JP2008262785A - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
- Publication number
- JP2008262785A JP2008262785A JP2007103972A JP2007103972A JP2008262785A JP 2008262785 A JP2008262785 A JP 2008262785A JP 2007103972 A JP2007103972 A JP 2007103972A JP 2007103972 A JP2007103972 A JP 2007103972A JP 2008262785 A JP2008262785 A JP 2008262785A
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- Prior art keywords
- negative electrode
- positive electrode
- secondary battery
- lithium ion
- ion secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
【解決手段】リチウムイオン二次電池は、正極5と、負極6と、多孔質絶縁層7と、非水電解質溶液とを備えている。多孔質絶縁層7は、正極5と負極6との間に設けられており、シャットダウン特性を有しない材料を含んでいる。また、正極5には膨張部材53が設けられており、負極6には膨張部材63が設けられている。
【選択図】図2
Description
実施形態1では、非水電解質二次電池としてリチウムイオン二次電池を例に挙げ、その構成を示す。
実施形態2では、正極および負極の構成が上記実施形態1とは異なる。以下では、上記実施形態1との相違点を中心に説明する。
実施形態3では、正極および負極の構成が上記実施形態1とは異なる。以下では、上記実施形態1との相違点を中心に説明する。
図6は、本変形例における電極群39の構成を示す断面図である。
実施形態4では、多孔質絶縁層の構成が上記実施形態1とは異なる。以下では、上記実施形態1との相違点を中心に説明する。
本発明は、上記実施形態1から5において、以下に示す構成であってもよい。
1.リチウムイオン二次電池の作製方法
(実施例1)
(正極の作製)
まず、平均粒子径が2μmである膨張黒鉛(熱膨張材料)100重量部に、ポリアクリル酸誘導体(結着剤)を4重量部と、適量のN−メチル−2−ピロリドン(N-Methyl-2-Pyrrolidone,以下、「NMP」と記す)(分散媒)とを混合して、不揮発分30重量%のスラリーを調製した。ここでは、エムテクニック(株)製のメディアレス分散機「クレアミックス(商品名)」を用いて膨張黒鉛粒子とポリアクリル酸誘導体とNMPとの混合物を攪拌し、膨張黒鉛とポリアクリル酸誘導体とをNMPに均一になるまで分散させた。
まず、メソフェーズ小球体を2800℃の高温で黒鉛化したもの(以下メソフェーズ黒鉛と称す)を負極活物質として用意した。その後、双腕式練合機を用いて、メソフェーズ黒鉛100重量部と、日本ゼオン製のSBRアクリル酸変性体であるBM−400B(固形分40重量部)2.5重量と、カルボキシメチルセルロースを1重量部と、適量の水とを攪拌させ、負極ペーストを作製した。そして、負極ペーストを厚さが18μmであるCu箔製の集電体の両面に塗布し、乾燥させた後に、圧延した。これにより、厚みが0.02mmである負極を得た。
エチレンカーボネートとジメチルカーボネートとの体積比が1:3である混合溶媒に5wt%のビニレンカーボネートを添加させ、1.4mol/m3の濃度でLiPF6を溶解させた。これにより、非水電解質溶液が得られた。
まず、負極の表面にコーティングされたアルミナを正極と負極とで挟むように正極および負極を配置して捲回した。これにより、極板群が形成された。
なお、実施例1のリチウムイオン二次電池には、PTC(Positive Temperture Coefficient)サーミスタおよびCIDを取り付けなかった。
(実施例2)
負極表面ではなく正極表面にアルミナ層(多孔質絶縁層、厚み20μm)を形成したこと以外は実施例1と同様にして、実施例2のリチウムイオン二次電池を完成させた。
(実施例3)
多孔質絶縁層としてアルミナ層ではなくポリプロピレン製のセパレータ(厚み20μm)を用いたこと以外は実施例1と同様にして、実施例3のリチウムイオン二次電池を完成させた。
(実施例4)
多孔質絶縁層としてアルミナ層ではなくアラミド製のセパレータ(厚み20μm)を用いたこと以外は実施例1と同様にして、実施例4のリチウムイオン二次電池を完成させた。
(比較例1)
