition of 50 mm.
（８）ポリオレフィン微多孔膜及び非水系二次電池用セパレータのシャットダウン温度は、以下の方法で求めた。
サンプルをΦ１９ｍｍに打ち抜き、非イオン性界面活性剤（花王社製エマルゲン２１０Ｐ）を３重量％溶解したメタノール溶液（メタノール：和光純薬社製）に切り出したサンプルを浸漬し、風乾した。サンプルをΦ１５．５ｍｍのＳＵＳ板に挟んだ。サンプルに電解液である１ＭのＬｉＢＦ４ プロピレンカーボネート／エチレンカーボネート（１／１重量比）（キシダ化学社製）を含浸させた。これを２０３２型コインセルに封入した。コインセルからリード線をとり、熱電対を付けてオーブンの中に入れた。昇温速度１．６℃／分で昇温させ、同時に交流インピーダンス法で振幅１０ｍＶ、周波数１００ｋＨｚにて該セルの抵抗を測定した。抵抗値が１０３ｏｈｍ・ｃｍ２以上となった温度をシャットダウン温度とした。
(8) The shutdown temperature of the polyolefin microporous membrane and the non-aqueous secondary battery separator was determined by the following method.
The sample was punched into Φ19 mm, and the sample cut out in a methanol solution (methanol: manufactured by Wako Pure Chemical Industries, Ltd.) in which 3% by weight of a nonionic surfactant (Emulgen 210P manufactured by Kao Corporation) was dissolved was immersed and air-dried. The sample was sandwiched between SUS plates with a diameter of 15.5 mm. The sample was impregnated with 1M LiBF 4 propylene carbonate / ethylene carbonate (1/1 weight ratio) (manufactured by Kishida Chemical Co., Ltd.) as an electrolyte. This was enclosed in a 2032 type coin cell. I took the lead from the coin cell, put a thermocouple, and put it in the oven. The temperature of the cell was increased at a rate of temperature increase of 1.6 ° C./min, and the resistance of the cell was measured at the same time by the AC impedance method at an amplitude of 10 mV and a frequency of 100 kHz. The temperature at which the resistance value reached 10 3 ohm · cm 2 or more was taken as the shutdown temperature.
（９）ポリオレフィン微多孔膜及び非水系二次電池用セパレータの熱収縮率は、サンプルを１０５℃で１時間加熱することによって測定した。なお、測定方向は機械方向である。 (9) The thermal shrinkage of the polyolefin microporous membrane and the separator for non-aqueous secondary batteries was measured by heating the sample at 105 ° C. for 1 hour. Note that the measurement direction is the machine direction.
（１０）非水系二次電池の放電性評価を、以下の方法で実施した。
１．６ｍＡ、４．２Ｖで８時間定電流・定電圧充電、１．６ｍＡ、２．７５Ｖで定電流放電の充放電サイクルを１０サイクル実施し、１０サイクル目に得られた放電容量をこの電池の放電容量とした。次に、１．６ｍＡ、４．２Ｖで８時間定電流・定電圧充電、１６ｍＡ、２．７５Ｖで定電流放電を行った。このとき得られた容量を１０サイクル目の電池の放電容量で割り、得られた数値を負荷特性の指標とした。
(10) The discharge property evaluation of the non-aqueous secondary battery was performed by the following method.
10 cycles of constant current / constant voltage charging at 1.6 mA, 4.2 V for 8 hours, and constant current discharge at 1.6 mA, 2.75 V were carried out 10 cycles, and the discharge capacity obtained at the 10th cycle was determined for this battery. Discharge capacity. Next, constant current / constant voltage charging was performed at 1.6 mA and 4.2 V for 8 hours, and constant current discharging was performed at 16 mA and 2.75 V. The capacity obtained at this time was divided by the discharge capacity of the battery at the 10th cycle, and the obtained value was used as an index of load characteristics.
