JP2015519711A - 二次電池用電極、その製造方法、それを含む二次電池、及びケーブル型二次電池 - Google Patents
二次電池用電極、その製造方法、それを含む二次電池、及びケーブル型二次電池 Download PDFInfo
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- JP2015519711A JP2015519711A JP2015515972A JP2015515972A JP2015519711A JP 2015519711 A JP2015519711 A JP 2015519711A JP 2015515972 A JP2015515972 A JP 2015515972A JP 2015515972 A JP2015515972 A JP 2015515972A JP 2015519711 A JP2015519711 A JP 2015519711A
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Classifications
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Abstract
Description
(1)負極の製造
銅からなるシート型集電体の一面に、ポリエチレンフィルムからなる第2支持層を圧着して形成させた。
実施例(1)で製造されたシート型の二次電池用負極と、リチウムホイルからなる正極との間にポリエチレンセパレータを介在することで、電極組立体を製造した。前記電極組立体を電池ケースに収納した後、エチレンカーボネートとジエチルカーボネートとを1:2の体積比で混合した非水溶媒に1M LiPF6が添加された電解液を注入してコイン型ハーフセルを製造した。
(1)負極の製造
銅からなるシート型の集電体の一面に、負極活物質として黒鉛、導電材としてデンカブラック及びバインダーとしてPVdFがそれぞれ70重量%、5重量%及び25重量%でNMP溶媒に分散された負極活物質スラリーを塗布して乾燥することで負極を製造した。
比較例(1)で製造された負極を使用することを除いて、実施例(2)と同様の方法でコイン型ハーフセルを製造した。
実施例及び比較例で製造された負極を二つ折りにした後、その模様を観察した。
実施例及び比較例で製造されたコイン型ハーフセルを用いて充放電特性を評価した。0.5Cの電流密度で5mVまで定電流充電した後、定電圧で5mVに一定に維持し、電流密度が0.005Cになれば充電を終了した。放電は0.5Cの電流密度で1.5Vまで定電流モードで放電した。同じ条件で充放電を25回繰り返した。
20 電極活物質層
20’ 電極活物質スラリー
30 第1支持層
40 第2支持層
50 コーティングブレード
100、200 ケーブル型二次電池
110、210 リチウムイオン供給コア部
120、220 内部集電体
130、230 内部電極活物質層
140、240 第1支持層
150、250 第2支持層
160、260 分離層
170、270 外部電極活物質層
180、280 外部集電体
190、290 保護被覆
Claims (61)
- 集電体;
前記集電体の一面に形成された電極活物質層;及び
前記電極活物質層上に形成された多孔性の第1支持層;を含むシート型の二次電池用電極。 - 前記集電体が、ステンレススチール、アルミニウム、ニッケル、チタン、焼成炭素もしくは銅;カーボン、ニッケル、チタンもしくは銀で表面処理されたステンレススチール;アルミニウム‐カドミウム合金;導電材で表面処理された非伝導性高分子;伝導性高分子;Ni、Al、Au、Ag、Pd/Ag、Cr、Ta、Cu、BaもしくはITOの金属粉末を含む金属ペースト;または黒鉛、カーボンブラックもしくは炭素ナノチューブの炭素粉末を含む炭素ペースト;から形成されたことを特徴とする請求項1に記載の二次電池用電極。
- 前記集電体が、メッシュ型集電体である請求項1に記載の二次電池用電極。
- 前記集電体が、導電材及びバインダーから構成された下塗層をさらに含む請求項1に記載の二次電池用電極。
- 前記導電材が、カーボンブラック、アセチレンブラック、ケッチェンブラック、炭素繊維、炭素ナノチューブ及びグラフェンからなる群より選択されるいずれか1つまたはこれらのうち2種以上の混合物を含む請求項4に記載の二次電池用電極。
