JP5834940B2 - Separator for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery - Google Patents

Separator for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery Download PDF

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JP5834940B2
JP5834940B2 JP2012008184A JP2012008184A JP5834940B2 JP 5834940 B2 JP5834940 B2 JP 5834940B2 JP 2012008184 A JP2012008184 A JP 2012008184A JP 2012008184 A JP2012008184 A JP 2012008184A JP 5834940 B2 JP5834940 B2 JP 5834940B2
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inorganic filler
insulating inorganic
electrolyte secondary
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JP2013149434A (en
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健太 石井
健太 石井
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • 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
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Description

本発明は、非水電解質二次電池用のセパレータ、及びこれを用いた非水電解質二次電池に関するものである。   The present invention relates to a separator for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the separator.

リチウムイオン二次電池等の非水電解質二次電池は、正極と、負極と、これらの間を絶縁するセパレータと、非水電解質とから概略構成されている。
従来、セパレータとしては、ポリオレフィン系等の多孔質樹脂フィルムが広く用いられている。 A non-aqueous electrolyte secondary battery such as a lithium ion secondary battery is generally composed of a positive electrode, a negative electrode, a separator that insulates between them, and a non-aqueous electrolyte.
Conventionally, as the separator, a porous resin film such as polyolefin is widely used.

従来の樹脂製セパレータと、絶縁性無機フィラー及び結着剤を含む剛性の高い耐熱性多孔質層（ＨＲＬ層）とからなるセパレータを用いた非水電解質二次電池がある。   There is a non-aqueous electrolyte secondary battery using a conventional separator made of resin and a separator composed of a highly heat-resistant porous layer (HRL layer) containing an insulating inorganic filler and a binder.

特許文献１には、水酸化アルミニウムあるいは水酸化マグネシウム等の２００〜４００℃において吸熱反応を生じる無機フィラーを含む耐熱性多孔質層が開示されている（請求項１、３等）。
特許文献１には、上記金属水酸化物の脱水反応により吸熱反応が起こり、難燃効果を発揮することが記載されている（段落００１５）。 Patent Document 1 discloses a heat-resistant porous layer containing an inorganic filler that causes an endothermic reaction at 200 to 400 ° C., such as aluminum hydroxide or magnesium hydroxide (Claims 1 and 3).
Patent Document 1 describes that an endothermic reaction occurs due to a dehydration reaction of the metal hydroxide and exhibits a flame retardant effect (paragraph 0015).

特開2011-028947号公報JP 2011-028947

非水電解質二次電池において、釘刺し又は圧壊等による電池の内部短絡が生じた場合、電池内部に局所的な異常発熱が起こる。
例えば電池容量５Ａｈ以下でエネルギー密度６０ｋＷｈ/ｍ３以下の低容量の非水電解質二次電池においては、釘刺し又は圧壊等による電池の内部短絡時の短絡電流がそれ程大きくないため、局所的な温度上昇はそれ程大きくない。かかる低容量の非水電解質二次電池であれば、特許文献１に記載の耐熱性多孔質層を用いることで、局所的な異常発熱による温度上昇を抑制することができる。 In a nonaqueous electrolyte secondary battery, when an internal short circuit of the battery occurs due to nail penetration or crushing, local abnormal heat generation occurs inside the battery.
For example, in a non-aqueous electrolyte secondary battery having a battery capacity of 5 Ah or less and an energy density of 60 kWh / m 3 or less, the short-circuit current at the time of an internal short-circuit of the battery due to nail penetration or crushing is not so large. The rise is not so great. With such a low-capacity non-aqueous electrolyte secondary battery, by using the heat-resistant porous layer described in Patent Document 1, temperature rise due to local abnormal heat generation can be suppressed.

しかしながら、例えば電池容量２０Ａｈ以上でエネルギー密度２８５ｋＷｈ/ｍ３以上の高容量の非水電解質二次電池においては、釘刺し又は圧壊等による電池の内部短絡時の短絡電流が大きく、エネルギー密度が大きいために蓄熱しやすく、電池内部の温度上昇が大きい。
特許文献１に記載の耐熱性多孔質層では、高容量の非水電解質二次電池において局所的な異常発熱が起こった場合、吸熱反応も局所的となり、電池全体の温度上昇を充分に抑制することが難しい。 However, for example, in a high capacity non-aqueous electrolyte secondary battery with a battery capacity of 20 Ah or more and an energy density of 285 kWh / m 3 or more, the short circuit current at the time of internal short circuit of the battery due to nail penetration or crushing is large, and the energy density is large. The temperature rise inside the battery is large.
In the heat-resistant porous layer described in Patent Document 1, when local abnormal heat generation occurs in a high-capacity nonaqueous electrolyte secondary battery, the endothermic reaction also becomes local, and the temperature rise of the entire battery is sufficiently suppressed. It is difficult.

本発明は上記事情に鑑みてなされたものであり、局所的な異常発熱が起こった場合においても、電池全体の温度上昇を効果的に抑制することが可能な非水電解質二次電池用のセパレータ、及びこれを用いた非水電解質二次電池を提供することを目的とするものである。   The present invention has been made in view of the above circumstances, and is a separator for a non-aqueous electrolyte secondary battery that can effectively suppress an increase in temperature of the entire battery even when local abnormal heat generation occurs. And a non-aqueous electrolyte secondary battery using the same.

本発明の非水電解質二次電池用のセパレータは、
多孔質の樹脂製セパレータと、当該樹脂製セパレータ上に形成された、絶縁性無機フィラーを含む耐熱性多孔質層とを含む非水電解質二次電池用のセパレータであって、
前記耐熱性多孔質層は、前記絶縁性無機フィラーとして、金属水酸化物及び／又は金属酸化物の水和物からなる第１の絶縁性無機フィラーと、熱伝導率が１０Ｗ／ｍ・Ｋ以上である第２の絶縁性無機フィラーとを含むものである。 The separator for the non-aqueous electrolyte secondary battery of the present invention is
A separator for a non-aqueous electrolyte secondary battery comprising a porous resin separator and a heat-resistant porous layer containing an insulating inorganic filler formed on the resin separator,
The heat-resistant porous layer has, as the insulating inorganic filler, a first insulating inorganic filler made of a metal hydroxide and / or a hydrate of metal oxide, and a thermal conductivity of 10 W / m · K or more. And a second insulating inorganic filler.

本発明の非水電解質二次電池は、正極と、負極と、上記の本発明の非水電解質二次電池用のセパレータとを備えたものである。   The nonaqueous electrolyte secondary battery of the present invention includes a positive electrode, a negative electrode, and the separator for the nonaqueous electrolyte secondary battery of the present invention.

本発明によれば、局所的な異常発熱が起こった場合においても、電池全体の温度上昇を効果的に抑制することが可能な非水電解質二次電池用のセパレータ、及びこれを用いた非水電解質二次電池を提供することができる。   According to the present invention, even when local abnormal heat generation occurs, a separator for a non-aqueous electrolyte secondary battery that can effectively suppress an increase in temperature of the entire battery, and a non-water using the same An electrolyte secondary battery can be provided.

本発明に係る非水電解質二次電池の構成例を模式的に示す全体図である。1 is an overall view schematically showing a configuration example of a nonaqueous electrolyte secondary battery according to the present invention. 図１の非水電解質二次電池の部分断面図である。It is a fragmentary sectional view of the nonaqueous electrolyte secondary battery of FIG. 本発明の非水電解質二次電池の釘刺し試験の様子を示す模式図である。It is a schematic diagram which shows the mode of the nail penetration test of the nonaqueous electrolyte secondary battery of this invention. 従来の非水電解質二次電池の釘刺し試験の様子を示す模式図である。It is a schematic diagram which shows the mode of the nail penetration test of the conventional nonaqueous electrolyte secondary battery. 実施例１の釘刺し試験の結果を示すグラフである。4 is a graph showing the results of a nail penetration test of Example 1. 実施例３の釘刺し試験の結果を示すグラフである。It is a graph which shows the result of the nail penetration test of Example 3. 比較例１の釘刺し試験の結果を示すグラフである。6 is a graph showing the results of a nail penetration test of Comparative Example 1. 比較例２の釘刺し試験の結果を示すグラフである。10 is a graph showing the results of a nail penetration test of Comparative Example 2.

