JP6386840B2 - 非水電解質二次電池および電池パック - Google Patents
非水電解質二次電池および電池パック Download PDFInfo
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Description
第1実施形態によれば、外装部材と、外装部材内に収納される負極と、外装部材内に収納される正極と、外装部材内に収納され、正極及び負極の間に配置されるセパレータと、外装部材内に収納される非水電解液とを含む非水電解質二次電池が提供される。
負極103は、負極集電体103a及び負極材料層103b(負極活物質含有層)を含む。負極材料層103bは、集電体103aの片面若しくは両面に形成され、活物質と、任意に導電剤及び結着剤を含む。
正極105は、正極集電体105a及び正極材料層105b(正極活物質含有層)を含む。正極材料層105bは、集電体105aの片面若しくは両面に形成され、活物質と、任意に導電剤及び結着剤を含む。
また、イオウ(S)又はフッ化カーボンも活物質として使用できる。
電解液は、例えば、電解質を有機溶媒に溶解することにより調製される液状非水電解質、又は、液状電解質と高分子材料を複合化したゲル状非水電解質であってよい。
実施の形態によれば、非水電解質二次電池用として用いられる電解液中の鎖状カーボネートの−20℃における自己拡散係数が1.4×10−10m2/sec以上2.0×10−10m2/secの範囲にある。
式中のDは拡散係数であり、GはPFG強度であり、Δは拡散時間であり、δはPFG印加時間であり、γは磁気回転比であり、Eはシグナルエコー強度であり、E0はGが最小の時のシグナルエコー強度である。式は、底がネイピア数eである指数関数である。
ln(E/E0)=−A×G2×D
と表すことができる。従って、PFG強度を変化させ、ピーク強度を観察し、上記式のプロットの傾きから拡散係数を算出することができる。式は、底がネイピア数eである対数関数である。以上の測定方法の詳細は、日本ゴム協会誌、第76巻、第9号、324p(2003)とJ.Phys.Chem. B, 103, 519 (1999)に記載されている。
セパレータ104は、例えば、ポリエチレン、ポリプロピレン、セルロース、またはポリフッ化ビニリデン(PVdF)を含む多孔質フィルム、または、合成樹脂製不織布から形成されてよい。中でも、ポリエチレン又はポリプロピレンから形成された多孔質フィルムは、一定温度において溶融し、電流を遮断することが可能であるため、安全性を向上できるセパレータ104である。
外装部材には、ラミネートフィルム製容器または金属製容器を用いることができる。ラミネートフィルムの厚さは0.5mm以下であることが好ましく、より好ましくは0.2mm以下である。金属製容器は、厚さ1mm以下であることが好ましく、より好ましい範囲は0.5mm以下であり、さらに好ましい範囲は0.2mm以下である。
第2実施形態に係る電池パックは、第1実施形態の非水電解質二次電池(単電池)を1個または複数有する。複数の単電池を備える場合、各単電池は電気的に直列もしくは並列に接続されている。第2実施形態に係る電池パックは、第1実施形態の非水電解質二次電池を電池用のセルとして用いる。
この場合、組電池の両側面に保護シートを配置し、熱収縮チューブを周回させた後、熱収縮チューブを熱収縮させて組電池を結束させる。
(実施例)
(実施例1)
(負極の作製)
負極活物質として粉末のスピネル型チタン酸リチウム(Li4Ti5O12)を85質量部と、導電剤としてアセチレンブラック10質量部と、結着剤としてPVdFを5質量部とを混合した負極合剤をNMPに加え、厚さ15μmのアルミ箔からなる集電体に塗布し、乾燥した。その後、プレス処理をして負極を作製した。
正極活物質として粉末の層状岩塩型コバルト酸リチウム(LiCoO2)を85質量部と、導電剤としてグラファイト5質量部とアセチレンブラック5質量部と、結着剤としてPVdFを5質量部とを混合した正極合剤をNMPに加え、厚さ15μmのアルミ箔からなる集電体に塗布し、乾燥した。その後、プレス処理をして正極を作製した。
作製した正極と負極を、セパレータを介して積層した。この積層物を、負極が外周側になるように渦巻き状に巻いて電極群を作製した。
セパレータとして、ポリエチレン製多孔質フィルム及びセルロースからなるセパレータを用いた。セパレータ中央部の厚さを1cm間隔で測定した厚さの平均値は12μmであった。内部に空孔として最大直径が30μmの孔径を持つものを使用した。
エチレンカーボネート(EC)とエチルメチルカーボネート(EMC)又はジエチルカーボネート(DEC)を体積比で1:2の割合で混合した混合溶媒に六フッ化リン酸リチウムを1.0mol/L溶解して非水電解溶液を調製した。調整した非水電解液溶液に、リチウムビス(オキサラト)ホウ酸(LiBOB)を電解液重量に対し1質量%となるよう混合した。