［参考例１］
ポリエチレンパウダーとしてＴｉｃｏｎａ社製ＧＵＲ２１２６（重量平均分子量４１５万、融点１４１℃）とＧＵＲＸ１４３（重量平均分子量５６万、融点１３５℃）、ポリプロピレンパウダーとしてプライムポリマー社製Ｆ１０３ＥＡ（重量平均分子量４８万、融点１６６℃）を用いた。ＧＵＲ２１２６とＧＵＲＸ１４３とＦ１０３ＥＡを１：８：１（重量比）となる様にして、ポリオレフィン濃度が３０重量％となるように流動パラフィン（松村石油研究所社製スモイルＰ−３５０：沸点４８０℃）とデカリン（和光純薬社製、沸点１９３℃）の混合溶媒中に溶解させ、ポリオレフィン溶液を作製した。該ポリオレフィン溶液の組成はポリオレフィン：流動パラフィン：デカリン＝３０：４５：２５（重量比）である。
[Reference Example 1]
Polyethylene powder GUR2126 (weight average molecular weight 41.50 million, melting point 141.degree. C.) and GURX 143 (weight average molecular weight 560,000, melting point 135.degree. C.) and polypropylene polymer F103EA (weight average molecular weight 480,000, melting point 166.degree. C.) ) Was used. Liquid paraffin (Smoyl P-350, boiling point 480 ° C. by Matsumura Oil Research Co., Ltd.) so that GUR2126, GURX143, and F103EA are 1: 8: 1 (weight ratio) and the polyolefin concentration is 30% by weight. A polyolefin solution was prepared by dissolving in a mixed solvent of decalin (manufactured by Wako Pure Chemical Industries, Ltd., boiling point 193 ° C.). The composition of the polyolefin solution is polyolefin: liquid paraffin: decalin = 30: 45: 25 (weight ratio).
このポリオレフィン溶液を１６８℃でダイから押し出し、水浴中で冷却してゲル状テープ（ベーステープ）を作製した。該ベーステープを６０℃で８分、９５℃で１５分乾燥し、該ベーステープを縦延伸、横延伸を逐次行う２軸延伸にて延伸した。ここで、縦延伸５．５倍、延伸温度は９０℃、横延伸は延伸倍率１１．０倍、延伸温度は１０５℃とした。横延伸の後に１２５℃で熱固定を行った。次にこれを塩化メチレン浴に浸漬し、流動パラフィンとデカリンを抽出した。その後、５０℃で乾燥し、１２０℃でアニール処理することでポリオレフィン微多孔膜を得た。得られたポリオレフィン微多孔膜はフィブリル状ポリオレフィンが網目状に交絡し、細孔を構成する構造を有するものであった。
得られたポリオレフィン微多孔膜の特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表１に示す。
This polyolefin solution was extruded from a die at 168 ° C. and cooled in a water bath to prepare a gel tape (base tape). The base tape was dried at 60 ° C. for 8 minutes and at 95 ° C. for 15 minutes, and the base tape was stretched by biaxial stretching in which longitudinal stretching and lateral stretching were sequentially performed. Here, the longitudinal stretching was 5.5 times, the stretching temperature was 90 ° C., the transverse stretching was 11.0 times the stretching ratio, and the stretching temperature was 105 ° C. After transverse stretching, heat setting was performed at 125 ° C. Next, this was immersed in a methylene chloride bath to extract liquid paraffin and decalin. Then, the polyolefin microporous film was obtained by drying at 50 degreeC and annealing at 120 degreeC. The resulting polyolefin microporous membrane had a structure in which fibrillar polyolefins were entangled in a network and constituted pores.
Table 1 shows the measurement results of the properties (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, thermal shrinkage rate) of the obtained polyolefin microporous membrane.
［参考例２］
ＧＵＲ２１２６とＧＵＲＸ１４３とＦ１０３ＥＡの比を０．８９：７．１１：２（重量比）にした以外は実施例１と同様にポリオレフィン微多孔膜を作成した。
得られたポリオレフィン微多孔膜の特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表１に示す。
[Reference Example 2]
A polyolefin microporous membrane was prepared in the same manner as in Example 1 except that the ratio of GUR2126, GURX143, and F103EA was 0.89: 7.11: 2 (weight ratio).