以下、本発明について詳述する。   Hereinafter, the present invention will be described in detail.

本発明は、非水電解質二次電池用のセパレータ、及びこれを備えた非水電解質二次電池に関するものである。   The present invention relates to a separator for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery including the separator.

図１及び図２に、非水電解質二次電池の構成例を模式的に示す。図１は全体図、図２は部分断面図である。いずれも模式図である。   FIG. 1 and FIG. 2 schematically show a configuration example of a nonaqueous electrolyte secondary battery. 1 is an overall view, and FIG. 2 is a partial cross-sectional view. Both are schematic diagrams.

図１に示す非水電解質二次電池１は、ケース１１内に、図２に示す積層体２０と、非水電解質（符号略）とが収容されたものである。
積層体２０は、正極２１と、負極２２と、セパレータ２５とが積層されたものである。
セパレータ２５は、従来広く用いられている多孔質の樹脂製セパレータ２３を基材とし、その上に、耐熱性多孔質層（ＨＲＬ（Ｈｅａｔ Ｒｅｓｉｓｔａｎｃｅ Ｌａｙｅｒ）層）２４が積層されたものである。
正極２１と負極２２との間において、樹脂製セパレータ２３及び耐熱性多孔質層２４の配置順序は特に制限されない。
図示する例では、正極２１側に耐熱性多孔質層２４が配置され、負極２２側に樹脂製セパレータ２３が配置されているが、逆でも構わない。
図示する例では、樹脂製セパレータ２３の片面に耐熱性多孔質層２４が形成されているが、耐熱性多孔質層２４は、樹脂製セパレータ２３の片面又は両面に形成することができる。 A non-aqueous electrolyte secondary battery 1 shown in FIG. 1 is a case in which a laminate 20 shown in FIG. 2 and a non-aqueous electrolyte (not shown) are accommodated in a case 11.
The laminate 20 is obtained by laminating a positive electrode 21, a negative electrode 22, and a separator 25.
The separator 25 includes a porous resin separator 23 that has been widely used in the past, and a heat-resistant porous layer (HRL (Heat Resistance Layer) layer) 24 laminated thereon.
The arrangement order of the resin separator 23 and the heat-resistant porous layer 24 is not particularly limited between the positive electrode 21 and the negative electrode 22.
In the illustrated example, the heat-resistant porous layer 24 is disposed on the positive electrode 21 side, and the resin separator 23 is disposed on the negative electrode 22 side.
In the illustrated example, the heat resistant porous layer 24 is formed on one surface of the resin separator 23, but the heat resistant porous layer 24 can be formed on one surface or both surfaces of the resin separator 23.

非水電解質二次電池１は、絶縁性無機フィラーを含む剛性の高い耐熱性多孔質層（ＨＲＬ層）２４を用いているので、耐外部応力に優れる。   Since the nonaqueous electrolyte secondary battery 1 uses a highly heat-resistant porous layer (HRL layer) 24 containing an insulating inorganic filler, it is excellent in external stress resistance.

非水電解質二次電池としては、リチウムイオン二次電池等が挙げられる。以下、リチウムイオン二次電池を例として、耐熱性多孔質層以外の主な構成要素について説明する。   Examples of the non-aqueous electrolyte secondary battery include a lithium ion secondary battery. Hereinafter, main components other than the heat-resistant porous layer will be described by taking a lithium ion secondary battery as an example.

＜正極＞
正極は、公知の方法により、アルミニウム箔などの正極集電体に正極活物質を塗布して、製造することができる。
公知の正極活物質としては特に制限なく、例えば、ＬｉＣｏＯ２、ＬｉＭｎＯ２、ＬｉＭｎ２Ｏ４、ＬｉＮｉＯ２、ＬｉＮｉｘＣｏ（１−ｘ）Ｏ２、及びＬｉＮｉｘＣｏｙＭｎ（１−ｘ−ｙ）Ｏ２等のリチウム含有複合酸化物等が挙げられる。
例えば、Ｎ−メチル−２−ピロリドン等の分散剤を用い、上記の正極活物質と、炭素粉末等の導電剤と、ポリフッ化ビニリデン（ＰＶＤＦ）等の結着剤とを混合して、スラリーを得、このスラリーをアルミニウム箔等の正極集電体上に塗布し、乾燥し、プレス加工して、正極を得ることができる。
正極の目付は特に制限なく、１．５〜１５ｍｇ／ｃｍ２が好ましい。正極の目付が過小では均一な塗布が難しく、過大では集電体から剥離する恐れがある。 <Positive electrode>
The positive electrode can be manufactured by applying a positive electrode active material to a positive electrode current collector such as an aluminum foil by a known method.
Known no particular limitation on the positive electrode active material, for example, LiCoO 2, LiMnO 2, LiMn 2 O 4, LiNiO 2, LiNi x Co (1-x) O 2, and LiNi x Co y Mn (1- x-y ) Lithium-containing composite oxides such as O 2 are listed.
For example, using a dispersant such as N-methyl-2-pyrrolidone, the above positive electrode active material, a conductive agent such as carbon powder, and a binder such as polyvinylidene fluoride (PVDF) are mixed to form a slurry. This slurry can be applied onto a positive electrode current collector such as an aluminum foil, dried, and pressed to obtain a positive electrode.
The basis weight of the positive electrode is not particularly limited and is preferably 1.5 to 15 mg / cm 2 . If the basis weight of the positive electrode is too small, uniform application is difficult, and if it is too large, there is a risk of peeling from the current collector.

正極活物質として金属リチウム等を用いる場合、金属リチウム等をそのまま正極として用いることができる。   When metallic lithium or the like is used as the positive electrode active material, metallic lithium or the like can be used as the positive electrode as it is.

＜負極＞
負極活物質としては特に制限なく、Ｌｉ／Ｌｉ＋基準で２．０Ｖ以下にリチウム吸蔵能力を持つものが好ましく用いられる。負極活物質としては、黒鉛等の炭素、金属リチウム、リチウム合金、リチウムイオンのド−プ・脱ド−プが可能な遷移金属酸化物／遷移金属窒化物／遷移金属硫化物、及び、これらの組合わせ等が挙げられる。 <Negative electrode>
The negative electrode active material is not particularly limited, and a material having a lithium storage capacity of 2.0 V or less on the basis of Li / Li + is preferably used. As the negative electrode active material, carbon such as graphite, metallic lithium, lithium alloy, transition metal oxide / transition metal nitride / transition metal sulfide capable of doping / dedoping lithium ions, and these A combination etc. are mentioned.

リチウムイオン二次電池において、負極活物質には、リチウムの吸蔵及び放出が可能な炭素材料が広く使用されている。特に黒鉛等の高結晶性炭素は、放電電位が平坦であり、真密度が高く、かつ充填性が良いなどの特性を有していることから、市販のリチウムイオン二次電池の多くの負極活物質として使用されている。したがって、負極活物質としては黒鉛等が特に好ましい。   In a lithium ion secondary battery, a carbon material capable of inserting and extracting lithium is widely used as a negative electrode active material. In particular, highly crystalline carbon such as graphite has characteristics such as a flat discharge potential, high true density, and good fillability. Therefore, many negative electrode actives of commercially available lithium ion secondary batteries are used. It is used as a substance. Accordingly, graphite and the like are particularly preferable as the negative electrode active material.

