JP2021086830A - 正極活物質およびこれを含むリチウム二次電池 - Google Patents
正極活物質およびこれを含むリチウム二次電池 Download PDFInfo
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- JP2021086830A JP2021086830A JP2020187914A JP2020187914A JP2021086830A JP 2021086830 A JP2021086830 A JP 2021086830A JP 2020187914 A JP2020187914 A JP 2020187914A JP 2020187914 A JP2020187914 A JP 2020187914A JP 2021086830 A JP2021086830 A JP 2021086830A
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明の一態様によれば、リチウムのインターカレーション/デインターカレーションが可能な一次粒子および前記一次粒子が凝集した二次粒子を含む正極活物質が提供される。
M1は、MnおよびAlから選ばれる少なくとも1つであり、
M2は、P、Sr、Ba、B、Ti、Zr、Mn、Al、W、Ce、Hf、Ta、Cr、F、Mg、Cr、V、Fe、Zn、Si、Y、Ga、Sn、Mo、Ge、Nd、GdおよびCuから選ばれる少なくとも1つであり、
M1とM2は、互いに異なる元素であり、
0.5≦w≦1.5、0≦x≦0.50、0≦y≦0.20、0≦z≦0.20、0<z’≦0.20である)
M1は、MnおよびAlから選ばれる少なくとも1つであり、
M2は、P、Sr、Ba、B、Ti、Zr、Mn、Al、W、Ce、Hf、Ta、Cr、F、Mg、Cr、V、Fe、Zn、Si、Y、Ga、Sn、Mo、Ge、Nd、GdおよびCuから選ばれる少なくとも1つであり、
M1とM2は、互いに異なる元素であり、
0.5≦w≦1.5、0≦x≦0.50、0≦y≦0.20、0≦z≦0.20、0<z’≦0.20である)
M3は、Ni、Mn、Co、Fe、Cu、Nb、Mo、Ti、Al、Cr、Zr、Zn、Na、K、Ca、Mg、Pt、Au、B、P、Eu、Sm、W、Ce、V、Ba、Ta、Sn、Hf、Ce、GdおよびNdから選ばれる少なくとも1つであり、
0≦a≦10、0≦b≦8、2≦c≦13である)
本発明のさらに他の態様によれば、正極集電体と、前記正極集電体上に形成された正極活物質層とを含む正極が提供され得る。ここで、前記正極活物質層は、本発明の多様な実施例による正極活物質を含むことができる。したがって、 正極活物質は、前述したところと同一なので、便宜上、具体的な説明を省略し、以下では、残りの前述しない構成のみについて説明することとする。
(1)実施例1
共沈法(co−precipitation method)により球形のNi0.80Co0.10Mn0.10(OH)2水酸化物前駆体を合成した。具体的に、90L級の反応器で硫酸ニッケル、硫酸コバルトおよび硫酸マンガンを80:1:1のモル比で混合した1.5Mの複合遷移金属硫酸水溶液に25wt%のNaOHと30wt%のNH4OHを投入した。反応器内のpHは、11.5を維持させ、この際の反応器の温度は、60℃に維持し、不活性ガスであるN2を反応器に投入して、製造された前駆体が酸化しないようにした。合成撹拌の完了後に、Filter press(F/P)装備を用いて洗浄および脱水を進めて、Ni0.8Co0.1Mn0.1(OH)2水酸化物前駆体を収得した。
前記Nb含有原料物質(Nb2O5)が焼成前に全体組成物のうち1.0mol%になるように混合した後、焼成炉でO2雰囲気を維持しつつ、860℃まで分当たり1℃で昇温して熱処理したことを除いて、実施例1と同じ方法で正極活物質を製造した。
