JP2023510562A - 電極、その製造方法、およびそれを含む二次電池 - Google Patents
電極、その製造方法、およびそれを含む二次電池 Download PDFInfo
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Images
Classifications
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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Abstract
Description
本発明は、電極、その製造方法、およびそれを含む二次電池に関する。
したがって、高出力を求める二次電池分野において、釘刺し安全性が向上した二次電池の開発が求められる状態である。
また、本発明の他の課題は、前述した電極の製造方法を提供することにある。
また、本発明のまた他の課題は、前記電極を含む二次電池に関する。
また、本発明は、前述した電極を含む二次電池を提供する。
以下、本発明について具体的に説明する。
本発明は、電極、具体的には、リチウム二次電池用電極に関する。
具体的に、本発明に係る電極は、電極活物質およびバインダー高分子を含む電極活物質シートと、メッシュ構造体を含む集電体と、を含み、前記メッシュ構造体の少なくとも一部は前記電極活物質シートに挿入されており、前記バインダー高分子の熱分解温度は270℃~315℃である。
前記電極活物質は、正極活物質および負極活物質から選択されてもよく、具体的には、負極活物質であってもよい。前記正極活物質および前記負極活物質は、当該分野で用いられる一般的な正極活物質および負極活物質が制限されずに用いられてもよい。
前記炭素系活物質は、人造黒鉛、天然黒鉛、ハードカーボン、ソフトカーボン、カーボンブラック、グラフェン、および繊維状炭素からなる群から選択される少なくとも1種を含んでもよく、好ましくは、人造黒鉛および天然黒鉛からなる群から選択された少なくとも1種を含んでもよい。
前記電極活物質は、前記電極活物質シート内に80重量%~99重量%、好ましくは90重量%~97重量%で含まれてもよい。
前記バインダー高分子の熱分解温度は270℃~315℃である。前記バインダー高分子の熱分解温度が前記範囲にある際に、バインダー高分子の耐熱性および強度が好ましいレベルに向上することができるため、外部物体により電極が貫通されるとしても電極の爆発可能性が顕著なレベルに減少できるとともに、電極活物質シートの抵抗の低減が可能であるため電極の出力特性を向上させることができる。
前記導電材は、当該電池に化学的変化を誘発せず且つ導電性を有するものであれば特に制限されず、例えば、天然黒鉛や人造黒鉛などの黒鉛;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、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラックなどのカーボンブラック;炭素繊維や金属繊維などの導電性繊維;カーボンナノチューブなどの導電性チューブ;フルオロカーボン;アルミニウム、ニッケル粉末などの金属粉末;酸化亜鉛、チタン酸カリウムなどの導電性ウィスカー;酸化チタンなどの導電性金属酸化物;ポリフェニレン誘導体などの導電性素材などが用いられてもよい。
前記電極活物質シートの厚さは50μm~500μm、好ましくは100μm~300μmであってもよい。
前記メッシュ構造体の少なくとも一部は、前記電極活物質シートに挿入される。本発明の電極によると、前記メッシュ構造体の少なくとも一部は、前記電極活物質シート内に挿入されてもよく、前記メッシュ構造体内のメッシュは、前記電極活物質シートの内部に存在してもよい。
また、本発明は、電極の製造方法、具体的には、前述した電極の製造方法を提供する。
図1を参照すると、本発明の電極の製造方法は、メッシュ構造体11を含む集電体10と、電極活物質およびバインダー高分子を含む電極活物質シート20a、20bとを準備するステップを含む。
前記メッシュ構造体11を含む集電体10は、前述した電極において説明したとおりである。
(a)電極活物質およびバインダー高分子を混合して顆粒型複合体を製造するステップ、
(b)前記顆粒型複合体を篩にかけるステップ、および
(c)前記顆粒型複合体を加圧して電極活物質シートを製造するステップ。
前記電極活物質および前記バインダー高分子は、前述した電極において説明したとおりである。
その他の電極活物質シート20a、20bに関する説明は、前述した電極において説明したとおりである。
また、本発明は、前述した電極を含む二次電池、より具体的には、リチウム二次電池を提供する。
前記非水系有機溶媒としては、例えば、N-メチル-2-ピロリジノン、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、γ-ブチロラクトン、1,2-ジメトキシエタン、テトラヒドロフラン、2-メチルテトラヒドロフラン、ジメチルスルホキシド、1,3-ジオキソラン、ホルムアミド、ジメチルホルムアミド、ジオキソラン、アセトニトリル、ニトロメタン、ギ酸メチル、酢酸メチル、リン酸トリエステル、トリメトキシメタン、ジオキソラン誘導体、スルホラン、メチルスルホラン、1,3-ジメチル-2-イミダゾリジノン、プロピレンカーボネート誘導体、テトラヒドロフラン誘導体、エーテル、プロピオン酸メチル、プロピオン酸エチルなどの非プロトン性有機溶媒が用いられてもよい。
実施例1
<電極活物質シートの製造>