負極は、公知の方法により、銅箔などの負極集電体に負極活物質を塗布して、製造することができる。
例えば、水等の分散剤を用い、上記の負極活物質と、変性スチレン−ブタジエン共重合体ラテックス等の結着剤と、必要に応じてカルボキシメチルセルロースＮａ塩（ＣＭＣ）等の増粘剤とを混合して、スラリーを得、このスラリーを銅箔等の負極集電体上に塗布し、乾燥し、プレス加工して、負極を得ることができる。
負極の目付は特に制限なく、１．５〜１５ｍｇ／ｃｍ２が好ましい。負極の目付が過小では均一な塗布が難しく、過大では集電体から剥離する恐れがある。 The negative electrode can be produced by applying a negative electrode active material to a negative electrode current collector such as a copper foil by a known method.
For example, using a dispersant such as water, the negative electrode active material described above, a binder such as a modified styrene-butadiene copolymer latex, and a thickener such as carboxymethyl cellulose Na salt (CMC) as necessary. Mixing is performed to obtain a slurry, and this slurry is applied onto a negative electrode current collector such as a copper foil, dried, and pressed to obtain a negative electrode.
The basis weight of the negative electrode is not particularly limited and is preferably 1.5 to 15 mg / cm 2 . If the basis weight of the negative electrode is too small, uniform application is difficult, and if it is too large, there is a risk of peeling from the current collector.

負極活物質として金属リチウム等を用いる場合、金属リチウム等をそのまま負極として用いることができる。   When metallic lithium or the like is used as the negative electrode active material, metallic lithium or the like can be used as it is as the negative electrode.

＜樹脂製セパレータ＞
樹脂製セパレータは、正極と負極とを電気的に絶縁し、かつリチウムイオンが透過可能な膜であればよく、多孔質高分子フィルムが好ましく使用される。
セパレータとしては例えば、ＰＰ（ポリプロピレン）製多孔質フィルム、ＰＥ（ポリエチレン）製多孔質フィルム、あるいは、ＰＰ（ポリプロピレン）−ＰＥ（ポリエチレン）の積層型多孔質フィルム等のポリオレフィン製多孔質フィルムが好ましく用いられる。 <Resin separator>
The resin separator may be a film that electrically insulates the positive electrode and the negative electrode and is permeable to lithium ions, and a porous polymer film is preferably used.
As the separator, for example, a porous film made of polyolefin such as a porous film made of PP (polypropylene), a porous film made of PE (polyethylene), or a laminated porous film of PP (polypropylene) -PE (polyethylene) is preferably used. It is done.

＜耐熱性多孔質層（ＨＲＬ層）＞
耐熱性多孔質層は上記の樹脂製セパレータを基材として形成され、絶縁性無機フィラーを含む層である。 <Heat-resistant porous layer (HRL layer)>
The heat resistant porous layer is a layer formed using the resin separator as a base material and containing an insulating inorganic filler.

絶縁性無機フィラーの材料としては、耐酸化性に優れ、化学的に安定なものが用いられる。
本発明の耐熱性多孔質層では、絶縁性無機フィラーとして、金属水酸化物及び／又は金属酸化物の水和物からなる第１の絶縁性無機フィラーと、熱伝導率が１０Ｗ／ｍ・Ｋ以上である第２の絶縁性無機フィラーとが用いられる。 As the material for the insulating inorganic filler, a material which is excellent in oxidation resistance and chemically stable is used.
In the heat resistant porous layer of the present invention, as the insulating inorganic filler, a first insulating inorganic filler made of a metal hydroxide and / or a hydrate of metal oxide, and a thermal conductivity of 10 W / m · K. The above-mentioned second insulating inorganic filler is used.

第１の絶縁性無機フィラーである金属水酸化物及び／又は金属酸化物の水和物は、脱水反応により吸熱反応を生じる。
吸熱反応は通常使用条件では起こらず、異常内部短絡時には直ちに吸熱反応が起こる必要がある。
第１の絶縁性無機フィラーとしては、２００〜５００℃において吸熱反応を生じるものが好ましい。 The metal hydroxide and / or metal oxide hydrate, which is the first insulating inorganic filler, undergoes an endothermic reaction by a dehydration reaction.
An endothermic reaction does not occur under normal use conditions, and an endothermic reaction must occur immediately upon an abnormal internal short circuit.
As a 1st insulating inorganic filler, what produces an endothermic reaction in 200-500 degreeC is preferable.

第１の絶縁性無機フィラーとしては例えば、水酸化アルミニウム（Ａｌ（ＯＨ）３）、水酸化マグネシウム（Ｍｇ（ＯＨ）２）、酸化アルミニウム水和物（Ａｌ２Ｏ３・Ｈ２Ｏ）、及び酸化マグネシウム水和物（ＭｇＯ・Ｈ２Ｏ）からなる群より選ばれた少なくとも１種が好ましい。これらは２００〜５００℃において吸熱反応を生じる。これらの熱伝導率は、１０Ｗ／ｍ・Ｋ未満である。 Examples of the first insulating inorganic filler include aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (OH) 2 ), aluminum oxide hydrate (Al 2 O 3 .H 2 O), and At least one selected from the group consisting of magnesium oxide hydrate (MgO.H 2 O) is preferable. These cause an endothermic reaction at 200-500 ° C. Their thermal conductivity is less than 10 W / m · K.

第２の絶縁性無機フィラーとしては、熱伝導率が１０Ｗ／ｍ・Ｋ以上のものを用いる。
第２の絶縁性無機フィラーとしては例えば、炭化珪素（ＳｉＣ）（熱伝導率１０Ｗ／ｍ・Ｋ）、酸化アルミニウム無水物（Ａｌ２Ｏ３）（熱伝導率３０Ｗ／ｍ・Ｋ）、酸化マグネシウム無水物（ＭｇＯ）（熱伝導率４０Ｗ／ｍ・Ｋ）、窒化珪素（Ｓｉ３Ｎ４）（熱伝導率５０Ｗ／ｍ・Ｋ）、酸化亜鉛（ＺｎＯ）（熱伝導率６０Ｗ／ｍ・Ｋ）、窒化ホウ素（ＢＮ）（熱伝導率１５０Ｗ／ｍ・Ｋ）、窒化アルミニウム（ＡｌＮ）（熱伝導率２００Ｗ／ｍ・Ｋ）、及びダイヤモンド（熱伝導率２０００Ｗ／ｍ・Ｋ）からなる群より選ばれた少なくとも１種が好ましい。 As the second insulating inorganic filler, those having a thermal conductivity of 10 W / m · K or more are used.
Examples of the second insulating inorganic filler include silicon carbide (SiC) (thermal conductivity 10 W / m · K), aluminum oxide anhydride (Al 2 O 3 ) (thermal conductivity 30 W / m · K), magnesium oxide. Anhydride (MgO) (thermal conductivity 40 W / m · K), silicon nitride (Si 3 N 4 ) (thermal conductivity 50 W / m · K), zinc oxide (ZnO) (thermal conductivity 60 W / m · K) Boron nitride (BN) (thermal conductivity 150 W / m · K), aluminum nitride (AlN) (thermal conductivity 200 W / m · K), and diamond (thermal conductivity 2000 W / m · K) At least one selected from the above is preferred.

第２の絶縁性無機フィラーとしては、熱伝導率が高い方が好ましい。
第２の絶縁性無機フィラーの熱伝導率は、３０Ｗ／ｍ・Ｋ以上が好ましく、５０Ｗ／ｍ・Ｋ以上がより好ましく、１００Ｗ／ｍ・Ｋ以上が特に好ましい。
第２の絶縁性無機フィラーとしては、窒化ホウ素（ＢＮ）、窒化アルミニウム（ＡｌＮ）、及びダイヤモンドからなる群より選ばれた少なくとも１種が好ましく、コスト等を考慮すれば、窒化ホウ素（ＢＮ）、及び／又は窒化アルミニウム（ＡｌＮ）が特に好ましい。 The second insulating inorganic filler preferably has a higher thermal conductivity.
The thermal conductivity of the second insulating inorganic filler is preferably 30 W / m · K or more, more preferably 50 W / m · K or more, and particularly preferably 100 W / m · K or more.
As the second insulating inorganic filler, at least one selected from the group consisting of boron nitride (BN), aluminum nitride (AlN), and diamond is preferable. In consideration of cost and the like, boron nitride (BN), And / or aluminum nitride (AlN) is particularly preferred.

