JP6521883B2 - 非水電解液電池、およびその製造方法 - Google Patents
非水電解液電池、およびその製造方法 Download PDFInfo
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- JP6521883B2 JP6521883B2 JP2016029931A JP2016029931A JP6521883B2 JP 6521883 B2 JP6521883 B2 JP 6521883B2 JP 2016029931 A JP2016029931 A JP 2016029931A JP 2016029931 A JP2016029931 A JP 2016029931A JP 6521883 B2 JP6521883 B2 JP 6521883B2
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- aqueous electrolyte
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- metal
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Classifications
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Description
負極活物質にLi−Al合金を使用する電池では、Li箔(特に断らない限り、Li合金箔を含む。以下同じ。)とAl箔(特に断らない限り、Al合金箔を含む。以下同じ。)とを貼り合わせて電池内に導入し、非水電解液の共存下でLiとAlとを反応させてLi−Al合金を形成させることが行われている。ところが、更に集電体となる金属箔〔Cu(銅)箔やCu合金箔など〕を、Li箔とAl箔との積層体に単に重ねただけで電池内に挿入すると、貯蔵後(特に高温環境下での貯蔵後)に電池の内部抵抗が増大して、貯蔵特性が十分に向上しない。
前記態様(1)の検討過程において、前記金属基材層が、Ni、TiおよびFeより選択される金属またはその合金で構成されている場合には、Li−Al合金が形成される際の体積変化による負極の変形を抑制する効果が高くなるため、金属基材層の両面にAl金属層を接合する場合だけでなく、金属基材層の片面のみにAl金属層の接合およびLi−Al合金の形成を行う場合であっても、電池の特性劣化を充分に抑制することが可能となることを見出し、非水電解液電池の態様(2)を完成するに至った。
実施例1
厚さ30μmのCu箔(引っ張り強さ:220N/mm2、体積固有抵抗:2×10−6Ω・cm)の両面に、それぞれ、厚さ30μmのAl箔を積層した25mm×40mmの大きさのクラッド材(積層金属箔)を負極前駆体として用いた。前記クラッド材の端部に、集電用のCu箔を超音波溶接し、更にそのCu箔の端部に、電池外部との導電接続のためのNiタブを超音波溶接したものを電池の組み立てに用いた。
mmの大きさに切断し、前記Al箔が露出する箇所に、電池外部との導電接続のためのAlタブを超音波溶接することにより、集電体の片面に20mm×30mmの大きさの正極合剤層を有する正極を作製した。
厚さ30μmのNi箔(引っ張り強さ:490N/mm2、体積固有抵抗:6.8×10−6Ω・cm)の両面に、それぞれ、厚さ30μmのAl箔を積層した25mm×40mmの大きさのクラッド材(積層金属箔)を負極前駆体として用いた以外は、実施例1と同様にして、定格容量30mAhの非水電解液電池を作製した。
厚さ30μmのCu箔の片面に、厚さ30μmのAl箔を積層した25mm×40mmの大きさのクラッド材(積層金属箔)を負極前駆体として用いた。前記クラッド材の端部に、集電用のCu箔を超音波溶接し、更にそのCu箔の端部に、電池外部との導電接続のためのNiタブを超音波溶接したものを電池の組み立てに用いた。
実施例1、2および比較例1の各電池について、定電流(6mA)−定電圧(4.0V)充電を行い、充電電流が0.3mAまで低下した時点で充電を終止し、電池を満充電状態とした。次いで、それぞれの電池をアルゴンガス雰囲気中で分解して負極を取り出し、その変形の程度を目視で確認した。なお、いずれの負極についても、クラッド材を構成するAl箔の正極合剤層と対向する部分にLi−Al合金が形成されており、周縁部の正極合剤層と対向していない部分は、Liと反応せずAlのままの状態で存在していた。
