JP7432018B2 - 正極添加剤を含む正極、その製造方法およびそれを含むリチウム二次電池 - Google Patents
正極添加剤を含む正極、その製造方法およびそれを含むリチウム二次電池 Download PDFInfo
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- JP7432018B2 JP7432018B2 JP2022578927A JP2022578927A JP7432018B2 JP 7432018 B2 JP7432018 B2 JP 7432018B2 JP 2022578927 A JP2022578927 A JP 2022578927A JP 2022578927 A JP2022578927 A JP 2022578927A JP 7432018 B2 JP7432018 B2 JP 7432018B2
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- positive electrode
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- lithium secondary
- secondary battery
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、一実施形態において、
集電体の一面または両面に正極活物質、正極添加剤、導電材およびバインダーを含有する第1スラリーを塗布して、第1合材層を形成する段階と、
第1合材層が形成された集電体に正極活物質、導電材およびバインダーを含有する第2スラリーを塗布して、第2合材層を形成する段階と、を含み、
上記第1および第2合材層を形成する段階は、第1および第2スラリー温度を40℃以下に制御する過程を含み、
上記第1合材層に対するX線回折(XRD)分析時、下記式1を満たす、リチウム二次電池用正極の製造方法を提供する:
A/B≦1
Bは、2θ=47.9±0.1°の範囲に現れるピークのうち最も強度が強いピークの強度を示す。
集電体と、該集電体の一面または両面に形成された合材層と、を含み、
上記合材層は、第1合材層と第2合材層が積層された2層構造であり、
上記第1合材層は、正極活物質、導電材、正極添加剤およびバインダーを含み、
上記第1合材層に対するX線回折(XRD)分析時、下記式1を満たす、リチウム二次電池用正極を提供する:
A/B≦1
Bは、2θ=47.9±0.1°の範囲に現れるピークのうち最も強度が強いピークの強度を示す。
LipCo(1-q)M1 qO4
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5である。
Lix[NiyCozMnwM2 v]Ou
M2は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
x、y、z、w、vおよびuは、それぞれ1.0≦x≦1.30、0.1≦y<0.95、0.01<z≦0.5、0.01<w≦0.5、0≦v≦0.2、1.5≦u≦4.5である。
本発明は、一実施形態において、
集電体と、該集電体の一面または両面に形成された合材層と、を含み、
上記合材層は、第1合材層と第2合材層が積層された2層構造であり、
上記第1合材層は、正極活物質、導電材、正極添加剤およびバインダーを含み、
上記第1合材層に対するX線回折(XRD)分析時、下記式1を満たすリチウム二次電池用正極を提供する:
A/B≦1
Bは、2θ=47.9±0.1°の範囲に現れるピークのうち最も強度が強いピークの強度を示す。
LipCo(1-q)M1 qO4
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5である。
Lix[NiyCozMnwM2 v]Ou
M2は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
x、y、z、w、vおよびuは、それぞれ1.0≦x≦1.30、0.1≦y<0.95、0.01<z≦0.5、0.01<w≦0.5、0≦v≦0.2、1.5≦u≦4.5である。
また、本発明は、一実施形態において、
集電体の一面または両面に正極活物質、正極添加剤、導電材およびバインダーを含有する第1スラリーを塗布して、第1合材層を形成する段階と、
第1合材層が形成された集電体に正極活物質、導電材およびバインダーを含有する第2スラリーを塗布して、第2合材層を形成する段階と、を含み、
上記第1合材層を形成する段階で、第1スラリー温度を40℃以下に制御する過程を含み、
上記第1合材層に対するX線回折(XRD)分析時、下記式1を満たすリチウム二次電池用正極の製造方法を提供する:
A/B≦1
Bは、2θ=47.9±0.1°の範囲に現れるピークのうち最も強度が強いピークの強度を示す。
また、本発明は、一実施形態において、
上述した本発明による正極と、負極と、上記正極と負極の間に位置する分離膜と、を含むリチウム二次電池を提供する。
正極活物質としてLiNi0.8Co0.1Mn0.1O2 95重量部、正極添加剤としてLi6CoO4 0.9重量部、バインダーとしてPVDF 1.6重量部、導電材としてカーボンブラック2.5重量部を秤量して、N-メチルピロリドン(NMP)溶媒中で混合して、第1合材層用第1スラリーを製造した。
1)第1合材層に対するXRDパターンの観察
リチウム二次電池用正極の製造時に温度による正極添加剤の変化を確認するために、実施例1~4および比較例1~4で製造されたリチウム二次電池用正極の第1合材層を対象にX線回折を測定し、測定されたX線回折から各正極添加剤に含まれた分率を算出した。このとき、上記X線回折は、Rigaku社のX線回折分析装置を利用し、1.5406Åの波長(Cu Ka radiation、40kV、100mA)を走査し、2θで15°~64°の範囲、5°/secの走査速度でX線回折パターンを得た。