非水電解質二次電池において、釘刺し又は圧壊等による電池の内部短絡が生じた場合、電池内部に局所的な異常発熱が起こる。
本発明の耐熱性多孔質層では、局所的な異常発熱が起こった場合、第１の絶縁性無機フィラーの脱水反応によって水蒸気が発生する。この水蒸気が膨張して異常発熱箇所の周囲に広がる。この反応は大きな吸熱反応であり、この反応により局所的に発生した熱が吸収される。これらの作用により、局所的な異常発熱による温度上昇が抑制される。
さらに、本発明の耐熱性多孔質層では、熱伝導性の高い第２の絶縁性無機フィラーを含んでいるので、異常発熱箇所から熱が面方向に良好に拡散され、局所的な異常発熱による温度上昇が抑制される。
以上の相乗効果で、局所的に異常発熱が生じた場合においても、電池全体の温度上昇が抑制され、電池ケースの破裂等が抑制される。 In a nonaqueous electrolyte secondary battery, when an internal short circuit of the battery occurs due to nail penetration or crushing, local abnormal heat generation occurs inside the battery.
In the heat resistant porous layer of the present invention, when local abnormal heat generation occurs, water vapor is generated by the dehydration reaction of the first insulating inorganic filler. This water vapor expands and spreads around the abnormal heat generation point. This reaction is a large endothermic reaction, and heat generated locally by this reaction is absorbed. By these actions, temperature rise due to local abnormal heat generation is suppressed.
Furthermore, since the heat-resistant porous layer of the present invention contains the second insulating inorganic filler having high thermal conductivity, heat is diffused well in the surface direction from the abnormal heat generation location, and local abnormal heat generation is caused. Temperature rise is suppressed.
Due to the above synergistic effect, even when abnormal heat generation occurs locally, the temperature rise of the entire battery is suppressed, and the battery case is prevented from being ruptured.

図３Ａ及び図３Ｂに、釘刺し試験における本発明の非水電解質二次電池と従来の非水電解質二次電池の相違を模式的に示す。
図３Ａは本発明の非水電解質二次電池の要部断面図、図３Ｂは従来の非水電解質二次電池の要部断面図である。
なお、図示する電池構成は例にすぎず、適宜設計変更される。
図３Ａにおいて、符号１は本発明の非水電解質二次電池、符号２１は正極、符号２２は負極、符号２３は樹脂製セパレータ、符号２４は耐熱性多孔質層、符号２５はセパレータ、符号３０は釘刺し試験で用いられる釘である。
図３Ｂにおいて、符号１０１は無機フィラーとして、金属水酸化物及び／又は金属酸化物の水和物からなる第１の絶縁性無機フィラーと、熱伝導率が１０Ｗ／ｍ・Ｋ以上である第２の絶縁性無機フィラーのいずれも用いられていない従来の非水電解質二次電池、符号１２１は正極、符号１２２は負極、符号１２３は樹脂製セパレータ、符号１２４は耐熱性多孔質層、符号１２５はセパレータ、符号１３０は釘刺し試験で用いられる釘である。
図３Ａ、図３Ｂ中の符号ＨＤは、熱拡散の様子を模式的に示すものである。 3A and 3B schematically show the difference between the nonaqueous electrolyte secondary battery of the present invention and the conventional nonaqueous electrolyte secondary battery in the nail penetration test.
FIG. 3A is a cross-sectional view of main parts of a nonaqueous electrolyte secondary battery of the present invention, and FIG. 3B is a cross-sectional view of main parts of a conventional nonaqueous electrolyte secondary battery.
The illustrated battery configuration is merely an example, and the design can be changed as appropriate.
In FIG. 3A, reference numeral 1 is a nonaqueous electrolyte secondary battery of the present invention, reference numeral 21 is a positive electrode, reference numeral 22 is a negative electrode, reference numeral 23 is a resin separator, reference numeral 24 is a heat-resistant porous layer, reference numeral 25 is a separator, reference numeral 30. Is a nail used in the nail penetration test.
In FIG. 3B, reference numeral 101 denotes a first insulating inorganic filler made of a metal hydroxide and / or a hydrate of a metal oxide as an inorganic filler, and a second having a thermal conductivity of 10 W / m · K or more. The conventional non-aqueous electrolyte secondary battery in which none of the insulating inorganic fillers is used, reference numeral 121 is a positive electrode, reference numeral 122 is a negative electrode, reference numeral 123 is a resin separator, reference numeral 124 is a heat-resistant porous layer, and reference numeral 125 is A separator 130 is a nail used in a nail penetration test.
A symbol HD in FIGS. 3A and 3B schematically shows a state of thermal diffusion.

図３Ｂに示す従来の非水電解質二次電池１０１では、局所的な異常発熱による温度上昇が抑制されず、異常発熱部分の樹脂製セパレータ１２３が熱によりダメージを受ける。具体的には、樹脂製セパレータ１２３の釘刺し部分の周囲が熱により溶解して、釘刺しにより形成された穴１２３Ｈが拡大し、この穴１２３Ｈの拡大により樹脂製セパレータ１２３が面収縮する。その結果、正極１２１の活物質と負極１２２の活物質とが接触して短絡が起こり、それに伴って大きな温度上昇が起こる。従来の非水電解質二次電池１０１では、局所的な異常発熱による温度上昇が抑制されないので、電池の破裂等が起こる恐れがある。   In the conventional nonaqueous electrolyte secondary battery 101 shown in FIG. 3B, the temperature rise due to local abnormal heat generation is not suppressed, and the resin separator 123 in the abnormal heat generation portion is damaged by heat. Specifically, the periphery of the nail piercing portion of the resin separator 123 is melted by heat, the hole 123H formed by the nail piercing is enlarged, and the resin separator 123 is contracted by the enlargement of the hole 123H. As a result, the active material of the positive electrode 121 and the active material of the negative electrode 122 come into contact with each other, causing a short circuit, and a large temperature increase is caused accordingly. In the conventional non-aqueous electrolyte secondary battery 101, the temperature rise due to local abnormal heat generation is not suppressed, and there is a risk of battery rupture or the like.

これに対して、図３Ａに示す本発明の非水電解質二次電池１では、上記したように耐熱性多孔質層２４の吸熱反応と熱拡散によって異常発熱による温度上昇が電池全体的に抑制されるので、樹脂製セパレータ２３が受けるダメージが小さく、樹脂製セパレータ２３に釘刺しにより形成される穴２３Ｈの拡大が抑制される。その結果、正極２１の活物質と負極２２の活物質との接触が抑制され、短絡による温度上昇が抑制される。本発明の非水電解質二次電池１では、耐熱性多孔質層２４によって異常発熱による温度上昇が電池全体的に抑制されるので、電池の破裂等が抑制される。   On the other hand, in the nonaqueous electrolyte secondary battery 1 of the present invention shown in FIG. 3A, the temperature rise due to abnormal heat generation is suppressed as a whole by the endothermic reaction and thermal diffusion of the heat resistant porous layer 24 as described above. Therefore, the damage received by the resin separator 23 is small, and the expansion of the hole 23H formed in the resin separator 23 by nail penetration is suppressed. As a result, contact between the active material of the positive electrode 21 and the active material of the negative electrode 22 is suppressed, and a temperature increase due to a short circuit is suppressed. In the nonaqueous electrolyte secondary battery 1 of the present invention, the temperature rise due to abnormal heat generation is suppressed by the heat-resistant porous layer 24 as a whole, and therefore, battery rupture or the like is suppressed.