Table 1 shows the measurement results of the properties (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, thermal shrinkage rate) of the obtained polyolefin microporous membrane.
［実施例１］
参考例１で得られたポリオレフィン微多孔膜を用い、この両面に耐熱性樹脂からなる耐熱性多孔質層を積層させて、本発明の非水系二次電池用セパレータを製造した。
具体的に、耐熱性樹脂として、ポリメタフェニレンイソフタルアミド（帝人テクノプロダクツ社製、コーネックス）を用いた。この耐熱性樹脂を、ジメチルアセトアミド（ＤＭＡｃ）とトリプロピレングリコール（ＴＰＧ）が重量比５０：５０となっている混合溶媒に溶解させて、塗工用スラリーを作製した。なお、塗工用スラリーにおけるポリメタフェニレンイソフタルアミドの濃度は５．５重量％となるように調整した。そして、マイヤーバーを２本対峙させ、その間に塗工液を適量のせた。この後、ポリオレフィン微多孔膜を、塗工液がのっているマイヤーバー間を通過させて、ポリオレフィン微多孔膜の表裏面に塗工液を塗工した。ここで、マイヤーバー間のクリアランスは２０μｍに設定し、マイヤーバーの番手は２本とも＃６を用いた。これを重量比で水：ＤＭＡｃ：ＴＰＧ＝５０：２５：２５で４０℃となっている凝固液中に浸漬し、次いで水洗・乾燥を行った。これにより、ポリオレフィン微多孔膜の表裏両面に耐熱性多孔質層が形成された非水系二次電池用セパレータを得た。
得られた非水系二次電池用セパレータの特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表２に示す。
[Example 1]
The polyolefin microporous membrane obtained in Reference Example 1 was used, and a heat-resistant porous layer made of a heat-resistant resin was laminated on both sides to produce a separator for a non-aqueous secondary battery of the present invention.
Specifically, polymetaphenylene isophthalamide (manufactured by Teijin Techno Products, Conex) was used as the heat resistant resin. This heat-resistant resin was dissolved in a mixed solvent of dimethylacetamide (DMAc) and tripropylene glycol (TPG) in a weight ratio of 50:50 to prepare a coating slurry. The concentration of polymetaphenylene isophthalamide in the coating slurry was adjusted to 5.5% by weight. Then, two Meyer bars were opposed to each other, and an appropriate amount of coating liquid was put between them. Thereafter, the polyolefin microporous film was passed between Mayer bars on which the coating liquid was placed, and the coating liquid was applied to the front and back surfaces of the polyolefin microporous film. Here, the clearance between the Meyer bars was set to 20 μm, and # 6 was used for both the Mayer bars. This was immersed in a coagulating liquid having a weight ratio of water: DMAc: TPG = 50: 25: 25 and 40 ° C., followed by washing and drying. This obtained the separator for non-aqueous secondary batteries in which the heat resistant porous layer was formed in the both surfaces of the polyolefin microporous film.
Table 2 shows the measurement results of the characteristics (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, heat shrinkage rate) of the obtained nonaqueous secondary battery separator.
