JP5734527B2 - ケーブル型二次電池 - Google Patents
ケーブル型二次電池 Download PDFInfo
- Publication number
- JP5734527B2 JP5734527B2 JP2014539887A JP2014539887A JP5734527B2 JP 5734527 B2 JP5734527 B2 JP 5734527B2 JP 2014539887 A JP2014539887 A JP 2014539887A JP 2014539887 A JP2014539887 A JP 2014539887A JP 5734527 B2 JP5734527 B2 JP 5734527B2
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- JP
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- Prior art keywords
- secondary battery
- type secondary
- polymer
- cable type
- current collector
- Prior art date
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- 229920000642 polymer Polymers 0.000 claims description 35
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- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
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- 239000011253 protective coating Substances 0.000 claims description 6
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
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- PWRLWCQANJNXOR-UHFFFAOYSA-N dilithium chloro(dioxido)borane Chemical compound [Li+].[Li+].[O-]B([O-])Cl PWRLWCQANJNXOR-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 3
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Images
Classifications
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- H01M2300/0094—Composites in the form of layered products, e.g. coatings
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Description
PVdF‐HFPに有機電解液(1MのLiPF6、エチレンカーボネート(EC)/プロピレンカーボネート(PC)=1/1)(EL)をPVdF‐HFP重量対比30、40、50、60、70及び80重量%になるように用意した。前記高分子を溶解させる溶媒としては、アセトンを使用した。その後、前記混合物をガラス板にキャストし、乾燥させて電解質膜を製造した。
下記の表1の組成比になるように混合物を製造した。前記混合物に紫外線開始剤であるベンゾインをポリエチレングリコールジメタクリレート(PEGDMA)対比3重量%添加し、それをガラス板にキャストして1分間紫外線を照射し、重合によって電解質膜を製造した。
PVdF‐HFPに有機電解液(1MのLiPF6、EC/PC=1/1)(EL)をPVdF‐HFP重量対比30重量%になるように用意した。前記高分子を溶解させる溶媒としては、アセトンを使用した。その後、前記混合物をガラス板にキャストし、乾燥させて第1電解質層を製造した。有機電解液(1MのLiPF6、EC/PC=1/1):PEO:PEGDMA=78:15.4:6.6重量比の混合物に紫外線開始剤であるベンゾインをPEGDMA対比3重量%添加し、それを前記第1電解質層に塗布して1分間紫外線を照射し、重合によって第2電解質層を形成することで多層高分子電解質膜を製造した。
11:第1電解質層
12:第2電解質層
100、200:ケーブル型二次電池
110、210:電解質層
120、220:内部電極
121、221:内部集電体
122、222:内部電極活物質層
130、230:外部電極
131、231:外部集電体
132、232:外部電極活物質層
140、240:保護被覆
Claims (16)
- 開放構造の内部集電体及び前記内部集電体の表面にコーティングされた内部電極活物質層を有する内部電極;前記内部電極を囲んで形成され、高分子電解質膜である電解質層;前記電解質層の外面を囲んで形成された外部電極活物質層と前記外部電極活物質層を囲んで形成された外部集電体を有する外部電極;及び前記外部電極を囲むように配置される保護被覆を備え、
