JP2022541837A - 高ニッケル電極シートおよびその製造方法 - Google Patents
高ニッケル電極シートおよびその製造方法 Download PDFInfo
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- JP2022541837A JP2022541837A JP2022504269A JP2022504269A JP2022541837A JP 2022541837 A JP2022541837 A JP 2022541837A JP 2022504269 A JP2022504269 A JP 2022504269A JP 2022504269 A JP2022504269 A JP 2022504269A JP 2022541837 A JP2022541837 A JP 2022541837A
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Abstract
Description
(第1正極合剤層形成用の第1正極スラリーの製造)
リチウム‐ニッケル‐コバルト‐マンガンの遷移金属酸化物として、ニッケルの含有量が遷移金属全体を基準にして80モル%である第1正極活物質(NCM811、D50は11μm)を用意し、カーボンブラック導電材及びPVDFバインダーをN‐メチルピロリドン溶媒中で重量比で96.5:1.5:2の割合で混合して、第1正極スラリー(粘度:5000Pa・s)を製造した。
リチウム‐ニッケル‐コバルト‐マンガンの遷移金属酸化物として、ニッケルの含有量が遷移金属全体を基準にして60モル%である第2正極活物質(NCM622、D50は11μm)を用意し、カーボンブラック導電材及びPVDFバインダーをN‐メチルピロリドン溶媒中で重量比で96.5:1.5:2の割合で混合して、第2正極スラリー(粘度:5000Pa・s)を製造した。
第1正極スラリーおよび上記第2正極スラリーをデュアルスロットダイコーターに供給し、上記コーターを用いて、アルミニウム集電体シートの一面に、上記第1正極スラリー及び上記第2正極スラリーを同時に塗布して、第1正極合剤層および第2正極合剤層を形成した。このとき、上記第1正極スラリーはスラリー塗布部の中央部位に、上記第2正極スラリーは上記第1正極スラリー塗布部の両側縁部位に、塗布されるようにした。そして、第2正極スラリー塗布部の幅の合計は、第1正極スラリー塗布部の幅の8%となるようにした。このとき、第1正極スラリーの単位面積当たりのローディング量は700mg/25cm2であり、第2正極スラリーの単位面積当たりのローディング量は560mg/25cm2である。また、第1正極合剤層のローディング量(A)に対する第2正極合剤層の単位面積当たりのローディング量(B)の割合(B/A)は0.8となるようにした。その後、第1正極合剤層および第2正極合剤層を含む正極シートを130℃で乾燥して圧延した。圧延後の第1正極合剤層と第2正極合剤層の各圧延密度を測定した結果、第1正極合剤層の圧延密度は3.8g/cm3、第2正極合剤層の圧延密度は2.47g/cm3であり、第1正極合剤層の圧延密度(a)に対する第2正極合剤層の圧延密度(b)の割合(b/a)は0.65であった。ここで、圧延密度の測定は、電極シートの第1正極合剤層および第2正極合剤層から、それぞれ特定の面積の正極を採取して、質量と体積を測定することによって計算した。
上記正極と上記負極でリチウム金属との間に多孔性のポリオレフィンセパレーターを介在して電極組立体を製造し、上記電極組立体をケース内部に位置させた後、ケース内部に電解液を注入してリチウム二次電池を製造した。このとき、エチレンカーボネート/ジメチルカーボネート/エチルメチルカーボネート(EC/DMC/EMCの混合体積比=3/4/3)からなる有機溶媒に1.0M濃度のリチウムヘキサフルオロフォスフェイト(LiPF6)を溶解させて製造した。
上記実施例1において、第2正極スラリーの単位面積当たりのローディング量と、第2正極合剤層の圧延密度とを、表1のように変更したことを除いては、実施例1と同様に電池を製造した。
上記実施例1において、第2正極スラリー中に含まれる第2正極活物質の種類を、ニッケルの含有量が3分の1であるものに変更し(NCM111、D50は11μm)、第2正極スラリーの単位面積当たりのローディング量と、第2正極合剤層の圧延密度とを、表1のように変更したことを除いては、実施例1と同様に電池を製造した。
上記実施例1において、第2正極スラリーの単位面積当たりのローディング量、第2正極合剤層の圧延密度を表1のように変更したことを除いては、実施例1と同様に電池を製造した。
実施例1~実施例4および比較例1~比較例2のリチウム二次電池に対して、電気化学充放電器を用いて初期(1回)充放電を行った。このとき、充電は4.2Vの電圧まで1/3C C‐rateの電流密度で電流を加えて行い、放電は同じ電流密度で2.5Vまで行った。このような充放電を総500回実施した。
