JP2013197100A - リチウム2次電池用セパレータ、2次電池、および2次電池の製造方法 - Google Patents
リチウム2次電池用セパレータ、2次電池、および2次電池の製造方法 Download PDFInfo
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- JP2013197100A JP2013197100A JP2013053432A JP2013053432A JP2013197100A JP 2013197100 A JP2013197100 A JP 2013197100A JP 2013053432 A JP2013053432 A JP 2013053432A JP 2013053432 A JP2013053432 A JP 2013053432A JP 2013197100 A JP2013197100 A JP 2013197100A
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Abstract
【解決手段】アミノ基、イソシアネート基、エポキシ基、メルカプト基およびこれらの組み合わせから選択された反応性官能基を含む有機−無機結合性シラン化合物、および無機化合物を含むコーティング層を含む、リチウム2次電池用セパレータ。
【選択図】図2
Description
[コーティング層を含むセパレータの製造]
(製造例1〜6)
アセトン75gにアルミナ25gを入れて攪拌した。さらに、前記アセトン75g、アルミナ25gの混合物に、下記表1に記載されたような添加剤2.5gを入れて攪拌した(溶液1)。前記添加剤は攪拌時にアルミナと反応してアルミナ表面にコーティングされる。
(実施例1)
正極製造:正極活物質としてLiCoO2を使用し、バインダーとしてはPVDF系バインダー、導電剤としてはSuper−P、ミキシング溶媒としてはNMP(N−メチル−2−ピロリドン)を使用して、94/3/3(質量比)の組成比でスラリーを製造した。その後、前記スラリーを12μmのアルミニウム集電体の上にコーティングした。これを乾燥させた後に圧延を施して正極板を製造した。前記PVDF系バインダーは、純粋にPVDF成分のみのバインダーと、COOH成分を含むPVDF系バインダーとを混合して使用した。
添加剤を使用しないことを除いては、製造例1と同様の方法でセパレータを製造し、これを使用して実施例1と同様の方法で電池を製造した。
実施例1の電池(図面において、Coupling Neoと称す)と比較例の電池(図面において、Neo V2と称す)に対して、下記条件下において充放電サイクル試験を行い、電池容量および電池の厚さの変化を測定した。
電池に対して前述のような充放電サイクル試験を行いながら、電池内部抵抗の増加率を測定した。その結果を図3に示した。図3から分かるように、充放電サイクルの回数が増加する場合、アミノプロピルトリエトキシシランを添加剤として含むセパレータを使用した実施例1の電池(Coupling NEO)は、内部抵抗増加率が比較例の電池(NEO V2)に比べてより小さいことが分かる。
実施例1のセパレータを使用して製造した電極と比較例の電極に対して、貫通試験を行った。貫通条件は、0.7Cおよび4.3Vで充電した後、30分間休止した状態で、直径2.5mmの鋼鉄棒(iron bar)を使用し、100mm/sの速度で貫通させ、発火の有無を観察した。
112 負極
113 セパレータ
114 正極
120 電池容器
140 封入部材
Claims (21)
- アミノ基、イソシアネート基、エポキシ基、メルカプト基およびこれらの組み合わせから選択された反応性官能基を含む有機−無機結合性シラン化合物、および無機化合物を含むコーティング層を含む、リチウム2次電池用セパレータ。
- 前記コーティング層に含まれる前記無機化合物は、前記反応性官能基を含む前記有機−無機結合性シラン化合物により形成された表面コーティング層を有する、請求項1に記載のリチウム2次電池用セパレータ。
- 前記表面コーティング層は、前記無機化合物の表面に連続または非連続で存在する、請求項2に記載のリチウム2次電池用セパレータ。
- 前記反応性官能基を含む有機−無機結合性シラン化合物は、エポキシアルキルアルコキシシラン、アミノアルキルアルコキシシラン、イソシアネートアルキルアルコキシシラン、メルカプトアルキルアルコキシシランおよびこれらの組み合わせから選択される、請求項1〜3のいずれか一項に記載のリチウム2次電池用セパレータ。
- 前記反応性官能基を含む有機−無機結合性シラン化合物は、ビニルアルキルアルコキシシラン、ハロゲン化アルキルアルコキシシラン、ビニルハロシラン、アルキルアシルオキシラン、およびこれらの組み合わせから選択された一つに、前記反応性官能基としてアミノ基、イソシアネート基、エポキシ基、メルカプト基およびこれらの組み合わせから選択された官能基が導入されたものである、請求項1〜3のいずれか一項に記載のリチウム2次電池用セパレータ。
- 前記無機化合物は、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2、BaTiO3、SiO2、およびこれらの組み合わせから選択された少なくとも一つを含む、請求項1〜5のいずれか一項に記載のリチウム2次電池用セパレータ。
- 前記セパレータの前記コーティング層は、ポリフッ化ビニリデン、ポリ(フッ化ビニリデン−ヘキサフルオロプロピレン)、COOH基で改質されたポリフッ化ビニリデン、ポリエチレンオキシド、ポリアクリロニトリル、ポリイミド、ポリアミック酸、ポリアミドイミド、アラミド、ポリビニルアセテート、ポリメチルメタクリレート、ポリビニルエーテル、およびこれらの組み合わせから選択されたバインダーをさらに含む、請求項1〜6のいずれか一項に記載のリチウム2次電池用セパレータ。
