JP6884829B2 - 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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- JP6884829B2 JP6884829B2 JP2019149041A JP2019149041A JP6884829B2 JP 6884829 B2 JP6884829 B2 JP 6884829B2 JP 2019149041 A JP2019149041 A JP 2019149041A JP 2019149041 A JP2019149041 A JP 2019149041A JP 6884829 B2 JP6884829 B2 JP 6884829B2
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- positive electrode
- active material
- electrode active
- lithium
- oxide
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- 229910052744 lithium Inorganic materials 0.000 title claims description 84
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- WYDJZNNBDSIQFP-UHFFFAOYSA-N [O-2].[Zr+4].[Li+] Chemical compound [O-2].[Zr+4].[Li+] WYDJZNNBDSIQFP-UHFFFAOYSA-N 0.000 claims description 10
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- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
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- 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 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
- 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
- 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
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 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
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 238000004448 titration Methods 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
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Description
(実施例1)
共沈法(co−precipitation method)により球形のNi0.92Co0.08(OH)2水酸化物前駆体を合成した。90L級の反応器でNiSO4・7H2OおよびCoSO4・7H2Oを92:8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、フィルタープレス(F/P)装備を利用して洗浄および脱水を進めて、Ni0.92Co0.08(OH)2水酸化物前駆体を収得した。
正極活物質がLi1.04Ni0.897Co0.084Al0.014W0.005O2の組成式を有するように、W含有原料物質(WO3)およびコバルト原料物質(Co(OH)2)と共に混合したことを除いて、実施例1と同じ方法で実施例2による正極活物質を製造した。
正極活物質がLi1.04Ni0.897Co0.079Al0.014W0.005Mg0.005O2の組成式を有するように、W含有原料物質(WO3)およびマグネシウム原料物質(Mg(OH)2)と共に混合したことを除いて、実施例1と同じ方法で実施例3による正極活物質を製造した。
正極活物質がLi1.04Ni0.897Co0.079Al0.014W0.005Mn0.005O2の組成式を有するように、W含有原料物質(WO3)およびマンガン原料物質(Mn(OH)2)と共に混合したことを除いて、実施例1と同じ方法で実施例4による正極活物質を製造した。
正極活物質がLi1.04Ni0.901Co0.079Al0.014W0.005Ti0.001O2の組成式を有するように、W含有原料物質(WO3)およびTi含有原料物質(TiO2)を使用したことを除いて、実施例1と同じ方法で実施例5による正極活物質を製造した。
正極活物質がLi1.04Ni0.904Co0.079Al0.014W0.005Zr0.001O2の組成式を有するように、W含有原料物質(WO3)およびZr含有原料物質(ZrO2)を使用したことを除いて、実施例1と同じ方法で実施例によるの正極活物質を製造した。
正極活物質がLi1.04Ni0.901Co0.078Al0.014W0.005Ti0.001Zr0.001O2の組成式を有するように、正極活物質をW含有原料物質(WO3)、Ti含有原料物質(TiO2)、およびZr含有物質を共に混合したことを除いて、実施例1と同じ方法で実施例7による正極活物質を製造した。
実施例1において正極活物質をW含有原料物質(WO3)と混合した後、600℃で1回だけ熱処理したことを除いて、実施例1と同じ方法で実施例8による正極活物質を製造した。
実施例1で製造された正極活物質をW含有原料物質(WO3)と混合しないことを除いて、実施例1と同じ方法で比較例1による正極活物質を製造した。