- 前記バインダーが、ポリフッ化ビニリデン(PVDF)、フッ化ビニリデン‐ヘキサフルオロプロピレン共重合体、ポリフッ化ビニリデン‐co-トリクロロエチレン、ポリブチルアクリレート、ポリメチルメタクリレート、ポリアクリロニトリル、ポリビニルピロリドン、ポリビニルアセテート、エチレンビニルアセテート共重合体、ポリエチレンオキサイド、ポリアリレート、セルロースアセテート、セルロースアセテートブチレート、セルロースアセテートプロピオネート、シアノエチルプルラン、シアノエチルポリビニルアルコール、シアノエチルセルロース、シアノエチルスクロース、プルラン、カルボキシルメチルセルロース、スチレンブタジエンゴム、アクリロニトリルスチレンブタジエン共重合体及びポリイミドからなる群より選択されたいずれか1つまたはこれらのうち2種以上の混合物である請求項4に記載の二次電池用電極。
- 前記集電体の少なくとも一面に、複数の凹部が形成された請求項1に記載の二次電池用電極。
- 前記複数の凹部が、連続的なパターンを有するか、又は、断続的なパターンを有する請求項7に記載の二次電池用電極。
- 前記連続的なパターンが、互いに離隔して長さ方向に形成された請求項8に記載の二次電池用電極。
- 前記断続的なパターンが、複数の孔により形成されている請求項8に記載の二次電池用電極。
- 前記複数の孔が、円形または多角形である請求項10に記載の二次電池用電極。
- 前記第1支持層が、メッシュ型多孔性膜または不織布である請求項1に記載の二次電池用電極。
- 前記第1支持層が、高密度ポリエチレン、低密度ポリエチレン、線形低密度ポリエチレン、超高分子量ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエステル、ポリアセタール、ポリアミド、ポリカーボネート、ポリイミド、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリフェニレンオキサイド、ポリフェニレンスルフィド及びポリエチレンナフタレートからなる群より選択されたいずれか1つまたはこれらのうち2種以上の混合物から形成された請求項1に記載の二次電池用電極。
- 前記第1支持層が、前記第1支持層上に、導電材及びバインダーを備える導電材コーティング層をさらに含む請求項1に記載の二次電池用電極。
- 前記導電材コーティング層中、前記導電材と前記バインダーとが80:20ないし99:1の重量比で存在する請求項14に記載の二次電池用電極。
- 前記導電材が、カーボンブラック、アセチレンブラック、ケッチェンブラック、炭素繊維、炭素ナノチューブ及びグラフェンからなる群より選択されるいずれか1つまたはこれらのうち2種以上の混合物を含む請求項14に記載の二次電池用電極。
- 前記バインダーが、ポリフッ化ビニリデン(PVDF)、フッ化ビニリデン‐ヘキサフルオロプロピレン共重合体、ポリフッ化ビニリデン‐co-トリクロロエチレン、ポリブチルアクリレート、ポリメチルメタクリレート、ポリアクリロニトリル、ポリビニルピロリドン、ポリビニルアセテート、エチレンビニルアセテート共重合体、ポリエチレンオキサイド、ポリアリレート、セルロースアセテート、セルロースアセテートブチレート、セルロースアセテートプロピオネート、シアノエチルプルラン、シアノエチルポリビニルアルコール、シアノエチルセルロース、シアノエチルスクロース、プルラン、カルボキシルメチルセルロース、スチレンブタジエンゴム、アクリロニトリルスチレンブタジエン共重合体及びポリイミドからなる群より選択されたいずれか1つまたはこれらのうち2種以上の混合物である請求項14に記載の二次電池用電極。
- 前記第1支持層が、前記第1支持層上に、無機物粒子とバインダー高分子との混合物を含む多孔性コーティング層をさらに含む請求項1に記載の二次電池用電極。
- 前記集電体の他面に形成された第2支持層をさらに含む請求項1に記載の二次電池用電極。
- 前記第2支持層が、高分子フィルムである請求項19に記載の二次電池用電極。
- 前記高分子フィルムが、ポリオレフィン、ポリエステル、ポリイミド及びポリアミドからなる群より選択されるいずれか1つまたはこれらのうち2種以上の混合物から形成される請求項20に記載の二次電池用電極。
- 前記二次電池用電極が負極である場合、