本発明によるリチウム二次電池用正極の性能を評価するために、下記のような実験を行った。
実施例および比較例で製造された各正極を使用してリチウム二次電池を製造した。具体的に、負極活物質として、天然黒鉛、カーボンブラック導電材およびPVDFバインダーをN-メチルピロリドン溶媒中で85:10:5の重量比で混合して、負極形成用スラリーを製造し、これを銅ホイルに塗布して、負極を製造した。実施例および比較例で製造された各正極と上記で製造された負極の間には、多孔質ポリエチレン(PE)フィルムからなる分離膜(厚さ:約16μm)を介在して積層させて、電極組立体を製造した。製造された電極組立体を電池ケースの内部に位置させた後、ケースの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、電解液は、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の混合体積比が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ホスフェート(LiPF6)を溶解させて製造した。
初期抵抗値の評価と同じ方法で、実施例と比較例で製造された正極をそれぞれ利用してリチウム二次電池を製造した。製造された各リチウム二次電池を対象に、25℃の温度で充電終止電圧4.25V、放電終止電圧2.5V、0.5C/0.5Cの条件で100回充放電(n=100)および200回充放電(n=200)を実施して、容量維持率を測定した。このとき、上記容量維持率は、下記式2を用いて算出し、その結果を下記表2に示した。
容量維持率(%)=(n回充放電時の放電容量/1回充放電時の放電容量)×100
Claims (14)
- 集電体の一面または両面に正極活物質、正極添加剤、導電材およびバインダーを含有する第1スラリーを塗布して、第1合材層を形成する段階と、
第1合材層が形成された集電体に正極活物質、導電材およびバインダーを含有する第2スラリーを塗布して、第2合材層を形成する段階と、を含み、
前記第1合材層および第2合材層を形成する段階は、第1スラリーおよび第2スラリー温度を40℃以下に制御する過程を含み、
前記第1合材層に対するX線回折(XRD)分析時、下記式1を満たす、リチウム二次電池用正極の製造方法:
[式1]
A/B≦1
Aは、2θ=38.5±0.1°の範囲に現れるピークのうち最も強度が強いピークの強度を示し、
Bは、2θ=47.9±0.1°の範囲に現れるピークのうち最も強度が強いピークの強度を示す。 - 前記第1合材層および第2合材層を形成する段階は、第1スラリー温度および第2スラリー温度を10℃~40℃の範囲に制御する過程を含む、請求項1に記載のリチウム二次電池用正極の製造方法。
- 第1合材層を形成する段階後に、第1合材層を圧延する第1圧延段階と、
第2合材層を形成する段階後に、第2合材層を圧延する第2圧延段階と、を含む、請求項1に記載のリチウム二次電池用正極の製造方法。 - 第1圧延段階は、0.5m/s~6m/sの速度で行われ、
第2圧延段階は、2m/s~7m/sの速度で行われ、
前記第2圧延段階が、第1圧延段階よりも速い速度で行われる、請求項3に記載のリチウム二次電池用正極の製造方法。 - 第1圧延段階は、10℃~40℃の温度で行われ、
第2圧延段階は、40℃~100℃温度で行われる、請求項3に記載のリチウム二次電池用正極の製造方法。 - 集電体と、該集電体の一面または両面に形成された合材層と、を含み、
前記合材層は、第1合材層と第2合材層が積層された2層構造であり、
前記第1合材層は、正極活物質、正極添加剤、導電材、およびバインダーを含み、
前記第1合材層に対するX線回折(XRD)分析時、下記式1を満たす、リチウム二次電池用正極:
[式1]
A/B≦1
Aは、2θ=38.5±0.1°の範囲に現れるピークのうち最も強度が強いピークの強度を示し、
Bは、2θ=47.9±0.1°の範囲に現れるピークのうち最も強度が強いピークの強度を示す。 - 正極添加剤は、下記化学式1で示すリチウムコバルト酸化物である、請求項6に記載のリチウム二次電池用正極:
[化学式1]
LipCo(1-q)M1 qO4
前記化学式1中、
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5である。 - 正極添加剤は、空間群がP42/nmcである正方晶系構造を有する、請求項7に記載のリチウム二次電池用正極。
- 正極添加剤の含有量は、第1合材層全重量に対して0.1~5重量%である、請求項6に記載のリチウム二次電池用正極。
- 正極活物質は、下記化学式2で示すリチウムニッケル複合酸化物である、請求項6に記載のリチウム二次電池用正極:
[化学式2]
Lix[NiyCozMnwM2 v]Ou
前記化学式2中、
M2は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
x、y、z、w、vおよびuは、それぞれ1.0≦x≦1.30、0.1≦y<0.95、0.01<z≦0.5、0.01<w≦0.5、0≦v≦0.2、1.5≦u≦4.5である。 - 第1合材層の平均厚さD1が、0.1μm~20μmの範囲にあり、
第2合材層の平均厚さD2が、50μm~300μmの範囲にある、請求項6に記載のリチウム二次電池用正極。 - 請求項6に記載の正極と、負極と、前記正極と負極の間に位置する分離膜と、を含むリチウム二次電池。
- 負極は、負極集電体と、該負極集電体上に位置し、負極活物質を含有する負極合材層と、を備え、
前記負極活物質は、炭素物質およびシリコン物質を含有する、請求項12に記載のリチウム二次電池。 - シリコン物質は、負極合材層100重量部に対して1~20重量部で含まれる、請求項13に記載のリチウム二次電池。
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