［実施例２］
参考例１で得られたポリオレフィン微多孔膜を用い、これに耐熱性樹脂と無機フィラーからなる耐熱性多孔質層を積層させて、本発明の非水系二次電池用セパレータを製造した。
具体的に、耐熱性樹脂として、ポリメタフェニレンイソフタルアミド（帝人テクノプロダクツ社製、コーネックス）を用いた。この耐熱性樹脂を、ジメチルアセトアミド（ＤＭＡｃ）とトリプロピレングリコール（ＴＰＧ）が重量比５０：５０となっている混合溶媒に溶解させた。このポリマー溶液に、無機フィラーとしてのα−アルミナ（岩谷化学工業社製、ＳＡ−１、平均粒子径０．８μｍ）を分散させて、塗工用スラリーを作製した。なお、塗工用スラリーにおけるポリメタフェニレンイソフタルアミドの濃度は５．５重量％となるようにし、かつ、ポリメタフェニレンイソフタルアミドと無機フィラーの重量比は２５：７５となるように調整した。そして、マイヤーバーを２本対峙させ、その間に塗工液を適量のせた。この後、ポリオレフィン微多孔膜を、塗工液がのっているマイヤーバー間を通過させて、ポリオレフィン微多孔膜の表裏面に塗工液を塗工した。ここで、マイヤーバー間のクリアランスは２０μｍに設定し、マイヤーバーの番手は２本とも＃６を用いた。これを重量比で水：ＤＭＡｃ：ＴＰＧ＝５０：２５：２５で４０℃となっている凝固液中に浸漬し、次いで水洗・乾燥を行った。これにより、ポリオレフィン微多孔膜の表裏両面に耐熱性多孔質層が形成された非水系二次電池用セパレータを得た。
得られた非水系二次電池用セパレータの特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表２に示す。
[Example 2]
The polyolefin microporous membrane obtained in Reference Example 1 was used, and a heat-resistant porous layer made of a heat-resistant resin and an inorganic filler was laminated thereon to produce the non-aqueous secondary battery separator of the present invention.
Specifically, polymetaphenylene isophthalamide (manufactured by Teijin Techno Products, Conex) was used as the heat resistant resin. This heat resistant resin was dissolved in a mixed solvent of dimethylacetamide (DMAc) and tripropylene glycol (TPG) in a weight ratio of 50:50. In this polymer solution, α-alumina (SA-1, manufactured by Iwatani Chemical Industry Co., Ltd., average particle size 0.8 μm) as an inorganic filler was dispersed to prepare a slurry for coating. The concentration of polymetaphenylene isophthalamide in the coating slurry was adjusted to 5.5% by weight, and the weight ratio of polymetaphenylene isophthalamide to inorganic filler was adjusted to 25:75. Then, two Meyer bars were opposed to each other, and an appropriate amount of coating liquid was put between them. Thereafter, the polyolefin microporous film was passed between Mayer bars on which the coating liquid was placed, and the coating liquid was applied to the front and back surfaces of the polyolefin microporous film. Here, the clearance between the Meyer bars was set to 20 μm, and # 6 was used for both the Mayer bars. This was immersed in a coagulating liquid having a weight ratio of water: DMAc: TPG = 50: 25: 25 and 40 ° C., followed by washing and drying. This obtained the separator for non-aqueous secondary batteries in which the heat resistant porous layer was formed in the both surfaces of the polyolefin microporous film.
Table 2 shows the measurement results of the characteristics (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, heat shrinkage rate) of the obtained nonaqueous secondary battery separator.
［実施例３］
無機フィラーに水酸化マグネシウム（協和化学工業社製、キスマ−５Ｐ、平均粒子径１・０μｍ）を使用した以外は、実施例２と同様に非水系二次電池用セパレータを得た。
得られた非水系二次電池用セパレータの特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表２に示す。
[Example 3]
A separator for a nonaqueous secondary battery was obtained in the same manner as in Example 2 except that magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma-5P, average particle size: 1.0 μm) was used as the inorganic filler.
Table 2 shows the measurement results of the characteristics (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, heat shrinkage rate) of the obtained nonaqueous secondary battery separator.
［実施例４］
ポリオレフィン微多孔膜として参考例２で得られたものを使用した以外は、実施例３と同様に非水系二次電池用セパレータを得た。
得られた非水系二次電池用セパレータの特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表２に示す。
[Example 4]
A separator for a non-aqueous secondary battery was obtained in the same manner as in Example 3 except that the polyolefin microporous film obtained in Reference Example 2 was used.