Claims (15)
- 集電体の少なくとも一面に正極合剤層が塗布された保持部及び無地部を含む電極シートであって、
前記保持部は、
電極シートの長さ方向に沿って中央部に形成され、リチウムニッケルコバルトマンガン酸化物の第1正極活物質を含む第1正極合剤層、及び
前記第1正極合剤層の一側または両側端部に形成され、前記第1正極活物質よりもニッケル含有量が低い第2正極活物質を含む第2正極合剤層を含み、
第2正極合剤層の圧延密度(b)が第1正極合剤層の圧延密度(a)よりも小さい、電極シート。 - 前記第1正極活物質中のニッケルの含有量が、遷移金属全体の含有量のうち70モル%以上である、請求項1に記載の電極シート。
- 前記第2正極活物質中のニッケルの含有量が、遷移金属全体の含有量のうち70モル%未満である、請求項1に記載の電極シート。
- 前記第2正極活物質中のニッケルの含有量が、遷移金属全体の含有量のうち45モル%~60モル%である、請求項3に記載の電極シート。
- 前記第1正極合剤層の圧延密度(a)に対する第2正極合剤層の圧延密度(b)の割合(b/a)が0.5~0.9である、請求項1に記載の電極シート。
- 前記第1正極合剤層の圧延密度(a)が2.5g/cm3~4.3g/cm3である、請求項1に記載の電極シート。
- 前記第2正極合剤層の幅が前記第1正極合剤層の幅の1~15%である、請求項1に記載の電極シート。
- 請求項1から7のいずれか一項に記載の電極シートの保持部及び無地部を、単位電極の形態及び大きさに合わせて打ち抜きした正極を含む、リチウム二次電池。
- 請求項1から7のいずれか一項に記載の電極シートを製造する方法であって、
前記第1正極活物質を含む第1正極スラリーおよび前記第2正極活物質を含む第2正極スラリーを集電体シート上に塗布して、第1正極合剤層及び第2正極合剤層を形成する塗布工程と、
乾燥工程と、
圧延工程と、を含み、
前記塗布工程において、前記第2正極スラリーは、電極シートの幅方向を基準として前記第1正極スラリーの一側または両側端部で、前記第1正極スラリーの塗布方向と平行に塗布され、
前記圧延工程において、第2正極合剤層の圧延密度は、第1正極合剤層の圧延密度よりも小さく圧延される、電極シートの製造方法。 - 前記塗布工程において、第2正極活物質中のニッケルの含有量が、遷移金属全体の含有量のうち45モル%~60モル%である、請求項9に記載の電極シートの製造方法。
- 前記塗布工程において、前記第2正極合剤層の単位面積当たりのローディング量が、前記第1正極合剤層の単位面積当たりのローディング量よりも小さい、請求項9に記載の電極シートの製造方法。
- 前記塗布工程において、第1正極合剤層の単位面積当たりのローディング量(A)に対する第2正極合剤層の単位面積当たりのローディング量(B)の割合(B/A)は、0.7~0.99である、請求項11に記載の電極シートの製造方法。
- 前記第1正極合剤層の圧延密度(a)に対する第2正極合剤層の圧延密度(a)の割合(b/a)が、0.5~0.9である、請求項9に記載の電極シートの製造方法。
- 前記塗布工程において、前記第2正極合剤層の幅が、第1正極合剤層の幅の1~15%である、請求項9に記載の電極シートの製造方法。
- 前記塗布工程において、第1正極スラリーおよび第2正極スラリーが同時に塗布される、請求項9に記載の電極シートの製造方法。
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- 2021-04-20 CN CN202180004573.XA patent/CN114127988B/zh active Active
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JP2014207201A (ja) * | 2013-04-16 | 2014-10-30 | トヨタ自動車株式会社 | 非水電解質二次電池 |
JP2019149269A (ja) * | 2018-02-27 | 2019-09-05 | トヨタ自動車株式会社 | リチウムイオン二次電池 |
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CN114127988A (zh) | 2022-03-01 |
US20220328808A1 (en) | 2022-10-13 |
EP3996169A1 (en) | 2022-05-11 |
EP3996169A4 (en) | 2022-10-26 |
WO2021225303A1 (ko) | 2021-11-11 |
JP7270833B2 (ja) | 2023-05-10 |
CN114127988B (zh) | 2024-06-28 |
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