前記電極活物質層は、天然黒鉛、人造黒鉛または炭素質材料;リチウム含有チタン複合酸化物(LTO);Si、Sn、Li、Zn、Mg、Cd、Ce、NiまたはFeである金属類(Me);前記金属類(Me)の合金類;前記金属類(Me)の酸化物(MeOx);及び前記金属類(Me)と炭素との複合体からなる群より選択されたいずれか1つの活物質またはこれらのうち2種以上の混合物を含み、
前記二次電池用電極が正極である場合、前記電極活物質層は、LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNiMnCoO2、及びLiNi1-x-y-zCoxM1yM2zO2(M1及びM2は互いに独立して、Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg及びMoからなる群より選択され、x、y及びzは互いに独立した酸化物組成元素の原子分率であって、0≦x<0.5、0≦y<0.5、0≦z<0.5、x+y+z≦1である)からなる群より選択されたいずれか1つの活物質またはこれらのうち2種以上の混合物を含む請求項1に記載の二次電池用電極。 - (S1)集電体の一面に、電極活物質スラリーを塗布する工程;
(S2)塗布された前記電極活物質スラリー上に多孔性の第1支持層を形成する工程;及び
(S3)前記(S2)工程の結果物を圧迫し、前記集電体と前記第1支持層との間に接着して互いに一体化した電極活物質層を形成する工程;を含むシート型二次電池用電極の製造方法。 - 前記電極活物質スラリーが、バインダー成分を含む請求項23に記載の二次電池用電極の製造方法。
- 前記(S2)工程で、前記バインダー成分が硬化する前に、塗布された前記電極活物質スラリー上に前記多孔性の第1支持層を形成する請求項24に記載の二次電池用電極の製造方法。
- 前記(S3)工程で、前記バインダー成分が硬化する前に、前記(S2)工程の結果物をコーティングブレードにより圧迫し、前記集電体と前記第1支持層との間に接着して互いに一体化した電極活物質層を形成する請求項24に記載の二次電池用電極の製造方法。
- 前記(S1)工程の前又は前記(S3)工程の後、前記集電体の他面に、第2支持層を圧迫して形成する工程をさらに含む請求項23に記載の二次電池用電極の製造方法。
- 正極、負極、前記正極と前記負極との間に介在されたセパレータ、及び電解質を含む二次電池において、
前記正極及び前記負極の少なくとも1つが、請求項1ないし請求項22のうちいずれか1項に記載の二次電池用電極である二次電池。 - 前記二次電池が、積層型、巻取型、積層/折畳型またはケーブル型である請求項28に記載の二次電池。
- 内部電極;
前記内部電極の外面を囲み、電極の短絡を防止する分離層;及び
前記分離層の外面を囲んで螺旋状に巻き取られた外部電極;を含み、
前記内部電極及び前記外部電極の1種以上が、請求項1ないし請求項22のうちいずれか1項に記載の二次電池用電極から形成されるケーブル型二次電池。 - 前記外部電極が、一方向に延びたストリップ構造である請求項30に記載のケーブル型二次電池。
- 前記外部電極が、幅方向に互いに重ならないように螺旋状に巻き取られている請求項30に記載のケーブル型二次電池。
- 前記外部電極が、前記外部電極の幅の2倍以内の間隔を置いて互いに離隔し、重ならないように螺旋状に巻き取られている請求項32に記載のケーブル型二次電池。
- 前記外部電極が、幅方向に互いに重なるように螺旋状に巻き取られている請求項30に記載のケーブル型二次電池。
- 前記外部電極が、重なる部分の幅が前記外部電極の幅の0.9倍以内になるように螺旋状に巻き取られている請求項34に記載のケーブル型二次電池。
- 前記内部電極が、中心部に空間が形成された中空型構造である請求項30に記載のケーブル型二次電池。
- 前記内部電極が、螺旋状に巻き取られた1つ以上の前記二次電池用電極を含む請求項36に記載のケーブル型二次電池。
- 前記内部電極の内部に、内部電極集電体コア部、電解質を含むリチウムイオン供給コア部、または充填コア部が備えられた請求項36に記載のケーブル型二次電池。
- 前記内部電極集電体コア部が、カーボンナノチューブ、ステンレススチール、アルミニウム、ニッケル、チタン、焼成炭素もしくは銅;カーボン、ニッケル、チタンもしくは銀で表面処理されたステンレススチール;アルミニウム‐カドミウム合金;導電材で表面処理された非伝導性高分子;または伝導性高分子から形成された請求項38に記載のケーブル型二次電池。
- 前記リチウムイオン供給コア部が、ゲル型ポリマー電解質及び支持体を含む請求項38に記載のケーブル型二次電池。