多孔質絶縁層としてアルミナ層ではなくポリエチレン製のセパレータ(厚み20μm)を用いたこと以外は実施例1と同様にして、比較例1のリチウムイオン二次電池を完成させた。
(比較例2)
正極集電体の表面に膨張黒鉛を点在させないこと以外は実施例1と同様にして、比較例2のリチウムイオン二次電池を完成させた。
(比較例3)
正極集電体の表面に膨張黒鉛を点在させないことと、多孔質絶縁層としてアルミナ層ではなくポリエチレン製のセパレータ(厚み20μm)を用いたこと以外は実施例1と同様にして、比較例3のリチウムイオン二次電池を完成させた。
2.リチウムイオン二次電池の評価方法
(釘刺し試験)
以上のようにして得られた実施例1〜4および比較例1〜3のリチウムイオン二次電池に対して釘刺し試験を行った。
1.45Aの一定電流で連続的に充電して、リチウムイオン二次電池の電極温度の変化とリチウムイオン二次電池の外観状態とを観察した。リチウムイオン二次電池に加えられる上限電圧を60Vとした。そして、リチウムイオン二次電池からの発煙が確認されなかった場合にはリチウムイオン二次電池の表面の最高温度を測定した。
3.結果と考察
得られた結果を表1に示す。釘刺し試験の結果を表1の発煙数に示し、過充電評価の結果を表1の過充電に示す。なお、表1の発煙数において、分母は試験を行ったリチウムイオン二次電池の個数であり、分子は発煙したリチウムイオン二次電池の個数である。また、過充電評価の結果では、温度は発煙しなかった場合の最高温度であり、「×」は発煙したことを示す。
2a 正極封口板
2b 負極封口板
3a 正極ガスケット
3b 負極ガスケット
5,15,25,35 正極
5a 正極リード
6,16,26,36 負極
6a 負極リード
7 多孔質絶縁層
8a 上部絶縁板
8b 下部絶縁板
9,19,29,39,49 電極群
51 正極集電体
52 正極合剤層
53 膨張部材
55 界面
61 負極集電体
62 負極合剤層
63 膨張部材
65 界面
71 金属化合物層
72 介在層
Claims (9)
- 正極と、負極と、前記正極と前記負極との間に保持された非水電解質溶液とを備え、
前記正極と前記負極との間には、シャットダウン特性を有していない材料を含む多孔質絶縁層が設けられており、
前記正極および前記負極の少なくとも一方の電極には、熱膨張材料を含む膨張部材が設けられている、非水電解質二次電池。 - 前記正極は、導電性の正極集電体と、前記正極集電体の表面に設けられリチウム複合酸化物を含む正極合剤層とを有し、
前記負極は、導電性の負極集電体と、前記負極集電体の表面に設けられリチウムイオンを電気化学的に吸蔵または放出可能な化合物を負極活物質として含む負極合剤層とを有し、
前記膨張部材は、前記正極集電体と前記正極合剤層との界面および前記負極集電体と前記負極合剤層との界面の少なくとも一方の界面に設けられている、請求項1に記載の非水電解質二次電池。 - 前記正極は、導電性の正極集電体と、前記正極集電体の表面に設けられリチウム複合酸化物を含む正極合剤層とを有し、
前記負極は、導電性の負極集電体と、前記負極集電体の表面に設けられリチウムイオンを電気化学的に吸蔵または放出可能な化合物を負極活物質として含む負極合剤層とを有し、
前記膨張部材は、前記正極合剤層および前記負極合剤層の少なくとも一方の合剤層内に設けられている、請求項1に記載の非水電解質二次電池。 - 前記シャットダウン特性を有しない材料は、金属化合物である、請求項1から3の何れか1つに記載の非水電解質二次電池。
- 前記多孔質絶縁層は、
前記金属化合物が含まれた金属化合物層と、
前記正極合剤層および前記負極合剤層の少なくとも一方の合剤層と前記金属化合物層との間に設けられた介在層と
を有している、請求項4に記載の非水電解質二次電池。 - 前記金属化合物は、マグネシア(MgO),シリカ(SiO2),アルミナ(Al2O3)およびジルコニア(ZrO2)のうちの少なくとも一種の金属酸化物である、請求項4または5に記載の非水電解質二次電池。
- 前記シャットダウン特性を有しない材料は、耐熱性高分子である、請求項1から6の何れか1つに記載の非水電解質二次電池。
- 前記多孔質絶縁層は、前記正極合剤層および前記負極合剤層の少なくとも一方の合剤層に接着されている、請求項1から7の何れか1つに記載の非水電解質二次電池。
- 前記熱膨張材料は、膨張黒鉛である、請求項1から8の何れか1つに記載の非水電解質二次電池。
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KR20080092281A (ko) | 2008-10-15 |
CN101286576A (zh) | 2008-10-15 |
US20080254355A1 (en) | 2008-10-16 |
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