- 前記セパレータは、ガラス繊維、ポリエステル、テフロン(登録商標)、ポリオレフィン、ポリテトラフルオロエチレン、およびこれらの組み合わせから選択された多孔性基材をさらに含む、請求項1〜7のいずれか一項に記載のリチウム2次電池用セパレータ。
- 前記セパレータの前記コーティング層は、前記多孔性基材の一面または両面に形成される、請求項8に記載のセパレータ。
- 前記セパレータの前記コーティング層は、前記無機化合物100質量部を基準に、前記反応性官能基を含む有機−無機結合性シラン化合物を1〜20質量部で含む、請求項1〜9のいずれか一項に記載のリチウム2次電池用セパレータ。
- 前記セパレータの前記コーティング層において、前記無機化合物:前記バインダーの質量比は、1:0.05〜1:5の範囲である、請求項7に記載のリチウム2次電池用セパレータ。
- 前記反応性官能基を含む有機−無機結合性シラン化合物は、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、3−アミノプロピルトリエトキシシラン、(3−トリメトキシシリルプロピル)ジエチレントリアミン、(2−アミノエチル)−3−アミノプロピルトリメトキシシラン、N−メチルアミノプロピルトリメトキシシラン、3−(トリエトキシシリル)プロピルイソシアネート、3−(トリメトキシシリル)プロピルイソシアネート、3−メルカプトプロピルトリメトキシシラン、ビス(3−(トリエトキシシリル)プロピル)−テトラスルフィド、ビニルトリス(2−メトキシエトキシ)シラン、3−メタクリルオキシプロピルトリメトキシシラン、3−クロロプロピルトリメトキシシラン、ビニルトリクロロシラン、メチルトリアセトキシシラン、およびこれらの組み合わせから選択された少なくとも一つを含む、請求項1に記載のリチウム2次電池用セパレータ。
- 正極、負極、および前記正極と負極との間に配置されたセパレータを含む2次電池であって、前記セパレータは、反応性官能基を含む有機−無機結合性シラン化合物および無機化合物を含むコーティング層を含み、前記反応性官能基は、アミノ基、イソシアネート基、エポキシ基、メルカプト基およびこれらの組み合わせから選択される、2次電池。
- 前記コーティング層において、前記無機化合物は、反応性官能基を含む前記有機−無機結合性シラン化合物により形成された表面コーティング層を有する、請求項13に記載の2次電池。
- 前記反応性官能基を含む有機−無機結合性シラン化合物は、エポキシアルキルアルコキシシラン、アミノアルキルアルコキシシラン、イソシアネートアルキルアルコキシシラン、メルカプトアルキルアルコキシシランおよびこれらの組み合わせから選択される、請求項13または14に記載の2次電池。
- 前記反応性官能基を含む有機−無機結合性シラン化合物は、ビニルアルキルアルコキシシラン、ハロゲン化アルキルアルコキシシラン、ビニルハロシラン、アルキルアシルオキシラン、およびこれらの組み合わせから選択された一つに、アミノ基、イソシアネート基、エポキシ基、メルカプト基およびこれらの組み合わせから選択された官能基が導入されたものである、請求項13または14に記載の2次電池。
- 前記無機化合物は、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2、BaTiO3、SiO2、およびこれらの組み合わせから選択される、請求項13〜16のいずれか一項に記載の2次電池。
- 前記セパレータのコーティング層は、前記無機化合物100質量部を基準に、前記反応性官能基を含む有機−無機結合性シラン化合物を1〜20質量部で含む、請求項13〜17のいずれか一項に記載の2次電池。
- 前記反応性官能基を含む有機−無機結合性シラン化合物は、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、3−アミノプロピルトリエトキシシラン、(3−トリメトキシシリルプロピル)ジエチレントリアミン、(2−アミノエチル)−3−アミノプロピルトリメトキシシラン、N−メチルアミノプロピルトリメトキシシラン、3−(トリエトキシシリル)プロピルイソシアネート、3−(トリメトキシシリル)プロピルイソシアネート、3−メルカプトプロピルトリメトキシシラン、ビス(3−(トリエトキシシリル)プロピル)−テトラスルフィド、ビニルトリス(2−メトキシエトキシ)シラン、3−メタクリルオキシプロピルトリメトキシシラン、3−クロロプロピルトリメトキシシラン、ビニルトリクロロシラン、メチルトリアセトキシシラン、およびこれらの組み合わせから選択される、請求項13または14に記載の2次電池。
- 前記セパレータの前記コーティング層において、前記無機化合物:バインダーの質量比は、1:0.05〜1:5の範囲である、請求項13〜19のいずれか一項に記載の2次電池。
- 請求項1に記載のセパレータ、正極、および負極を電極組立体として形成する段階と、および前記電極組立体に電解質を提供する段階とを含む請求項13に記載の2次電池の製造方法。
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Also Published As
Publication number | Publication date |
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CN103311483B (zh) | 2017-08-01 |
EP2639854B1 (en) | 2020-05-06 |
EP2639854A1 (en) | 2013-09-18 |
KR20130105334A (ko) | 2013-09-25 |
CN103311483A (zh) | 2013-09-18 |
US20130244080A1 (en) | 2013-09-19 |
KR101865171B1 (ko) | 2018-06-07 |
JP6282401B2 (ja) | 2018-02-21 |
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