JP2013080676A - 耐熱絶縁層付セパレータ - Google Patents
耐熱絶縁層付セパレータ Download PDFInfo
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- JP2013080676A JP2013080676A JP2011221243A JP2011221243A JP2013080676A JP 2013080676 A JP2013080676 A JP 2013080676A JP 2011221243 A JP2011221243 A JP 2011221243A JP 2011221243 A JP2011221243 A JP 2011221243A JP 2013080676 A JP2013080676 A JP 2013080676A
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- heat
- insulating layer
- resistant insulating
- separator
- resistant
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Abstract
Description
図1は、本発明の代表的な一実施形態である、平板積層型(扁平型)のリチウムイオン二次電池(以下、単に「積層型電池」ともいう)の全体構造を模式的に表した断面概略図である。
集電体11、12は導電性材料から構成される。集電体の大きさは、電池の使用用途に応じて決定される。例えば、高エネルギー密度が要求される大型の電池に用いられるのであれば、面積の大きな集電体が用いられる。本実施形態のリチウムイオン電池は、好ましくは大型の電池であり、用いられる集電体の大きさは、例えば長辺が100mm以上であり、好ましくは100mm×100mm以上であり、より好ましくは200mm×200mm以上である。集電体の厚さについても特に制限はない。集電体の厚さは、通常は1〜100μm程度である。集電体の形状についても特に制限されない。図1に示す積層型電池10では、集電箔のほか、網目形状(エキスパンドグリッド等)等を用いることができる。
活物質層13または15は活物質を含み、必要に応じてその他の添加剤をさらに含む。
電解質層17は、基材としての本実施形態のセパレータの面方向中央部に電解質が保持されてなる構成を有する。本実施形態のセパレータを用いることで、積層時の端部のカールの発生を抑制することができるため、信頼性の高い電池を安定的に製造することができる。
本実施形態では、セパレータとして、樹脂多孔質基体と、前記樹脂多孔質基体の少なくとも一方の面に形成された、耐熱粒子およびバインダを含む耐熱絶縁層と、を備え、前記耐熱粒子がαアルミナを含み、下記数式1で表されるパラメータXが0.018〜0.336である耐熱絶縁層付セパレータを用いることを特徴とする。
樹脂多孔質基体としては、例えば、上記電解液を吸収保持する有機樹脂を含む多孔性シート、織布または不織布を挙げることができる。好ましくは、前記多孔性シートは微多孔質のポリマーで構成される微多孔質膜である。このようなポリマーとしては、例えば、ポリエチレン(PE)、ポリプロピレン(PP)などのポリオレフィン;PP/PE/PPの3層構造をした積層体、ポリイミド、アラミドなどが挙げられる。特に、ポリオレフィン系微多孔質膜は、有機溶媒に対して化学的に安定であるという性質があり、電解液との反応性を低く抑えることができることから好ましい。
本実施形態では、耐熱絶縁層を構成する耐熱粒子の材質としては、融点または熱軟化点が150℃以上、好ましくは240℃以上である、耐熱性の高いものを用いる。このような耐熱性の高い材質を用いることで、電池内部温度が150℃近くに達してもセパレータの収縮を有効に防止することができる。その結果、電池の電極間ショートの誘発を防ぐことができるため、温度上昇による性能低下が起こりにくい電池が得られうる。
本実施形態のセパレータの製造方法は特に制限されないが、例えば、樹脂多孔質基体の両面に、融点または熱軟化点が150℃以上である耐熱粒子を含有する、スラリー状の耐熱絶縁層形成用組成物を塗布した後、乾燥する方法が用いられうる。
本実施形態のセパレータに染み込ませることのできる電解液としては、電解質として、LiClO4、LiAsF6、LiPF5、LiBOB、LiCF3SO3およびLi(CF3SO2)2の少なくとも1種類を用い、溶媒として、エチレンカーボネート(EC)、プロピレンカーボネート、ジエチルカーボネート(DEC)、ジメチルカーボネート、メチルエチルカーボネート、1,2−ジメトキシエタン、1,2−ジエトキシエタン、テトラヒドロフラン、1,3−ジオキソランおよびγ−ブチルラクトンよりなるエーテル類から少なくとも1種類を用い、前記電解質を前記溶媒に溶解させることにより、電解質の濃度が0.5〜2Mに調整されているものであるが、本発明はこれらに何ら制限されるべきものではない。
本発明のゲル電解質層では、本実施形態のセパレータにゲル電解質を含浸、塗布などにより保持させてなるものである。
電池外部に電流を取り出す目的で、集電板を用いてもよい。集電板は集電体やリードに電気的に接続され、電池外装材であるラミネートシートの外部に取り出される。
電池外装材29としては、公知の金属缶ケースを用いることができるほか、発電要素を覆うことができる、アルミニウムを含むラミネートフィルムを用いた袋状のケースが用いられうる。該ラミネートフィルムには、例えば、PP、アルミニウム、ナイロンをこの順に積層してなる3層構造のラミネートフィルム等を用いることができるが、これらに何ら制限されるものではない。高出力化や冷却性能に優れ、EV、HEV用の大型機器用電池に好適に利用することができるという観点から、ラミネートフィルムが望ましい。