共沈法(co−precipitation method)により球形のNi0.94Co0.03Mn0.03(OH)2水酸化物前駆体を合成した後、これにLiOHおよびNb含有原料物質(Nb2O5)を添加した後、焼成して、リチウム複合酸化物を製造するものの、前記Nb含有原料物質(Nb2O5)が焼成前に全体組成物のうち1.0mol%になるように混合した後、焼成炉でO2雰囲気を維持しつつ、780℃まで分当たり1℃で昇温して熱処理したことを除いて、実施例1と同じ方法で正極活物質を製造した。
前記Nb含有原料物質(Nb2O5)を焼成前に混合せず、焼成炉でO2雰囲気を維持しつつ、810℃まで分当たり1℃で昇温して熱処理したことを除いて、実施例1と同じ方法で正極活物質を製造した。
前記Nb含有原料物質(Nb2O5)を焼成前に全体組成物のうち2.0mol%になるように混合した後、焼成炉でO2雰囲気を維持しつつ、860℃まで分当たり1℃で昇温して熱処理したことを除いて、実施例1と同じ方法で正極活物質を製造した。
前記Nb含有原料物質(Nb2O5)が焼成前に全体組成物のうち0.5mol%になるように混合した後、焼成炉でO2雰囲気を維持しつつ、760℃まで分当たり1℃で昇温して熱処理したことを除いて、実施例3と同じ方法で正極活物質を製造した。
前記Nb含有原料物質(Nb2O5)が焼成前に全体組成物のうち2.0mol%になるように混合した後、焼成炉でO2雰囲気を維持しつつ、820℃まで分当たり1℃で昇温して熱処理したことを除いて、実施例3と同じ方法で正極活物質を製造した。
合成された前駆体にLiOHおよびNb含有原料物質(Nb2O5)を全体組成物のうち0.5mol%になるように混合した後、焼成炉でO2雰囲気を維持しつつ、830℃まで分当たり5℃で昇温して15時間の間熱処理した後、自然冷却して、リチウム複合酸化物を得たことを除いて、実施例1と同じ方法で正極活物質を製造した。
合成された前駆体にLiOHおよびNb含有原料物質(Nb2O5)を全体組成物のうち0.5mol%になるように混合した後、焼成炉でO2雰囲気を維持しつつ、830℃まで分当たり1℃で昇温して、20時間の間熱処理した後、自然冷却して、リチウム複合酸化物を得たことを除いて、実施例1と同じ方法で正極活物質を製造した。
製造例1によって製造された正極活物質それぞれ94wt%、カーボンブラック(carbon black)3wt%、PVDFバインダー3wt%をN−メチル−2ピロリドン(NMP)30gに分散させて、正極スラリーを製造した。前記正極スラリーを厚さ15μmの正極集電体であるアルミニウム(Al)薄膜に塗布および乾燥し、ロールプレス(roll press)を実施して、正極を製造した。正極のローディングレベルは、10mg/cm2であり、電極密度は、3.2g/cm3であった。
実施例1、比較例1および比較例2による正極活物質(二次粒子)それぞれをCross−section Polisher(加速電圧5.0kV、4時間ミーリング)で断面処理した後、断面TEM写真を得た。ここで、前記正極活物質の平均粒径は、10μmであり、断面TEM写真上で前記正極活物質の最表面からの距離が0〜4μmである領域を表面部(第1領域)と定義し、前記正極活物質の真ん中から0〜2μmである領域を中心部(第2領域)と定義した。
W2:第2領域(正極活物質の真ん中から0〜2μmである領域)内全体一次粒子の平均縦横比
W3:第1領域内一次粒子のうちW1より小さい縦横比を有する一次粒子の平均縦横比
W4:第1領域内一次粒子のうちW1より大きい縦横比を有する一次粒子の平均縦横比
P:第1領域内一次粒子のうちW1より小さい縦横比を有する一次粒子の比率
製造例2によって製造されたリチウム二次電池を電気化学分析装置(Toyo、Toscat−3100)を利用して25℃、電圧範囲3.0V〜4.3V、0.2C〜5.0Cの放電率を適用して充放電実験を実施して、初期充電容量、初期放電容量、初期可逆効率およびレート特性を測定した。