前記高分子電解質膜は、重量比が50:50より大きく80:20以下である第1高分子と第1有機電解液との混合物を含む第1電解質層;及び前記第1電解質層の少なくとも片面に形成され、重量比が20:80ないし50:50である第2高分子と第2有機電解液との混合物を含む第2電解質層を備え、
前記開放構造の内部集電体が、その内部に電解質を含むリチウムイオン供給コア部を更に含むことを特徴とする
ケーブル型二次電池。 - 前記第1高分子が、極性非架橋高分子であることを特徴とする請求項1に記載のケーブル型二次電池。
- 前記極性非架橋高分子が、ポリアクリロニトリル、ポリビニルクロライド、ポリフッ化ビニリデン、フッ化ビニリデン‐ヘキサフルオロプロピレン共重合体、ポリエチレンイミン、ポリメチルメタクリレート、ポリブチルアクリレート、ポリビニルピロリドン、ポリビニルアセテート、及びエチレンビニルアセテート共重合体からなる群より選択された1種または2種以上の混合物であることを特徴とする請求項2に記載のケーブル型二次電池。
- 前記第2高分子が、極性非架橋高分子、オキサイド系非架橋高分子、及び高分子架橋構造体からなる群より選択された1種または2種以上の混合物であることを特徴とする請求項1〜3のいずれか一項に記載のケーブル型二次電池。
- 前記極性非架橋高分子が、ポリアクリロニトリル、ポリビニルクロライド、ポリフッ化ビニリデン、フッ化ビニリデン‐ヘキサフルオロプロピレン共重合体、ポリエチレンイミン、ポリメチルメタクリレート、ポリブチルアクリレート、ポリビニルピロリドン、ポリビニルアセテート、及びエチレンビニルアセテート共重合体からなる群より選択された1種または2種以上の混合物であることを特徴とする請求項4に記載のケーブル型二次電池。
- 前記オキサイド系非架橋高分子が、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリオキシメチレン、及びポリジメチルシロキサンからなる群より選択された1種または2種以上の混合物であることを特徴とする請求項4に記載のケーブル型二次電池。
- 前記高分子架橋構造体が、2個以上の官能基を有する単量体の重合体、または2個以上の官能基を有する単量体と1個の官能基を有する極性単量体との共重合体であることを特徴とする請求項4に記載のケーブル型二次電池。
- 前記2個以上の官能基を有する単量体が、トリメチロールプロパンエトキシレートトリアクリレート、ポリエチレングリコールジメタクリレート、ポリエチレングリコールジアクリレート、ジビニルベンゼン、ポリエステルジメタクリレート、ジビニルエーテル、トリメチロールプロパン、トリメチロールプロパントリメタクリレート、及びエトキシ化ビスフェノールAジメタクリレートからなる群より選択された1種または2種以上の混合物であることを特徴とする請求項7に記載のケーブル型二次電池。
- 前記1個の官能基を有する極性単量体が、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、メチルアクリレート、ブチルアクリレート、エチレングリコールメチルエーテルアクリレート、エチレングリコールメチルエーテルメタクリレート、アクリロニトリル、ビニルアセテート、塩化ビニル、及びフッ化ビニルからなる群より選択された1種または2種以上の混合物であることを特徴とする請求項7または8に記載のケーブル型二次電池。
- 前記第1有機電解液及び前記第2有機電解液が、互いに独立して、リチウム塩を含有することを特徴とする請求項1〜9のいずれか一項に記載のケーブル型二次電池。
- 前記リチウム塩が、LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、クロロほう酸リチウム、低級脂肪族カルボン酸リチウム、及びテトラフェニルホウ酸リチウムからなる群より選択された1種または2種以上であることを特徴とする請求項10に記載のケーブル型二次電池。
- 前記第1有機電解液及び前記第2有機電解液が、互いに独立して、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ビニレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、エチルメチルカーボネート、γ‐ブチロラクトン、スルホラン、メチルアセテート、及びメチルプロピオネートからなる群より選択された1種または2種以上であることを特徴とする請求項10または11に記載のケーブル型二次電池。
- 前記内部電極が、互いに平行に配置された2以上の電極で形成されたことを特徴とする請求項1〜12のいずれか一項に記載のケーブル型二次電池。
- 前記内部電極が負極であり、前記外部電極が正極であるか、または、前記内部電極が正極であり、前記外部電極が負極であることを特徴とする請求項1〜13のいずれか一項に記載のケーブル型二次電池。
- 前記開放構造の内部集電体が、巻き取られたワイヤ型集電体またはメッシュ型集電体であることを特徴とする請求項1〜14のいずれか一項に記載のケーブル型二次電池。
- 前記外部集電体が、パイプ型集電体、巻き取られたワイヤ型集電体またはメッシュ型集電体であることを特徴とする請求項1〜15のいずれか一項に記載のケーブル型二次電池。
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