- 前記リチウムイオン供給コア部が、液体電解質及び多孔性担体を含む請求項38に記載のケーブル型二次電池。
- 前記電解質が、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ブチレンカーボネート(BC)、ビニレンカーボネート(VC)、ジエチルカーボネート(DEC)、ジメチルカーボネート(DMC)、エチルメチルカーボネート(EMC)、メチルホルメート(MF)、γ‐ブチロラクトン(γ‐BL)、スルホラン、メチルアセテート(MA)、またはメチルプロピオネート(MP)を使用した非水電解液;PEO、PVdF、PVdF‐HFP、PMMA、PANまたはPVAcを使用したゲル型高分子電解質;及びPEO、ポリプロピレンオキサイド(PPO)、ポリエーテルイミン(PEI)、ポリエチレンスルフィド(PES)またはポリビニルアセテート(PVAc)を使用した固体電解質;からなる群より選択された電解質を含む請求項38に記載のケーブル型二次電池。
- 前記電解質が、リチウム塩をさらに含む請求項38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、クロロホウ酸リチウム、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いずれか1つまたはこれらのうち2種以上の混合物である請求項43に記載のケーブル型二次電池。
- 前記充填コア部が、ワイヤ、繊維、粉末、メッシュ、または発泡体の形状を有する高分子樹脂、ゴム、または無機物から形成された請求項38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請求項30に記載のケーブル型二次電池。
- 前記分離層が、電解質層またはセパレータである請求項30に記載のケーブル型二次電池。
- 前記電解質層が、PEO、PVdF、PVdF‐HFP、PMMA、PANまたはPVAcを使用したゲル型高分子電解質;及びPEO、ポリプロピレンオキサイド(PPO)、ポリエーテルイミン(PEI)、ポリエチレンスルフィド(PES)またはポリビニルアセテート(PVAc)を使用した固体電解質;からなる群より選択された電解質を含む請求項47に記載のケーブル型二次電池。
- 前記電解質層が、リチウム塩をさらに含む請求項47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、クロロホウ酸リチウム、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いずれか1つまたはこれらのうち2種以上の混合物である請求項49に記載のケーブル型二次電池。
- 前記セパレータが、エチレン単独重合体、プロピレン単独重合体、エチレン‐ブテン共重合体、エチレン‐ヘキセン共重合体及びエチレン‐メタクリレート共重合体からなる群より選択されたポリオレフィン系高分子から形成された多孔性高分子基材;ポリエステル、ポリアセタール、ポリアミド、ポリカーボネート、ポリイミド、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリフェニレンオキサイド、ポリフェニレンスルフィド及びポリエチレンナフタレートからなる群より選択された高分子から形成された多孔性高分子基材;無機物粒子とバインダー高分子との混合物から形成された多孔性基材;または前記多孔性高分子基材の少なくとも一面上に形成され、無機物粒子とバインダー高分子との混合物を含む多孔性コーティング層を備えたセパレータである請求項47に記載のケーブル型二次電池。
- 前記多孔性高分子基材が、多孔性高分子フィルム基材、または、多孔性不織布基材である請求項51に記載のケーブル型二次電池。
- 前記外部電極の外面を囲んでいる保護被覆をさらに含む請求項30に記載のケーブル型二次電池。
- 前記保護被覆が、高分子樹脂で形成された請求項53に記載のケーブル型二次電池。
- 前記高分子樹脂が、PET、PVC、HDPE及びエポキシ樹脂からなる群より選択されるいずれか1つまたはこれらのうち2種以上の混合物を含む請求項54に記載のケーブル型二次電池。
- 前記保護被覆が、水分遮断層をさらに含む請求項54に記載のケーブル型二次電池。
- 前記水分遮断層が、アルミニウムまたは液晶高分子から形成された請求項56に記載のケーブル型二次電池。