Table 2 shows the measurement results of the characteristics (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, heat shrinkage rate) of the obtained nonaqueous secondary battery separator.
［実施例５］
コバルト酸リチウム（ＬｉＣｏＯ２：日本化学工業社製）８９．５重量部、アセチレンブラック（電気化学工業社製デンカブラック）４．５重量部、ポリフッ化ビニリデン（クレハ化学社製）６重量部となるように、Ｎ−メチル−ピロリドンを用いてこれらを混練し、スラリーを作製した。得られたスラリーを厚さが２０μｍのアルミ箔上に塗布乾燥後プレスし、１００μｍの正極を得た。
メソフェーズカーボンマイクロビーズ（ＭＣＭＢ：大阪瓦斯化学社製）８７重量部、アセチレンブラック（電気化学工業社製商品名デンカブラック）３重量部、ポリフッ化ビニリデン（クレハ化学社製）１０重量部となるようにＮ−メチル−２ピロリドンを用いてこれらを混練し、スラリーを作製した。得られたスラリーを厚さが１８μｍの銅箔上に塗布乾燥後プレスし、９０μｍの負極を得た。
上記正極及び負極を、実施例１で作製した非水系二次電池用セパレータを介して対向させた。これに電解液を含浸させアルミラミネートフィルムからなる外装に封入して非水系二次電池を作製した。ここで、電解液には１Ｍ ＬｉＰＦ６ エチレンカーボネート／エチルメチルカーボネート（３／７重量比）（キシダ化学社製）を用いた。
ここで、この試作電池は正極面積が２×１．４ｃｍ２、負極面積は２．２×１．６ｃｍ２で、設定容量は８ｍＡｈ（４．２Ｖ−２．７５Ｖの範囲）である。
得られた非水系二次電池の特性（放電容量、負荷特性）の測定結果を表３に示す。
[Example 5]
Lithium cobalt oxide (LiCoO 2 : manufactured by Nippon Chemical Industry Co., Ltd.) 89.5 parts by weight, acetylene black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.) 4.5 parts by weight, polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) 6 parts by weight Thus, these were kneaded using N-methyl-pyrrolidone to prepare a slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 μm, dried and pressed to obtain a positive electrode having a thickness of 100 μm.
87 parts by weight of mesophase carbon micro beads (MCMB: manufactured by Osaka Gas Chemical Co., Ltd.), 3 parts by weight of acetylene black (trade name Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 10 parts by weight of polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) These were kneaded using N-methyl-2pyrrolidone to prepare a slurry. The obtained slurry was applied onto a copper foil having a thickness of 18 μm, dried and pressed to obtain a negative electrode having a thickness of 90 μm.
The positive electrode and the negative electrode were opposed to each other through the non-aqueous secondary battery separator produced in Example 1. This was impregnated with an electrolytic solution and sealed in an exterior made of an aluminum laminate film to produce a non-aqueous secondary battery. Here, 1M LiPF 6 ethylene carbonate / ethyl methyl carbonate (3/7 weight ratio) (manufactured by Kishida Chemical Co., Ltd.) was used as the electrolytic solution.
Here, this prototype battery has a positive electrode area of 2 × 1.4 cm 2 , a negative electrode area of 2.2 × 1.6 cm 2 , and a set capacity of 8 mAh (in the range of 4.2V-2.75V).
Table 3 shows the measurement results of the characteristics (discharge capacity, load characteristics) of the obtained nonaqueous secondary battery.
［実施例６］
非水系二次電池用セパレータとして実施例２で得られたものを使用した以外は、実施例５と同様に非水系二次電池を得た。
得られた非水系二次電池の特性（放電容量、負荷特性）の測定結果を表３に示す。
[Example 6]
A nonaqueous secondary battery was obtained in the same manner as in Example 5 except that the separator obtained in Example 2 was used as the separator for the nonaqueous secondary battery.
Table 3 shows the measurement results of the characteristics (discharge capacity, load characteristics) of the obtained nonaqueous secondary battery.