Claims (14)
- リチウムのインターカレーション/デインターカレーションが可能な一次粒子および前記一次粒子が凝集した二次粒子を含み、
前記一次粒子の平均縦横比は、前記二次粒子の中心部から前記二次粒子の表面部に向かって増加する勾配を有し、かつ
前記一次粒子内金属ドーパントの含量が増加するに従って前記二次粒子の表面部内全体一次粒子の平均縦横比と前記二次粒子の中心部内全体一次粒子の平均縦横比の差異が減少する、正極活物質。 - 前記二次粒子の中心部から前記二次粒子の表面部までの距離をR、前記二次粒子の中心部からの距離が4/5R〜Rである領域を第1領域(R1)、前記二次粒子の中心部からの距離が0〜2/5Rである領域を第2領域(R2)というとき、
前記第1領域内全体一次粒子の平均縦横比(W1)と前記第2領域内全体一次粒子の平均縦横比(W2)の比(W1/W2)は、2.217未満である、請求項1に記載の正極活物質。 - 前記平均縦横比(W1)と前記平均縦横比(W2)の比(W1/W2)は、1.280超過である、請求項2に記載の正極活物質。
- 前記第1領域内一次粒子のうち前記平均縦横比(W1)より小さい縦横比を有する一次粒子の比率は、45%以上である、請求項2に記載の正極活物質。
- 前記第1領域内一次粒子のうち前記平均縦横比(W1)より小さい縦横比を有する一次粒子の平均縦横比(W3)と前記平均縦横比(W2)の比(W3/W2)は、0.984超過1.465未満である、請求項4に記載の正極活物質。
- 前記第1領域内一次粒子のうち前記平均縦横比(W1)より大きい縦横比を有する一次粒子の平均縦横比(W4)と前記平均縦横比(W2)の比(W4/W2)は、1.793超過3.076未満である、請求項4に記載の正極活物質。
- 前記平均縦横比(W1)は、4.083未満である、請求項2に記載の正極活物質。
- 前記平均縦横比(W2)は、1.842未満である、請求項2に記載の正極活物質。
- 前記金属ドーパントは、Nbを含む、請求項1に記載の正極活物質。
- 前記一次粒子は、下記の化学式1で表される、請求項9に記載の正極活物質。
LiwNi1−(x+y+z+z’)CoxM1yM2zNbz’O2 [化学式1]
(ここで、
M1は、MnおよびAlから選ばれる少なくとも1つであり、
M2は、P、Sr、Ba、B、Ti、Zr、Mn、Al、W、Ce、Hf、Ta、Cr、F、Mg、Cr、V、Fe、Zn、Si、Y、Ga、Sn、Mo、Ge、Nd、GdおよびCuから選ばれる少なくとも1つであり、
M1とM2は、互いに異なる元素であり、
0.5≦w≦1.5、0≦x≦0.50、0≦y≦0.20、0≦z≦0.20、0<z’≦0.20である) - 前記平均縦横比(W1)と前記平均縦横比(W2)の比(W1/W2)は、前記z’が増加するに従って減少する、請求項10に記載の正極活物質。
- 前記一次粒子間の界面および前記二次粒子の表面から選ばれる領域のうち少なくとも一部をカバーするコーティング層を含み、
前記コーティング層は、下記の化学式2で表される少なくとも1つの酸化物を含む、請求項1に記載の正極活物質。
LiaM3bOc [化学式2]
(ここで、M3は、Ni、Mn、Co、Fe、Cu、Nb、Mo、Ti、Al、Cr、Zr、Zn、Na、K、Ca、Mg、Pt、Au、B、P、Eu、Sm、W、Ce、V、Ba、Ta、Sn、Hf、Ce、GdおよびNdから選ばれる少なくとも1つであり、0≦a≦10、0≦b≦8、2≦c≦13である) - 請求項1〜12のいずれか1項に記載の正極活物質を含む正極。
- 請求項13に記載の正極を使用するリチウム二次電池。
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