「発明が解決しようとする課題」の項で述べたように、例えば電池容量５Ａｈ以下でエネルギー密度６０ｋＷｈ/ｍ３以下の低容量の非水電解質二次電池においては、釘刺し又は圧壊等による電池の内部短絡時の短絡電流がそれ程大きくないため、局所的な温度上昇はそれ程大きくない。かかる低容量の非水電解質二次電池であれば、「背景技術」の項で挙げた特許文献１に記載の耐熱性多孔質層でも、局所的な異常発熱による温度上昇を抑制することができる。 As described in the section “Problems to be Solved by the Invention”, for example, in a low capacity non-aqueous electrolyte secondary battery having a battery capacity of 5 Ah or less and an energy density of 60 kWh / m 3 or less, a battery by nail penetration or crushing is used. Since the short circuit current at the time of internal short circuit is not so large, the local temperature rise is not so large. With such a low-capacity non-aqueous electrolyte secondary battery, even the heat-resistant porous layer described in Patent Document 1 mentioned in the section “Background Art” can suppress a temperature rise due to local abnormal heat generation. .

しかしながら、例えば電池容量２０Ａｈ以上でエネルギー密度２８５ｋＷｈ/ｍ３以上の高容量の非水電解質二次電池においては、釘刺し又は圧壊等による電池の内部短絡時の短絡電流が大きく、エネルギー密度が大きいために蓄熱しやすく、電池内部の温度上昇が大きい。
特許文献１に記載の耐熱性多孔質層では、高容量の非水電解質二次電池において局所的な異常発熱が起こった場合、吸熱反応も局所的となり、電池全体の温度上昇を充分に抑制することが難しい。 However, for example, in a high capacity non-aqueous electrolyte secondary battery with a battery capacity of 20 Ah or more and an energy density of 285 kWh / m 3 or more, the short circuit current at the time of internal short circuit of the battery due to nail penetration or crushing is large, and the energy density is large. The temperature rise inside the battery is large.
In the heat-resistant porous layer described in Patent Document 1, when local abnormal heat generation occurs in a high-capacity nonaqueous electrolyte secondary battery, the endothermic reaction also becomes local, and the temperature rise of the entire battery is sufficiently suppressed. It is difficult.

本発明のセパレータでは、例えば電池容量２０Ａｈ以上でエネルギー密度２８５ｋＷｈ/ｍ３以上の高容量の非水電解質二次電池においても、電池全体の温度上昇を充分に抑制することができる。 In the separator of the present invention, for example, even in a high capacity non-aqueous electrolyte secondary battery having a battery capacity of 20 Ah or more and an energy density of 285 kWh / m 3 or more, the temperature rise of the whole battery can be sufficiently suppressed.

本発明の耐熱性多孔質層は、絶縁性無機フィラーとして、上記の第１の絶縁性無機フィラーと第２の絶縁性無機フィラーのみを含むことができる。
本発明の耐熱性多孔質層は、絶縁性無機フィラーとして、必要に応じて他の公知の任意の絶縁性無機フィラーを含むことができる。
第１、第２の絶縁性無機フィラー以外の任意成分の絶縁性無機フィラーとしては例えば、酸化珪素（ＳｉＯ２）（熱伝導率１Ｗ／ｍ・Ｋ）、酸化チタン（ＴｉＯ２）（熱伝導率８Ｗ／ｍ・Ｋ）、及び酸化ジルコニウム（ＺｒＯ２）（熱伝導率３Ｗ／ｍ・Ｋ）等が挙げられる。これらは１種又は２種以上用いることができる。 The heat-resistant porous layer of the present invention can contain only the first insulating inorganic filler and the second insulating inorganic filler as the insulating inorganic filler.
The heat-resistant porous layer of the present invention can contain any other known insulating inorganic filler as the insulating inorganic filler, if necessary.
Examples of the optional insulating inorganic filler other than the first and second insulating inorganic fillers include silicon oxide (SiO 2 ) (thermal conductivity 1 W / m · K), titanium oxide (TiO 2 ) (thermal conductivity). 8 W / m · K), zirconium oxide (ZrO 2 ) (thermal conductivity 3 W / m · K), and the like. These can be used alone or in combination of two or more.

すべての絶縁性無機フィラーに対する第１、第２の絶縁性無機フィラーの量が多い程、温度上昇の抑制効果が高く、好ましい。
すべての絶縁性無機フィラーの合計１００質量部に対して、第１の絶縁性無機フィラーと第２の絶縁性無機フィラーとの合計量が１０質量部以上であることが好ましく、２０質量部以上であることがより好ましく、５０質量部以上であることがより好ましく、８０質量部以上であることがより好ましく、９０質量部以上であることがより好ましく、１００質量部又はそれに近いことが最も好ましい。 The larger the amount of the first and second insulating inorganic fillers relative to all the insulating inorganic fillers, the higher the effect of suppressing the temperature rise, which is preferable.
It is preferable that the total amount of the first insulating inorganic filler and the second insulating inorganic filler is 10 parts by mass or more with respect to a total of 100 parts by mass of all the insulating inorganic fillers. More preferably, it is more preferably 50 parts by mass or more, more preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and most preferably 100 parts by mass or close thereto.

第１の絶縁性無機フィラーと第２の絶縁性無機フィラーとの配合比は特に制限されない。第１の絶縁性無機フィラーの量が過小では、脱水反応による吸熱反応が不充分となる恐れがある。
第１の絶縁性無機フィラーによる吸熱反応によって異常発熱による温度上昇を直ちに抑制し、その上で、第２の絶縁性無機フィラーにより効果的に熱を拡散させることが好ましい。
したがって、第１の絶縁性無機フィラーと第２の絶縁性無機フィラーとの合計１００質量部に対して、第１の絶縁性無機フィラーが５０質量部以上であることが好ましい。ただし、第１の絶縁性無機フィラーが過剰では、第２の絶縁性無機フィラーによる熱拡散効果が充分に発現しなくなる恐れがある。
第１の絶縁性無機フィラーと第２の絶縁性無機フィラーとの合計１００質量部に対して、第１の絶縁性無機フィラーの量が５０〜８０質量部であることが好ましく、６０〜７０質量部であることが特に好ましい。 The blending ratio of the first insulating inorganic filler and the second insulating inorganic filler is not particularly limited. If the amount of the first insulating inorganic filler is too small, the endothermic reaction due to the dehydration reaction may be insufficient.
It is preferable to immediately suppress an increase in temperature due to abnormal heat generation by the endothermic reaction by the first insulating inorganic filler, and then effectively diffuse the heat by the second insulating inorganic filler.
Therefore, it is preferable that the first insulating inorganic filler is 50 parts by mass or more with respect to 100 parts by mass in total of the first insulating inorganic filler and the second insulating inorganic filler. However, if the first insulating inorganic filler is excessive, the thermal diffusion effect by the second insulating inorganic filler may not be sufficiently exhibited.
It is preferable that the amount of the first insulating inorganic filler is 50 to 80 parts by mass with respect to a total of 100 parts by mass of the first insulating inorganic filler and the second insulating inorganic filler, and 60 to 70 parts by mass. Part is particularly preferred.

通常、耐熱性多孔質層は結着剤を含む。
結着剤としては公知のものを使用でき、例えばポリフッ化ビニリデン（ＰＶＤＦ）、変性アクリルゴム、及びこれらの組合わせ等が挙げられる。
一般に、結着剤は、電池構成後に非水電解質を吸収して膨潤する。このため、結着剤の添加量は、少ない方が好ましい。上記のポリフッ化ビニリデン及びアクリルゴムは、少量でも結着効果を示すため、その添加量を少なくすることができ、好ましい。結着剤の量は特に制限されず、絶縁性フィラーを良好に結着でき、非水電解質の吸収による膨潤を抑制するには、例えば絶縁性フィラー１００質量部に対して０．３〜８．５質量部が好ましい。 Usually, the heat-resistant porous layer contains a binder.
A well-known thing can be used as a binder, For example, a polyvinylidene fluoride (PVDF), modified acrylic rubber, these combinations, etc. are mentioned.
In general, the binder swells by absorbing the nonaqueous electrolyte after the battery construction. For this reason, it is preferable that the amount of the binder added is small. The above-mentioned polyvinylidene fluoride and acrylic rubber are preferable because they show a binding effect even in a small amount, and can be added in a small amount. The amount of the binder is not particularly limited, and in order to bind the insulating filler satisfactorily and to suppress swelling due to absorption of the nonaqueous electrolyte, for example, 0.3 to 8. 5 parts by mass is preferred.