Ni0.92Co0.08(OH)2水酸化物前駆体をLi含有原料物質であるLiOHおよびAl含有原料物質であるAl2O3と共にミキサーを用いて混合し、焼成炉でO2雰囲気を維持しつつ、分当たり1℃で昇温して熱処理温度650℃で10時間維持した後、自然冷却した。
比較例2において正極活物質とW含有原料物質(WO3)を混合した後、700℃で1回だけ熱処理したことを除いて、比較例2と同じ方法で比較例3による正極活物質を製造した。
Ni0.92Co0.08(OH)2水酸化物前駆体をLi含有原料物質であるLiOHおよびAl含有原料物質であるAl2O3と共にミキサーを用いて混合し、焼成炉でO2雰囲気を維持しつつ、分当たり1℃で昇温して熱処理温度650℃で10時間維持した後、自然冷却した。
Ni0.92Co0.08(OH)2水酸化物前駆体をLi含有原料物質であるLiOHおよびAl含有原料物質であるAl2O3と共にミキサーを用いて混合し、焼成炉でO2雰囲気を維持しつつ、分当たり1℃で昇温して熱処理温度650℃で10時間維持した後、自然冷却した。
図1〜図4は、実施例7によって製造された正極活物質に対する透過電子顕微鏡(TEM)分析およびTEM/EDSマッピンク結果を示したものであり、図5は、TEM/EDSマッピンク結果によって測定されたドーピング金属元素(Zr、Ti、W)の含量を示すグラフ(line sum spectrum)である。
実施例および比較例によって製造された正極活物質に対してX線回折(XRD)分析を行って、正極活物質のうちリチウム合金酸化物が存在するか否かを確認した。XRD分析は、Cu Kαradiation(1.540598Å)を利用したBruker D8 Advance回折計(diffractometer)を利用して行った。
実施例および比較例によってそれぞれ製造された正極活物質に対する未反応リチウムの測定は、pH滴定(pH titration)によりpH4になるまで使用された0.1MのHClの量で測定した。まず、実施例および比較例によってそれぞれ製造された正極活物質それぞれ5gをDIW 100mlに入れて15分間撹拌した後、フィルタリングし、フィルタリングされた溶液50mlを取った後、これに0.1MのHClを加えてpH変化によるHClの消耗量を測定して、Q1およびQ2を決定し、これを通じて未反応のLiOHおよびLi2CO3を計算した。
M2=73.89(Li2CO3 Molecular weight)
SPL Size=(Sample weight×Solution Weight)/Water Weight
LiOH(wt%)=[(Q1−Q2)×C×M1×100]/(SPL Size×1000)
Li2CO3(wt%)=[2×Q2×C×M2/2×100]/(SPL Size×1000)
実施例および比較例によってそれぞれ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。
前記で製造されたリチウム二次電池(コインセル)に対して25℃で0.15Cの定電流(CC)で4.25Vになるまで充電し、以後、4.25Vの定電圧(CV)で充電して、充電電流が0.05mAhになるまで1回目の充電を行った。以後、20分間放置した後、0.1Cの定電流で3.0Vになるまで放電して、1サイクル目の放電容量を測定した。第1充放電時の充電容量、放電容量および充放電効率を下記の表2に示した。
前記で製造されたリチウム二次電池(コインセル)に対して25℃で1Cの定電流(CC)で3.0V以上4.25V以下の駆動電圧の範囲内で充/放電を100回実施した。これにより、常温での充放電100回実施後、初期容量に対する100サイクル目の放電容量の比率であるサイクル容量維持率(capacity retention)を測定した。
Claims (6)
- 1次粒子と前記1次粒子が凝集して形成された2次粒子とを含むリチウム複合酸化物;と
前記1次粒子間の界面および前記2次粒子の表面のうち少なくとも一部に存在する少なくとも1種のリチウム合金酸化物と;
を含み、かつ
前記リチウム合金酸化物は、前記2次粒子の表面部から前記2次粒子の中心部に向かって減少する濃度勾配を示す、
正極活物質であって、
前記リチウム合金酸化物は、
下記の式2で表される第1リチウム合金酸化物と;
下記の式3で表される少なくとも1種の第2リチウム合金酸化物と;
を含み、
前記第1リチウム合金酸化物および前記第2リチウム合金酸化物は、前記2次粒子の表面部から前記2次粒子の中心部に向かって減少する濃度勾配を示し、
前記第2リチウム合金酸化物の濃度減少率は、前記第1リチウム合金酸化物の濃度減少率より大きい、
正極活物質。
Li d W e O f (式2)
(ここで、0≦d≦6、0<e≦6、0<f≦10である。)
Li g M2 h O i (式3)
(ここで、
M2は、Ti、Zr、Mg、V、B、Mo、Zn、Nb、Ba、Ta、Fe、Cr、Sn、Hf、Ce、NdおよびGdから選ばれる少なくとも一つであり、
0≦g≦6、0<h≦6、0<i≦10である。) - 前記第2リチウム合金酸化物は、
下記の式4で表されるリチウムジルコニウム酸化物と;
下記の式5で表されるリチウムチタン酸化物と;
を含む、
請求項1に記載の正極活物質。
LijZrkOl (式4)
(ここで、0≦j≦6、0<k≦6、0<l≦10である。)
LimTinOp (式5)
(ここで、0≦m≦6、0<n≦6、0<p≦10である。) - 前記リチウムジルコニウム酸化物の濃度減少率は、前記リチウムチタン酸化物の濃度減少率より大きい、
請求項2に記載の正極活物質。 - 前記リチウム複合酸化物を形成する前記1次粒子は、下記の式6で表される、
請求項1に記載の正極活物質。
LiwNi1−(x+y+z)CoxM3yM4zO2 (式6)
(ここで、
M3は、MnおよびAlから選ばれる少なくとも一つであり、
M4は、Ti、Zr、Mg、V、B、Mo、Zn、Nb、Ba、Ta、Fe、Cr、Sn、Hf、Ce、W、NdおよびGdから選ばれる少なくとも一つを含み、
0.5≦w≦1.5、0≦x≦0.50、0≦y≦0.20、0≦z≦0.20である。) - 請求項1〜4のいずれか1項に記載の正極活物質と;
導電材と;
バインダーと;
を含む正極スラリー組成物。 - 請求項1〜4のいずれか1項に記載の正極活物質を含む正極を使用するリチウム二次電池。
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