きる。
図2は、平板積層型リチウムイオン二次電池の外観を表した斜視図である。
X線回析装置(マックサイエンス社製 MTP18VAHF、CuKα線、電圧:40kV、電流:200mA)を用いて耐熱絶縁層付セパレータの耐熱絶縁層のXRD測定を行い、前記耐熱絶縁層を構成する耐熱粒子全体に含まれるαアルミナのピーク面積の割合(Cα)を算出した。
耐熱絶縁層付セパレータの樹脂多孔質基体とは反対側の耐熱絶縁層の表面のレーザー顕微画像を、オリンパス社製 LEXT−OLS3000を用いて撮影し、下記数式3を用いて10点平均粗さ(Rzjis)を算出した。
最深の谷底から深い順に5番目までの谷深さ平均の和
Zpj:粗さ曲線で最高の山頂から高い順にj番目の山高さ
Zvj:粗さ曲線で最深の谷底から深い順にj番目の谷深さ
<実施例1>
耐熱粒子であるアルミナ粒子(Cα=0.07)95質量部とカルボキシメチルセルロース(ダイセル化学工業社製)5質量部とを適量の水に均一に分散させて分散液を得た。当該分散液を、樹脂多孔質基体であるポリエチレン(PE、膜厚 17.8μm)の片面にグラビアコーターを用いて塗布して塗膜を得た。当該塗膜を温風乾燥し、耐熱絶縁層の厚みが5.3μmおよび耐熱絶縁層の十点平均粗さが1.45μmである耐熱絶縁層付セパレータを作製した。
Cαが0.1であるアルミナ粒子を用いたことを除いては実施例1と同様に耐熱絶縁層付セパレータを作製した。
Cαが0.15であるアルミナ粒子を用いたことを除いては実施例1と同様に耐熱絶縁層付セパレータを作製した。
Cαが0.2であるアルミナ粒子を用いたことを除いては実施例1と同様に耐熱絶縁層付セパレータを作製した。
Cαが0.33であるアルミナ粒子を用い、耐熱絶縁層付セパレータの耐熱絶縁層の厚みを8.9μmおよび耐熱絶縁層の十点平均粗さを2.97μmとしたことを除いては実施例1と同様に耐熱絶縁層付セパレータを作製した。
Cαが0.43であるアルミナ粒子を用いたことを除いては実施例1と同様に耐熱絶縁層付セパレータを作製した。
Cαが0.68であるアルミナ粒子を用いたことおよび耐熱絶縁層付セパレータの耐熱絶縁層の十点平均粗さを1.46μmとしたことを除いては実施例1と同様に耐熱絶縁層付セパレータを作製した。
Cαが1であるアルミナ粒子を用い、耐熱絶縁層付セパレータの耐熱絶縁層の厚みを7.9μmおよび耐熱絶縁層の十点平均粗さを1.38μmとしたことを除いては実施例1と同様に耐熱絶縁層付セパレータを作製した。
耐熱絶縁層付セパレータの耐熱絶縁層の厚みを5.3μmおよび耐熱絶縁層の十点平均粗さを1.325μmとしたことを除いては実施例8と同様に耐熱絶縁層付セパレータを作製した。
耐熱絶縁層付セパレータの耐熱絶縁層の十点平均粗さを1.58μmとしたことを除いては実施例9と同様に耐熱絶縁層付セパレータを作製した。
耐熱絶縁層付セパレータの耐熱絶縁層の厚みを4.8μmおよび耐熱絶縁層の十点平均粗さを1.48μmとしたことを除いては実施例8と同様に耐熱絶縁層付セパレータを作製した。
耐熱絶縁層付セパレータの耐熱絶縁層の十点平均粗さを1.7μmとしたことを除いては実施例9と同様に耐熱絶縁層付セパレータを作製した。
耐熱絶縁層付セパレータの耐熱絶縁層の十点平均粗さを1.749μmとしたことを除いては実施例9と同様に耐熱絶縁層付セパレータを作製した。
Cαが0.04であるアルミナ粒子を用い、耐熱絶縁層付セパレータの耐熱絶縁層の十点平均粗さを1.95μmとしたことを除いては実施例1と同様に耐熱絶縁層付セパレータを作製した。
耐熱絶縁層付セパレータの耐熱絶縁層の十点平均粗さを1.79μmとしたことを除いては実施例9と同様に耐熱絶縁層付セパレータを作製した。
耐熱絶縁層付セパレータの評価として、180°剥離試験を以下のように行った。結果を表1に示す。
実施例1〜13および比較例1または2において作製した耐熱絶縁層付セパレータの耐熱絶縁層側面をセロハンテープ(ニチバン社製)で補強し、10mm幅で約150mm長さに裁断した。当該耐熱絶縁層付セパレータを両面テープ(ニチバン社製)により金属土台に貼り付け固定した。その後、前記耐熱絶縁層側面のセロハンテープを10mm剥がし、測定器(STA−1150;ORIENTEC社製)に取り付けた。引張速度100mm/min、剥離距離80mmの条件で、80mm分の前記耐熱絶縁層を剥がし、剥離強度を測定した。
実施例1〜13は、いずれもパラメータXが0.018〜0.336の範囲内にあり、耐熱絶縁層の剥離強度は30mN/mmより大きく、耐熱絶縁層の耐熱粒子の粉落ちはみられなかった。いずれの実施例においても、耐熱粒子全体に含まれるαアルミナのXRDにおける割合、すなわち、Cαは0.06よりも大きかった。
11 正極集電体、
12 負極集電体、
13 正極活物質層、
15 負極活物質層、
17 電解質層、
19 単電池層、
21 発電要素、
25 正極集電板、
27 負極集電板、
29 電池外装材(ラミネートフィルム)。
Claims (6)
- 前記パラメータXが0.04〜0.33であることを特徴とする、請求項1に記載の耐熱絶縁層付セパレータ。
- 前記パラメータXが0.07〜0.30であることを特徴とする、請求項1または2に記載の耐熱絶縁層付セパレータ。
- 前記Cαが0.06以上であることを特徴とする、請求項1〜3のいずれか1項に記載の耐熱絶縁層付セパレータ
- 請求項1〜5のいずれか1項に記載の耐熱絶縁層付セパレータが、正極および負極の間に介在してなることを特徴とする、電気デバイス。
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