本発明のセパレータの製造方法は特に制限されない。本発明のセパレータは例えば、樹脂製セパレータを基材とし、その片面又は両面に、絶縁性フィラーと結着剤と分散媒とを混合して得られたペーストを塗布し、遠赤外線あるいは熱風等で乾燥することで、製造することができる。   The manufacturing method of the separator of the present invention is not particularly limited. The separator of the present invention is, for example, a resin separator as a base material, and a paste obtained by mixing an insulating filler, a binder, and a dispersion medium is applied to one side or both sides of the separator. It can be manufactured by drying.

＜非水電解質＞
非水電解質としては公知のものが使用でき、液状、ゲル状もしくは固体状の非水電解質が使用できる。
例えば、プロピレンカーボネ−トあるいはエチレンカーボネ−ト等の高誘電率カーボネート溶媒と、ジエチルカーボネート、メチルエチルカーボネート、ジメチルカーボネート等の低粘度カーボネート溶媒との混合溶媒に、リチウム含有電解質を溶解した非水電界液が好ましく用いられる。
混合溶媒としては例えば、エチレンカーボネート（ＥＣ）／ジメチルカーボネート（ＤＭＣ）／エチルメチルカーボネート（ＥＭＣ）の混合溶媒が好ましく用いられる。
リチウム含有電解質としては例えば、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、Ｌｉ２ＳｉＦ６、ＬｉＯＳＯ２ＣｋＦ（２ｋ＋１）（ｋ＝１〜８の整数）、ＬｉＰＦｎ｛ＣｋＦ（２ｋ＋１）｝（６−ｎ）（ｎ＝１〜５の整数、ｋ＝１〜８の整数）等のリチウム塩、及びこれらの組合わせが挙げられる。 <Nonaqueous electrolyte>
As the non-aqueous electrolyte, known ones can be used, and liquid, gel-like or solid non-aqueous electrolytes can be used.
For example, a lithium-containing electrolyte is dissolved in a mixed solvent of a high dielectric constant carbonate solvent such as propylene carbonate or ethylene carbonate and a low viscosity carbonate solvent such as diethyl carbonate, methyl ethyl carbonate, or dimethyl carbonate. A water electrolysis solution is preferably used.
As the mixed solvent, for example, a mixed solvent of ethylene carbonate (EC) / dimethyl carbonate (DMC) / ethyl methyl carbonate (EMC) is preferably used.
Examples of the lithium-containing electrolyte include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , Li 2 SiF 6 , LiOSO 2 C k F (2k + 1) (k = 1 to 8), LiPF n {C k F (2k + 1) )} (6-n) ( n = 1~5 integer, k = 1 to 8 integer) lithium salts such as, and combinations thereof.

＜ケース＞
ケースとしては公知のものが使用できる。
二次電池の型としては、円筒型、コイン型、角型、あるいはフィルム型等があり、所望の型に合わせてケースを選定することができる。 <Case>
A well-known case can be used.
The secondary battery type includes a cylindrical type, a coin type, a square type, a film type, and the like, and a case can be selected according to a desired type.

以上説明したように、本発明によれば、局所的な異常発熱が起こった場合においても、電池全体の温度上昇を効果的に抑制することが可能な非水電解質二次電池用のセパレータ、及びこれを用いた非水電解質二次電池を提供することができる。   As described above, according to the present invention, even when local abnormal heat generation occurs, a separator for a non-aqueous electrolyte secondary battery that can effectively suppress an increase in temperature of the entire battery, and A non-aqueous electrolyte secondary battery using this can be provided.

本発明に係る実施例及び比較例について説明する。   Examples and comparative examples according to the present invention will be described.

[実施例１〜３、比較例１〜２]
実施例１〜３及び比較例１〜２では、耐熱性多孔質層の製造条件を変更する以外は、同一条件として、リチウムイオン二次電池を製造した。 [Examples 1-3, Comparative Examples 1-2]
In Examples 1-3 and Comparative Examples 1-2, lithium ion secondary batteries were manufactured under the same conditions except that the manufacturing conditions of the heat-resistant porous layer were changed.

＜セパレータ＞
実施例１においては、第１のフィラーとしての酸化アルミニウム水和物（Ａｌ２Ｏ３・Ｈ２Ｏ）と、第２のフィラーとしての窒化ホウ素（ＢＮ）とを質量比７０：３０で乾式混合した。得られた混合粉末９７質量部と、変性アクリロニトリルゴムの８質量％ＮＭＰ溶液３７．５質量部と、適量のＮＭＰとを混合し、練合機にてよく混合して、耐熱性多孔質層形成用の塗布ペーストを調製した。
２０μｍ厚のポリエチレン製多孔質セパレータを基材とし、この上に上記の塗布ペーストを塗布した。熱風乾燥及び真空乾燥により溶媒を除去して、耐熱性多孔質層を形成した。耐熱性多孔質層の厚みは８μｍであった。
以上のようにして、セパレータを得た。
実施例１の耐熱性多孔質層の組成を表１に示す。 <Separator>
In Example 1, dry mixing of aluminum oxide hydrate (Al 2 O 3 .H 2 O) as the first filler and boron nitride (BN) as the second filler at a mass ratio of 70:30. did. 97 parts by mass of the obtained mixed powder, 37.5 parts by mass of an 8% by mass NMP solution of modified acrylonitrile rubber, and an appropriate amount of NMP are mixed and mixed well in a kneader to form a heat resistant porous layer. A coating paste was prepared.
A polyethylene porous separator having a thickness of 20 μm was used as a base material, and the coating paste was applied thereon. The solvent was removed by hot air drying and vacuum drying to form a heat resistant porous layer. The thickness of the heat resistant porous layer was 8 μm.
A separator was obtained as described above.
The composition of the heat-resistant porous layer of Example 1 is shown in Table 1.

実施例２、３及び比較例１、２においては、耐熱性多孔質層の組成を表１に示すものとした以外は、実施例１と同様にして、セパレータを得た。   In Examples 2 and 3 and Comparative Examples 1 and 2, separators were obtained in the same manner as in Example 1 except that the composition of the heat-resistant porous layer was as shown in Table 1.

＜正極＞
正極活物質として、一般式ＬｉＣｏＯ２で表されるリチウム複合酸化物を用いた。
分散剤としてＮ−メチル−２−ピロリドンを用い、上記の正極活物質と、導電剤であるアセチレンブラックと、結着剤であるＰＶＤＦとを９０／７／３（質量比）で混合して、電極層形成用ペーストを得た。
上記電極層形成用ペーストを集電体であるアルミニウム箔上にドクターブレード法で塗布し、１５０℃で３０分間乾燥し、プレス機械を用いてプレス加工して、電極層を形成した。
以上のようにして、正極を得た。正極電極層は、目付２０ｍｇ／ｃｍ２、密度３．０ｇ／ｃｍ３とした。 <Positive electrode>
As the positive electrode active material, a lithium composite oxide represented by the general formula LiCoO 2 was used.
Using N-methyl-2-pyrrolidone as a dispersant, mixing the above positive electrode active material, acetylene black as a conductive agent, and PVDF as a binder at 90/7/3 (mass ratio), An electrode layer forming paste was obtained.
The electrode layer forming paste was applied onto an aluminum foil as a current collector by a doctor blade method, dried at 150 ° C. for 30 minutes, and pressed using a press machine to form an electrode layer.
As described above, a positive electrode was obtained. The positive electrode layer had a basis weight of 20 mg / cm 2 and a density of 3.0 g / cm 3 .