［実施例７］
非水系二次電池用セパレータとして実施例３で得られたものを使用した以外は、実施例５と同様に非水系二次電池を得た。
得られた非水系二次電池の特性（放電容量、負荷特性）の測定結果を表３に示す。
[Example 7]
A nonaqueous secondary battery was obtained in the same manner as in Example 5 except that the separator obtained in Example 3 was used as the separator for the nonaqueous secondary battery.
Table 3 shows the measurement results of the characteristics (discharge capacity, load characteristics) of the obtained nonaqueous secondary battery.
［実施例８］
非水系二次電池用セパレータとして実施例４で得られたものを使用した以外は、実施例５と同様に非水系二次電池を得た。
得られた非水系二次電池の特性（放電容量、負荷特性）の測定結果を表３に示す。
[Example 8]
A nonaqueous secondary battery was obtained in the same manner as in Example 5 except that the separator obtained in Example 4 was used as the separator for the nonaqueous secondary battery.
Table 3 shows the measurement results of the characteristics (discharge capacity, load characteristics) of the obtained nonaqueous secondary battery.
［参考例３］
ポリエチレンのみを使用した事以外、参考例１と同様にポリオレフィン微多孔膜を得た。
得られたポリオレフィン微多孔膜の特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表１に示す。
[Reference Example 3]
A polyolefin microporous membrane was obtained in the same manner as in Reference Example 1 except that only polyethylene was used.
Table 1 shows the measurement results of the properties (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, thermal shrinkage rate) of the obtained polyolefin microporous membrane.
［参考例４］
ポリプロピレンパウダーとしてプライムポリマー社製Ｆ１０３ＥＡ（重量平均分子量４８万、融点１６６℃）を用いた。ポリプロピレンを２００℃で融解させ、ダイから押し出し、９０℃の冷却ロールに導かれ、２５℃の冷風で冷却してベーステープを作成した。
該積層ベーステープを縦延伸、横延伸を逐次行う２軸延伸にて延伸した。ここで、縦延伸６倍、延伸温度は１２０℃、横延伸は延伸倍率９倍、延伸温度は１３５℃とした。横延伸の後に１５５℃で熱固定を行った。その後、１５０℃でアニール処理することでポリオレフィン微多孔膜を得た。得られたポリオレフィン微多孔膜はフィブリル状ポリオレフィンが網目状に交絡し、細孔を構成する構造を有するものであった。
得られたポリオレフィン微多孔膜の特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表１に示す。
[Reference Example 4]
As a polypropylene powder, F103EA (weight average molecular weight 480,000, melting point 166 ° C.) manufactured by Prime Polymer Co., Ltd. was used. Polypropylene was melted at 200 ° C., extruded from a die, guided to a cooling roll at 90 ° C., and cooled with cold air at 25 ° C. to prepare a base tape.
The laminated base tape was stretched by biaxial stretching in which longitudinal stretching and lateral stretching were sequentially performed. Here, the longitudinal stretching was 6 times, the stretching temperature was 120 ° C., the transverse stretching was 9 times the stretching ratio, and the stretching temperature was 135 ° C. After transverse stretching, heat setting was performed at 155 ° C. Then, the polyolefin microporous film was obtained by annealing at 150 degreeC. The resulting polyolefin microporous membrane had a structure in which fibrillar polyolefins were entangled in a network and constituted pores.
Table 1 shows the measurement results of the properties (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, thermal shrinkage rate) of the obtained polyolefin microporous membrane.
［比較例１］
ポリオレフィン微多孔膜として参考例３で得られたものを使用した以外は、実施例３と同様に非水系二次電池用セパレータを得た。
得られた非水系二次電池用セパレータの特性（膜厚、目付、ガーレ値、空孔率、膜抵抗、突刺強度、引張強度、シャットダウン温度、熱収縮率）の測定結果を表２に示す。
[Comparative Example 1]
A separator for a nonaqueous secondary battery was obtained in the same manner as in Example 3 except that the polyolefin microporous film obtained in Reference Example 3 was used.