きく湾曲している様子が認められた。
実施例1、2および比較例1の各電池について、定電流(6mA)−定電圧(4.0V)充電を行い、充電電流が0.3mAまで低下した時点で充電を終止した。次いで、6mAの定電流で放電(放電終止電圧:2V)させて放電容量(初期放電容量)を測定し、更に、前記充電条件で充電を行って電池を満充電状態とした。いずれの電池も初期放電容量は30mAhであった。
実施例1、2および比較例1の各電池について、定電流(15mA)−定電圧(4.0V)充電(ただし、充電電流が1.5mAまで低下した時点で充電を終止)、および、30mAの電流値で24分間の放電(放電容量:12mAh)による充放電サイクルを繰り返した。放電終了時の電池電圧が2Vより低くなるまでのサイクル数により、各電池の充放電サイクル特性を評価した。
厚さ30μmのCu箔の片面に、厚さ100μmのAl箔を積層したクラッド材(積層金属箔)のAl層の表面に、厚さ50μmのLi箔を重ね、これを円形に打ち抜いて負極用の積層体とした。
00によって封止されている。
厚さ100μmのAl箔の片面に、厚さ50μmのLi箔を重ね、これを円形に打ち抜き、更に厚さ30μmの円形のCu箔と重ね合わせて負極用の積層体とした以外は比較例2と同様にして、2016コイン形セルを作製した。
実施例3
実施例1の非水電解液電池と充放電装置とを組み合わせることにより、非水電解液電池システムを構成した。
実施例1のクラッド材について、Al箔の厚さを10μmとした以外は、実施例と同様にして電極体を作製し、更に、この電極体を用いた以外は、実施例1と同様にして非水電解液電池を作製した。
実施例1のクラッド材について、Al箔の厚さを100μmとした以外は、実施例1と同様にして電極体を作製し、更に、この電極体を用いた以外は、実施例1と同様にして非水電解液電池を作製した。
100 負極、負極前駆体(負極用積層体)
101 積層金属箔
101a 金属基材層
101b Al金属層
102 Li箔
103 Al活性層
200 正極
300 セパレータ
400 正極缶
500 負極缶
600 樹脂製のパッキング
700 ラミネートフィルム外装体
Claims (9)
- 正極と負極とがセパレータを介して重ねられた平板状の電極体と、非水電解液とを有する非水電解液電池であって、
前記負極は、Liと合金化しない金属基材層と、前記金属基材層に接合されたAl活性層とを含有する積層体を有し、
前記Al活性層の少なくとも表面側には、Li−Al合金が形成されており、
前記金属基材層は、Ni、TiおよびFeより選択される金属またはその合金で構成されており、
前記Al活性層は、前記金属基材層の片面にAl金属層が接合された積層金属箔における前記Al金属層がLiと反応して形成されたものであり、
前記積層金属箔は、前記金属基材層の厚みを100としたときの前記Al金属層の厚みが、10以上200未満であることを特徴とする非水電解液電池。 - 前記金属基材層は、体積固有抵抗が80×10−6Ω・cm以下の材料で構成されている請求項1に記載の非水電解液電池。
- 前記Al活性層の面積が、10cm2以上である請求項1または2に記載の非水電解液電池。
- 前記金属基材層の厚みが、10〜50μmである請求項1〜3のいずれかに記載の非水電解液電池。
- 前記正極は、正極活物質としてリチウム含有複合酸化物を含有している請求項1〜4のいずれかに記載の非水電解液電池。
- 正極と負極とがセパレータを介して重ねられた平板状の電極体と、非水電解液とを有する非水電解液電池の製造方法であって、
Ni、TiおよびFeより選択される金属またはその合金で構成された金属基材層の片面にAl金属層が接合された積層金属箔を用い、
前記積層金属箔において、前記金属基材層の厚みを100としたときの前記Al金属層の厚みを、10以上200未満とし、
前記Al金属層の少なくとも表面側にLi−Al合金を形成してAl活性層とすることを特徴とする非水電解液電池の製造方法。 - 前記積層金属箔がクラッド材である請求項6に記載の非水電解液電池の製造方法。
- 前記積層金属箔の金属基材層の厚みが、10〜50μmである請求項6または7に記載の非水電解液電池の製造方法。
- 前記積層金属箔のAl金属層の厚みが、10〜150μmである請求項6〜8のいずれかに記載の非水電解液電池の製造方法。
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