＜負極＞
負極活物質として、黒鉛を用いた。
分散剤として水を用い、上記の負極活物質と、結着剤である変性スチレン−ブタジエン共重合体ラテックス（ＳＢＲ）と、増粘剤であるカルボキシメチルセルロースＮａ塩（ＣＭＣ）とを９７／２／１（質量比）で混合して、スラリーを得た。
上記電極層形成用ペーストを集電体であるアルミニウム箔上にドクターブレード法で塗布し、１５０℃で３０分間乾燥し、プレス機械を用いてプレス加工して、電極層を形成した。
以上のようにして、負極を得た。負極電極層は、目付１０ｍｇ／ｃｍ２、密度１．４ｇ／ｃｍ３とした。 <Negative electrode>
Graphite was used as the negative electrode active material.
Using water as a dispersant, the above-described negative electrode active material, modified styrene-butadiene copolymer latex (SBR) as a binder, and carboxymethyl cellulose Na salt (CMC) as a thickener are 97/2 / 1 (mass ratio) was mixed to obtain a slurry.
The electrode layer forming paste was applied onto an aluminum foil as a current collector by a doctor blade method, dried at 150 ° C. for 30 minutes, and pressed using a press machine to form an electrode layer.
A negative electrode was obtained as described above. The negative electrode layer had a basis weight of 10 mg / cm 2 and a density of 1.4 g / cm 3 .

＜非水電解質＞
エチレンカーボネート（ＥＣ）／ジメチルカーボネート（ＤＭＣ）／エチルメチルカーボネート（ＥＭＣ）＝３／４／３（体積比）の混合溶液を溶媒とし、電解質としてリチウム塩であるＬｉＰＦ６を１ｍｏｌ／Ｌの濃度で溶解して、非水電界液を調製した。 <Nonaqueous electrolyte>
A mixed solution of ethylene carbonate (EC) / dimethyl carbonate (DMC) / ethyl methyl carbonate (EMC) = 3/4/3 (volume ratio) is used as a solvent, and LiPF 6 which is a lithium salt is used as an electrolyte at a concentration of 1 mol / L. It melt | dissolved and the nonaqueous electric field liquid was prepared.

＜リチウムイオン二次電池の製造＞
上記の正極と負極と耐熱性多孔質層と非水電解液と角型の缶ケースとを用い、公知方法により、容量２５Ａｈでエネルギー密度２５０ｋＷｈ/ｍ３のリチウムイオン二次電池を製造した。 <Manufacture of lithium ion secondary batteries>
A lithium ion secondary battery having a capacity of 25 Ah and an energy density of 250 kWh / m 3 was manufactured by a known method using the positive electrode, the negative electrode, the heat-resistant porous layer, the non-aqueous electrolyte, and the rectangular can case.

＜釘刺し試験＞
各例において得られたリチウムイオン二次電池について、釘刺し試験を実施した。
得られたリチウムイオン二次電池を４．１Ｖまでフル充電した後、３５℃の恒温槽内にて３時間保持した。その後、リチウムイオン二次電池を恒温槽外に取り出し、２０ｍｍ／ｓｅｃの速度にて電池側方から外径６ｍｍφの釘刺しを実施した。 <Nail penetration test>
A nail penetration test was performed on the lithium ion secondary batteries obtained in each example.
The obtained lithium ion secondary battery was fully charged to 4.1 V, and then held in a thermostatic bath at 35 ° C. for 3 hours. Thereafter, the lithium ion secondary battery was taken out of the thermostatic chamber, and nail piercing with an outer diameter of 6 mmφ was performed from the side of the battery at a speed of 20 mm / sec.

プラス外部端子とマイナス外部端子を電圧計に接続し、電圧変化を測定した。
釘刺し部分の温度と缶表面温度の経時変化を測定した。
また、発煙蒸気量を目視にて評価した。発煙蒸気量は、金属水酸化物及び／又は金属酸化物の水和物からなる第１の絶縁性無機フィラーの脱水反応により生成される水蒸気量に相関する。脱水反応により生成される水蒸気量が多ければ、発煙蒸気量は多くなる。 The positive external terminal and the negative external terminal were connected to a voltmeter, and the voltage change was measured.
Changes in the nail penetration temperature and the can surface temperature over time were measured.
Further, the amount of fuming vapor was visually evaluated. The amount of fuming vapor correlates with the amount of water vapor generated by the dehydration reaction of the first insulating inorganic filler made of metal hydroxide and / or metal oxide hydrate. If the amount of water vapor generated by the dehydration reaction is large, the amount of fuming vapor increases.

結果を、図４〜図７及び表１に示す。
図４は、実施例１の釘刺し試験の結果を示すグラフである。
図５は、実施例３の釘刺し試験の結果を示すグラフである。
図６は、比較例１の釘刺し試験の結果を示すグラフである。
図７は、比較例２の釘刺し試験の結果を示すグラフである。
表中の電池内部の釘刺し部分の温度と缶表面温度は、最高到達温度である。
実施例１と実施例２の釘刺し試験の結果を示すグラフは同様の傾向であったので、実施例２については、釘刺し試験の結果を示すグラフを省略した。 The results are shown in FIGS. 4 to 7 and Table 1.
FIG. 4 is a graph showing the results of the nail penetration test of Example 1.
FIG. 5 is a graph showing the results of the nail penetration test of Example 3.
FIG. 6 is a graph showing the results of the nail penetration test of Comparative Example 1.
FIG. 7 is a graph showing the results of the nail penetration test of Comparative Example 2.
In the table, the temperature of the nail penetration inside the battery and the surface temperature of the can are maximum temperatures.
Since the graphs showing the results of the nail penetration test of Example 1 and Example 2 had the same tendency, the graphs showing the results of the nail penetration test were omitted for Example 2.

耐熱性多孔質層の絶縁性無機フィラーとして酸化アルミニウム水和物と窒化ホウ素（ＢＮ）又は炭化珪素（ＳｉＣ）とを用いた実施例１〜３では、比較例１、２に比して、釘刺し部分と缶表面のいずれについても、釘刺し直後の温度上昇自体が抑制され、かつ、その後も良好な温度降下が見られた。
特に、酸化アルミニウム水和物と窒化ホウ素又は炭化珪素（ＳｉＣ）との配合比を７０：３０、又は６０：４０とした実施例１、２では、釘刺し部分と缶表面のいずれについても、釘刺し直後の温度上昇が効果的に抑制され、かつ、その後の温度降下も顕著であった。
実施例１〜３では、酸化アルミニウム水和物の脱水反応による吸熱反応と、熱伝導性の高い窒化ホウ素又は炭化珪素による熱拡散が良好に起こり、電池全体の温度上昇が抑制され、良好な温度降下が得られたと考えられる。 In Examples 1 to 3 using aluminum oxide hydrate and boron nitride (BN) or silicon carbide (SiC) as the insulating inorganic filler of the heat-resistant porous layer, compared with Comparative Examples 1 and 2, the nail For both the pierced portion and the can surface, the temperature increase immediately after the nail puncture was suppressed, and a good temperature decrease was observed thereafter.
In particular, in Examples 1 and 2 in which the blending ratio of aluminum oxide hydrate to boron nitride or silicon carbide (SiC) was set to 70:30 or 60:40, both the nail piercing portion and the can surface had a nail. The temperature increase immediately after the stab was effectively suppressed, and the subsequent temperature decrease was also remarkable.
In Examples 1 to 3, the endothermic reaction due to the dehydration reaction of aluminum oxide hydrate and the thermal diffusion due to boron nitride or silicon carbide having high thermal conductivity occur favorably, the temperature rise of the entire battery is suppressed, and the good temperature It is thought that a descent was obtained.