Table 2 shows the measurement results of the characteristics (film thickness, basis weight, Gurley value, porosity, membrane resistance, puncture strength, tensile strength, shutdown temperature, heat shrinkage rate) of the obtained nonaqueous secondary battery separator.
［比較例２］
ポリオレフィン微多孔膜として参考例４で得られたものを使用した以外は、実施例３と同様に非水系二次電池用セパレータを得る事を試みたが、ポリオレフィン微多孔膜上で塗工用スラリーがはじかれてしまい、非水系二次電池用セパレータを得る事はできなかった。
[Comparative Example 2]
An attempt was made to obtain a separator for a non-aqueous secondary battery in the same manner as in Example 3 except that the polyolefin microporous film obtained in Reference Example 4 was used. As a result, the separator for a non-aqueous secondary battery could not be obtained.
［比較例３］
非水系二次電池用セパレータとして比較例１で得られたものを使用した以外は、実施例５と同様に非水系二次電池を得た。
得られた非水系二次電池の特性（放電容量、負荷特性）の測定結果を表３に示す。
[Comparative Example 3]
A non-aqueous secondary battery was obtained in the same manner as in Example 5 except that the separator obtained in Comparative Example 1 was used as the separator for the non-aqueous secondary battery.
Table 3 shows the measurement results of the characteristics (discharge capacity, load characteristics) of the obtained nonaqueous secondary battery.
本発明の非水系二次電池用セパレータは、ポリオレフィン多孔質基材と、耐熱性樹脂を含んで形成され前記ポリオレフィン多孔質基材の片面又は両面に積層された耐熱性多孔質層と、を備えた非水系二次電池用セパレータであって、前記ポリオレフィン多孔質基材は、ポリエチレンと他のポリオレフィンを含むことで、シャットダウン特性及び耐熱性に加え、機械強度に優れた非水系二次電池用セパレータが得られる。これにより、これを使用した非水系二次電池の安全性を確かなものとする。 A separator for a non-aqueous secondary battery according to the present invention includes a polyolefin porous substrate, and a heat resistant porous layer formed by including a heat resistant resin and laminated on one or both surfaces of the polyolefin porous substrate. A separator for non-aqueous secondary batteries, wherein the polyolefin porous substrate contains polyethylene and other polyolefins, so that it has excellent mechanical strength in addition to shutdown characteristics and heat resistance. Is obtained. This ensures the safety of the non-aqueous secondary battery using this.
Claims (8)
前記ポリオレフィン多孔質基材は、ポリエチレンとポリエチレン以外のポリオレフィンを含むことを特徴とする非水系二次電池用セパレータ。 A non-aqueous secondary battery separator comprising a polyolefin porous substrate, and a heat-resistant porous layer formed by including a heat-resistant resin and laminated on one or both surfaces of the polyolefin porous substrate,
The polyolefin porous substrate contains a polyolefin other than polyethylene and polyethylene, and is a separator for a non-aqueous secondary battery.
請求項１〜７のいずれか１項に記載の非水系二次電池用セパレータを用いたことを特徴とする非水系二次電池。 A non-aqueous secondary battery that obtains an electromotive force by doping or dedoping lithium,
A non-aqueous secondary battery using the separator for a non-aqueous secondary battery according to claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012172618A1 (en) | 2011-06-16 | 2012-12-20 | パナソニック株式会社 | Array microphone device and gain control method |
| WO2017051514A1 (en) * | 2015-09-25 | 2017-03-30 | 三洋電機株式会社 | Cylindrical nonaqueous electrolyte secondary battery |
-
2009
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012172618A1 (en) | 2011-06-16 | 2012-12-20 | パナソニック株式会社 | Array microphone device and gain control method |
| WO2017051514A1 (en) * | 2015-09-25 | 2017-03-30 | 三洋電機株式会社 | Cylindrical nonaqueous electrolyte secondary battery |
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