バインダー高分子としては、第1バインダー高分子としてスチレン-ブタジエンゴム、および第2バインダー高分子としてポリテトラフルオロエチレン(重量平均分子量:40,000g/mol)を90:10の重量比で混合したものを用いた。熱重量分析法(TGA)により測定された前記バインダー高分子の熱分解温度は297℃であった。
前記顆粒型複合体をシート状で配置し、ロールプレスで線圧による加圧を行い、シート状の電極活物質シートを製造した。
横×縦×高さが36mm×56mm×0.05mmであり、メッシュ直径が1mmであり、メッシュの孔の広さが1mm2(横1mm×縦1mm)である銅メッシュ構造体を含む集電体を準備した。
第1バインダー高分子および第2バインダー高分子を95:5の重量比で混合したものをバインダー高分子(熱分解温度:308℃)として用いたことを除いては、実施例1と同様の方法で負極を製造した。
第1バインダー高分子および第2バインダー高分子を80:20の重量比で混合したものをバインダー高分子(熱分解温度:284℃)として用いたことを除いては、実施例1と同様の方法で負極を製造した。
バインダー高分子として、実施例1で用いられた第2バインダー高分子(熱分解温度:326℃)のみを用いたことを除いては、実施例1と同様の方法で負極を製造した。
バインダー高分子として、実施例1で用いられた第1バインダー高分子(熱分解温度:263℃)のみを用いたことを除いては、実施例1と同様の方法を行った。しかし、比較例2の場合、用いられたバインダー高分子の分散性が低いため、負極自体の製造が不可能であった。
実施例1で用いられた負極活物質、バインダー高分子としてスチレン-ブタジエンゴムおよびカルボキシメチルセルロースを2:1の重量比で混合したもの、および導電材としてカーボンブラック(製品名:Super-C、製造会社:Timcal)を95:4:1の重量比で蒸留水に添加し、負極スラリーを製造した。
<二次電池の製造>
正極活物質としてLiNi0.8Co0.1Mn0.1O2、導電材としてカーボンブラック、バインダーとしてPVdFを94:3.5:2.5の重量比で混合し、N-メチル-2-ピロリドン(NMP)に添加し、正極スラリーを製造した。製造された正極スラリーをアルミニウム集電体にコーティングし、乾燥および圧延後に一定大きさに切断し、正極を製造した。
実験例1:釘刺し安全性テスト
実施例1~3、比較例1~3で製造された二次電池を0.1C、4.2Vの条件でフル充電した後、直径10mmの釘を25mm/sの速度で下降させて電池の中央部を通過させ、電池を通過して出た釘の長さが10mmである地点で貫通実験を完了した。実施例1~3、比較例1~3で製造された二次電池を5個準備し、上記のような貫通実験を5回繰り返し行った。
11:メッシュ構造体
12:メッシュ孔
20a、20b:電極活物質シート
30a、30b:ロールプレス
Claims (12)
- 電極活物質およびバインダー高分子を含む電極活物質シートと、
メッシュ構造体を含む集電体と、
を含み、
前記メッシュ構造体の少なくとも一部は前記電極活物質シートに挿入されており、
前記バインダー高分子の熱分解温度は270℃~315℃である、電極。 - 前記バインダー高分子は、第1バインダー高分子および第2バインダー高分子を含み、
前記第1バインダー高分子は、スチレン-ブタジエンゴム、ポリビニリデンフルオライド、ポリビニリデンフルオライド-ヘキサフルオロプロピレンコポリマー、ポリアクリロニトリル、ポリメチルメタクリレート、ポリビニルアルコール、カルボキシメチルセルロース、デンプン、ヒドロキシプロピルセルロース、再生セルロース、ポリビニルピロリドン、ポリエチレン、ポリプロピレン、ポリアクリル酸、エチレン-プロピレン-ジエンモノマー、およびフッ素ゴムからなる群から選択される少なくとも1種であり、
前記第2バインダー高分子は、ポリテトラフルオロエチレンである、請求項1に記載の電極。 - 前記バインダー高分子は、前記第1バインダー高分子および前記第2バインダー高分子を60:40~99.9:0.1の重量比で含む、請求項2に記載の電極。
- 前記バインダー高分子は、前記電極活物質シート内に0.5重量%~20重量%で含まれる、請求項1から3の何れか一項に記載の電極。
- 前記メッシュ構造体は、銅、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、およびアルミニウム-カドミウム合金からなる群から選択された少なくとも1種を含む、請求項1から4の何れか一項に記載の電極。
- 前記電極は、負極である、請求項1から5の何れか一項に記載の電極。
- 前記電極活物質は、炭素系活物質およびシリコン系活物質の中から選択された少なくとも1種である、請求項6に記載の電極。
- 前記メッシュ構造体内のメッシュの孔の広さは、0.010mm2~225mm2である、請求項1から7の何れか一項に記載の電極。
- メッシュ構造体を含む集電体と、電極活物質およびバインダー高分子を含む電極活物質シートとを準備するステップと、
前記電極活物質シートを前記集電体上に位置させて加圧し、前記メッシュ構造体の少なくとも一部を前記電極活物質シートに挿入させるステップと、
を含む、請求項1から8の何れか一項に記載の電極の製造方法。 - 前記電極活物質シートは、下記ステップを含む方法により製造される、請求項9に記載の電極の製造方法。
(a)電極活物質およびバインダー高分子を混合して顆粒型複合体を製造するステップ、
(b)前記顆粒型複合体を篩にかけるステップ、および
(c)前記顆粒型複合体を加圧して電極活物質シートを製造するステップ。 - 前記加圧は、線圧で行われる、請求項9または10に記載の電極の製造方法。
- 請求項1から8の何れか一項に記載の電極を含む二次電池。
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