これに対して、耐熱性多孔質層の絶縁性無機フィラーとして窒化ホウ素のみを用いた比較例１では、釘刺し直後から、釘刺し部分と缶表面の温度差は小さく、窒化ホウ素によって熱拡散が良好に拡散されたことが確認された。しかしながら、比較例１では、金属水酸化物及び／又は金属酸化物の水和物からなる第１の絶縁性無機フィラーを用いていないので、脱水反応による吸熱反応が起こらず、釘刺し部分と缶表面の温度上昇は大きかった。   On the other hand, in Comparative Example 1 using only boron nitride as the insulating inorganic filler of the heat-resistant porous layer, the temperature difference between the nail penetration portion and the can surface is small immediately after nail penetration, and thermal diffusion is caused by boron nitride. It was confirmed that it was diffused well. However, in Comparative Example 1, since the first insulating inorganic filler made of metal hydroxide and / or metal oxide hydrate is not used, the endothermic reaction due to dehydration does not occur, and the nail piercing portion and the can The temperature rise on the surface was large.

耐熱性多孔質層の絶縁性無機フィラーとして酸化アルミニウム水和物のみを用いた比較例２では、熱伝導率の高い第２の絶縁性無機フィラーを用いていないので、熱拡散が進まず、釘刺し部分と缶表面の温度差は大きくなった。そのため、釘刺し直後の缶表面の温度上昇は抑制されたが、その分、釘刺し部分に熱がこもり、釘刺し部分の温度上昇が大きくなった。
比較例２では、酸化アルミニウム水和物の脱水反応による吸熱反応が生じるので、比較例１に比べると、釘刺し部分の温度上昇は多少抑制されたが、釘刺し部分の温度上昇が脱水反応による吸熱反応では吸熱しきれず、釘刺し部分の温度上昇を良好に抑制することができなかった。そのため、釘刺し部分は、釘刺し直後の温度上昇が大きく、かつその後の温度降下が小さく、高い温度状態が持続した。
また、釘刺し直後の缶表面の温度上昇は抑制されたものの、時間の経過と共に徐々に釘刺し部分の周囲に熱が拡散するため、釘刺し部分に近い温度になるまで缶表面の温度は上昇を続けた。 In Comparative Example 2 in which only aluminum oxide hydrate was used as the insulating inorganic filler of the heat resistant porous layer, the second insulating inorganic filler having high thermal conductivity was not used. The temperature difference between the stab and the can surface increased. For this reason, the temperature rise on the can surface immediately after nail penetration was suppressed, but heat was accumulated in the nail penetration portion, and the temperature increase in the nail penetration portion was increased accordingly.
In Comparative Example 2, an endothermic reaction occurs due to the dehydration reaction of aluminum oxide hydrate. Therefore, compared with Comparative Example 1, the temperature increase in the nail piercing portion was somewhat suppressed, but the temperature increase in the nail piercing portion was due to the dehydration reaction. In the endothermic reaction, the endotherm could not be absorbed and the temperature rise at the nail penetration could not be suppressed well. Therefore, the temperature of the nail piercing portion was large immediately after the nail piercing and the temperature drop thereafter was small, and the high temperature state was maintained.
In addition, although the temperature rise on the can surface immediately after nail penetration was suppressed, the heat gradually spreads around the nail penetration portion over time, so the temperature on the can surface increased until the temperature was close to the nail penetration portion. Continued.

Figure 0005834940
Figure 0005834940

本発明の耐熱性多孔質層は、プラグインハイブリッド車（ＰＨＶ）あるいは電気自動車（ＥＶ）に搭載されるリチウムイオン二次電池等の非水電解質二次電池に好ましく適用できる。   The heat-resistant porous layer of the present invention can be preferably applied to a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery mounted on a plug-in hybrid vehicle (PHV) or an electric vehicle (EV).

１ 非水電解質二次電池
１１ ケース
１２ 端子
２０ 積層体
２１ 正極
２２ 負極
２３ 樹脂製セパレータ
２４ 耐熱性多孔質層（ＨＲＬ層）
２５ セパレータ
３０ 釘 DESCRIPTION OF SYMBOLS 1 Nonaqueous electrolyte secondary battery 11 Case 12 Terminal 20 Laminate 21 Positive electrode 22 Negative electrode 23 Resin separator 24 Heat resistant porous layer (HRL layer)
25 Separator 30 Nail

Claims (8)

多孔質の樹脂製セパレータと、当該樹脂製セパレータ上に形成された、絶縁性無機フィラーを含む耐熱性多孔質層とを含む非水電解質二次電池用のセパレータであって、
前記耐熱性多孔質層は、前記絶縁性無機フィラーとして、金属水酸化物及び／又は金属酸化物の水和物からなる第１の絶縁性無機フィラーと、熱伝導率が１００Ｗ／ｍ・Ｋ以上である第２の絶縁性無機フィラーとを含む非水電解質二次電池用のセパレータ。 A separator for a non-aqueous electrolyte secondary battery comprising a porous resin separator and a heat-resistant porous layer containing an insulating inorganic filler formed on the resin separator,
The heat-resistant porous layer has, as the insulating inorganic filler, a first insulating inorganic filler made of a metal hydroxide and / or a hydrate of metal oxide, and a thermal conductivity of 100 W / m · K or more. The separator for nonaqueous electrolyte secondary batteries containing the 2nd insulating inorganic filler which is. 前記第１の絶縁性無機フィラーは、２００〜５００℃の温度範囲において吸熱反応を起こす材料からなる請求項１に記載の非水電解質二次電池用のセパレータ。   The separator for a non-aqueous electrolyte secondary battery according to claim 1, wherein the first insulating inorganic filler is made of a material that causes an endothermic reaction in a temperature range of 200 to 500 ° C. 前記第１の絶縁性無機フィラーは、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム水和物、及び酸化マグネシウム水和物からなる群より選ばれた少なくとも１種である請求項１又は２に記載の非水電解質二次電池用のセパレータ。   The first insulating inorganic filler is at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, aluminum oxide hydrate, and magnesium oxide hydrate. Separator for non-aqueous electrolyte secondary battery. 前記第２の絶縁性無機フィラーは、窒化ホウ素（ＢＮ）、窒化アルミニウム（ＡｌＮ）、及びダイヤモンドからなる群より選ばれた少なくとも１種である請求項１〜３のいずれかに記載の非水電解質二次電池用のセパレータ。 The nonaqueous electrolyte according to any one of claims 1 to 3, wherein the second insulating inorganic filler is at least one selected from the group consisting of boron nitride (BN), aluminum nitride (AlN), and diamond. Separator for secondary battery. すべての前記絶縁性無機フィラーの合計１００質量部に対して、前記第１の絶縁性無機フィラーと前記第２の絶縁性無機フィラーとの合計量が１０〜１００質量部である請求項１〜４のいずれかに記載の非水電解質二次電池用のセパレータ。 Per 100 parts by weight of all of the insulating inorganic filler, according to claim 1-4 total amount of the second insulating inorganic filler and the first insulating inorganic filler is 10 to 100 parts by weight A separator for a non-aqueous electrolyte secondary battery according to any one of the above. 前記第１の絶縁性無機フィラーと前記第２の絶縁性無機フィラーとの合計１００質量部に対して、前記第１の絶縁性無機フィラーの量が５０〜８０質量部である請求項１〜５のいずれかに記載の非水電解質二次電池用のセパレータ。 Per 100 parts by weight of the said first insulating inorganic filler second insulating inorganic filler, according to claim 1-5 the amount of the first insulating inorganic filler is 50 to 80 parts by weight A separator for a non-aqueous electrolyte secondary battery according to any one of the above. 正極と、負極と、請求項１〜６のいずれかに記載の非水電解質二次電池用のセパレータとを備えた非水電解質二次電池。 A nonaqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a separator for a nonaqueous electrolyte secondary battery according to any one of claims 1 to 6 . リチウムイオン二次電池である請求項７に記載の非水電解質二次電池。 The nonaqueous electrolyte secondary battery according to claim 7 , which is a lithium ion secondary battery.
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