電解液中のEMC及びDEC(鎖状カーボネート)の拡散係数を以下の方法によって測定した。アルゴンガスで置換されたグローブボックス内で電池を解体し、電解液を取り出した。得られた電解液を100μL採取し、日本電子社製ECA−400のミクロ管に導入し、1H−NMR測定を行った。試料部を−20℃になるまで冷却し、2時間保持した後、測定を行った。得られたスペクトルの化学シフト値から、EMC又はDECのピークを特定した。続いて、PFGの印加時間を4.0msec、拡散時間を200msecとし、PFG強度を0.02T/m以上0.3T/m以下の範囲で20点変えて測定しピーク減衰強度の変化を求めた。得られたプロットの傾きから、溶媒成分の自己拡散係数を算出した。得られた溶媒の自己拡散係数は1.8×10−10m2secであった。
実施例2〜16及び比較例1〜6は、表1と表2に示す条件で実施例1と同様に電極群、非水電解質二次電池の作製、自己拡散係数の評価、正極及び負極塗布量の調整を行った。
実施例1〜16及び比較例1〜6の電池を用いて充放電試験を行い、初回充放電容量を測定した。充放電は、25℃の恒温槽内で、1000mAの電流値で1.5V〜3Vの範囲で行った。
実施例1〜16及び比較例1〜6の電池を用いてレート抵抗の測定を行なった。電池を1000mAで充電後に放電を5000mAの電流値で行い、放電容量を測定した。1000mAにおける放電容量に対する比率をレート特性として算出した。
実施例1〜16及び比較例1〜6の電池を用いて低温抵抗の測定を行なった。電池を充電後に−20℃の恒温槽内に2時間設置し、電池の温度を調整した。放電を1000mAの電流値で行い、−20℃の放電容量を測定した。25℃における放電容量に対する比率を低温特性として算出した。
実施例1〜16及び比較例1〜6の電池を用いて、60℃の高温環境下で電極劣化の加速試験を行った。100サイクル繰り返し充放電を行い(充電/放電で1サイクルとする)、放電容量維持率を調べた。充放電は、正負極間の電圧が1.5V〜3.0Vの電位範囲で、放電電流値1000mAの条件で行った。容量維持率は、1000mAでの初回放電容量を基準として算出した。
実施例1〜16及び比較例1〜6の電池に対して行った上記の特性評価の結果を表3に示す。
Claims (8)
- 外装部材と、
前記外装部材内に収納されるチタン含有酸化物を含む負極と、
前記外装部材内に収納される正極と、
前記外装部材内に収納され、前記正極及び負極の間に配置されるセパレータと、
前記外装部材内に収納される非水電解液とを含む非水電解質二次電池であって、
前記非水電解液の溶媒に少なくとも一種類以上の鎖状カーボネート類を含み、
前記鎖状カーボネートの−20℃における自己拡散係数が1.4×10−10m2/sec以上2.0×10−10m2/sec以下であり、
前記セパレータが10μm以上100μm以下の直径を有する空孔を含んでいる非水電解質二次電池。 - 前記非水電解液は、LiBF 4 、LiBOB、LiH 2 PO 3 ,Li 2 HPO 3 ,Li 2 PO 2 ,LiPO 2 F 2 、LiFSI、LiTFSI、LiClO 4 及びLiAsF 6 からなる群より選ばれる1種以上及びLiPF 6 を含む電解質を含む請求項1に記載の非水電解質二次電池。
- 前記セパレータの厚さが2μm以上30μm以下である請求項1又は2に記載の非水電解質二次電池。
- 前記セパレータの厚さが3μm以上15μm以下である請求項1乃至3のいずれか1項に記載の非水電解質二次電池。
- 前記非水電解質二次電池の−20℃における1kHzの交流電圧印加時の抵抗大きさをRsol、0.1Hzの交流電圧印加時の抵抗大きさをRctとするとき、Rsol<20Ω・cm2およびRct<120Ω・cm2を満たす請求項1乃至4のいずれか1項に記載の非水電解質二次電池。
- 前記非水電解質二次電池の−20℃における1kHzの交流電圧印加時の抵抗大きさをRsol、0.1Hzの交流電圧印加時の抵抗大きさをRctとするとき、Rsol/Rct>0.16を満たす請求項1乃至5のいずれか1項に記載の非水電解質二次電池。
- 前記非水電解質二次電池の−20℃における1kHzの交流電圧印加時の抵抗大きさをRsol、0.1Hzの交流電圧印加時の抵抗大きさをRctとするとき、0.3>Rsol/Rct>0.16を満たす請求項1乃至6のいずれか1項に記載の非水電解質二次電池。
- 請求項1乃至7のいずれか1項に記載の非水電解質二次電池をセルとして用いた電池パック。
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