- 電解質を含むリチウムイオン供給コア部;
前記リチウムイオン供給コア部の外面を囲み、集電体及び電極活物質層を備える内部電極;
前記内部電極の外面を囲み、電極の短絡を防止する分離層;及び
前記分離層の外面を囲んで螺旋状に巻き取られ、集電体及び電極活物質層を備える外部電極;を含み、
前記内部電極及び前記外部電極の1つ以上が、請求項1ないし請求項22のうちいずれか1項に記載の二次電池用電極から形成されるケーブル型二次電池。 - 互いに平行に配置された2以上の内部電極;
前記内部電極の外面を囲み、電極の短絡を防止する分離層;及び
前記分離層の外面を囲んで螺旋状に巻き取られた外部電極;を含み、
前記内部電極及び前記外部電極の1つ以上が、請求項1ないし請求項22のうちいずれか1項に記載の二次電池用電極から形成されるケーブル型二次電池。 - 電解質を含む2以上のリチウムイオン供給コア部;
前記リチウムイオン供給コア部それぞれの外面を囲み、集電体及び電極活物質層をそれぞれ備えて互いに平行に配置される2以上の内部電極;
前記内部電極の外面を囲み、電極の短絡を防止する分離層;及び
前記分離層の外面を囲んで螺旋状に巻き取られ、集電体及び電極活物質層を備える外部電極;を含み、
前記内部電極及び前記外部電極の1つ以上が、請求項1ないし請求項22のうちいずれか1項に記載の二次電池用電極から形成されるケーブル型二次電池。 - 前記内部電極が、螺旋状に巻き取られた1つ以上の前記二次電池用電極を含む請求項60に記載のケーブル型二次電池。
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JP2017188467A (ja) * | 2013-05-07 | 2017-10-12 | エルジー・ケム・リミテッド | 二次電池用電極、その製造方法、それを含む二次電池、及びケーブル型二次電池 |
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JP7127209B2 (ja) | 2018-12-03 | 2022-08-29 | エルジー エナジー ソリューション リミテッド | フレキシブル電極、それを含む二次電池及びフレキシブル二次電池 |
WO2021171999A1 (ja) * | 2020-02-26 | 2021-09-02 | 株式会社村田製作所 | 導電性基体および二次電池 |
JP7347647B2 (ja) | 2020-02-26 | 2023-09-20 | 株式会社村田製作所 | 導電性基体および二次電池 |
Also Published As
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KR101470555B1 (ko) | 2014-12-10 |
EP2830126A1 (en) | 2015-01-28 |
US20140370350A1 (en) | 2014-12-18 |
US20140370349A1 (en) | 2014-12-18 |
KR101567968B1 (ko) | 2015-11-10 |
US9972861B2 (en) | 2018-05-15 |
CN204441379U (zh) | 2015-07-01 |
KR101775098B1 (ko) | 2017-09-05 |
CN104466191A (zh) | 2015-03-25 |
EP2830126B1 (en) | 2019-07-03 |
WO2014182060A1 (ko) | 2014-11-13 |
JP6576975B2 (ja) | 2019-09-18 |
EP2830126A4 (en) | 2016-03-02 |
CN104466191B (zh) | 2018-01-23 |
KR20150063339A (ko) | 2015-06-09 |
JP2017188467A (ja) | 2017-10-12 |
KR20140132307A (ko) | 2014-11-17 |
US9203104B2 (en) | 2015-12-01 |
KR20140132291A (ko) | 2014-11-17 |
JP6240176B2 (ja) | 2017-11-29 |
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