JP5791432B2 - 正極活物質、その製造方法及びそれを採用した正極並びにリチウム電池 - Google Patents
正極活物質、その製造方法及びそれを採用した正極並びにリチウム電池 Download PDFInfo
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- JP5791432B2 JP5791432B2 JP2011188503A JP2011188503A JP5791432B2 JP 5791432 B2 JP5791432 B2 JP 5791432B2 JP 2011188503 A JP2011188503 A JP 2011188503A JP 2011188503 A JP2011188503 A JP 2011188503A JP 5791432 B2 JP5791432 B2 JP 5791432B2
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Description
[化1]
LixMeyMzPO4−dXd
[化1]
LixMeyMzPO4−dXd
実施例1
常温で、平均粒径200nmのLiFePO4(Phostech Lithium Inc.)300mgを、シリカチューブファーネスに入れ、ファーネス内部を真空状態にした。前記LiFePO4には、カーボン・コーティング層が形成されている。次に、前記ファーネスを真空状態で、10分間常温で300℃まで加熱した後、チャンバ内部を温度300℃及び圧力760Torrで維持しつつ、アンモニアガス(99.98%)を500sccm(standard cubic centimeters per minute)の流速で10分間供給し、その後は流速を下げ、100sccm条件で20分間供給し、全てで30分間窒素ドーピングを行った。窒素ドーピング終了後、アンモニアガス流入を中断させた後、ファーネス内部を再び真空状態にして常温まで冷却させた。
ファーネス内部温度を400℃に維持したことを除いては、実施例1と同じ方法で、正極活物質を製造した。
ファーネス内部温度を500℃に維持したことを除いては、実施例1と同じ方法で、正極活物質を製造した。
ファーネス内部温度を600℃に維持したことを除いては、実施例1と同じ方法で、正極活物質を製造した。
実施例1で使われた平均粒径200nmのLiFePO4(Phostech Lithium Inc.)を窒素ドーピング段階なしにそのまま正極活物質として使用した。
実施例5
実施例1で合成された正極活物質粉末と炭素導電剤(Super P)とを82:10の重量比で均一に混合した後、ポリフッ化ビニリデン(PVDF)結着剤溶液を添加し、活物質:炭素導電剤:結着剤=82:10:8の重量比になるようにスラリを製造した。前記スラリを、ドクターブレードを使用して、アルミニウム集電体上に100μmの間隔をおいて塗布し、120℃で乾燥させて正極板を製造した。
前記実施例1で製造された正極活物質の代りに、前記実施例2で製造された正極活物質を使用したことを除いては、前記実施例5と同じ方法で製造した。
前記実施例1で製造された正極活物質の代りに、前記実施例3で製造された正極活物質を使用したことを除いては、前記実施例5と同じ方法で製造した。
前記実施例1で製造された正極活物質の代りに、前記実施例4で製造された正極活物質を使用したことを除いては、前記実施例5と同じ方法で製造した。
前記実施例1で製造された正極活物質の代りに、前記比較例1の正極活物質を使用したことを除いては、前記実施例5と同じ方法で製造した。
前記実施例1ないし4及び比較例1で製造された正極活物質粉末に対して、XRD(X−ray diffraction)実験を行い、その結果の一部を図1に示した。XRDは、浦項加速機研究所(Pohang Accelerator Laboratory)で、Synchrotron high resolution X−ray sourceを使用して測定した。
前記実施例1ないし4及び比較例1で製造された正極活物質粉末に対して、XPS(X−ray photoelectron spectroscopy)実験を行い、その結果の一部を図2に示した。XPS実験に使われた機器は、PHI社モデルQ2000であり、X−rayソースはmono Al kα(1486.6eV)を使用した。
前記実施例1ないし4及び比較例1で製造された正極活物質粉末に対して常温でメスバウアー分光(Moessbauer spectroscopy)実験を行い、その結果の一部を図3A〜図3C及び下記表2に示した。メスバウアー分光を測定するために、Rhマトリックスに含まれた57Coソースを使用した。測定された値は、標準α−Feホイルをレファレンスとして使用し、補正(calibration)されて図3A〜図3Cに示されている。
前記実施例1〜4及び比較例1で製造された正極活物質粉末に対してTEM実験を行い、その結果の一部を図4Aないし図4Cに示した。
前記実施例5ないし8及び比較例2で製造された前記コインセルを、常温でリチウム金属対比で2.5〜4.1Vの電圧範囲で、0.1Cレートの定電流で充電させつつ、放電時の電流密度が上昇することによる放電容量を図5に示した。放電時の電流密度は、それぞれ0.1C、0.2C、0.5C、1C、2C、5C、10C、20C及び30Cレートであった。
前記実施例5ないし8及び比較例2で製造された前記コインセルを、常温でリチウム金属対比で2.5〜4.1Vの電圧範囲で、50サイクルまでは1Cレートの定電流で充放電させ、51ないし100サイクルで、10Cレートの高率で定電流充放電させつつ放電容量を測定し、その結果を図6に示した。
2 負極
3 正極
4 セパレータ
5 電池ケース
6 キャップアセンブリ
Claims (20)
- オリビン構造を有する材料を含むコアと、
前記コアの少なくとも一部にドーピングされた窒素原子と、を含む正極活物質であって、
前記コアが窒素及び酸素を含み、前記コアが、X線光電スペクトルで、398ないし400eVの結合エネルギーを有する窒素ピーク、及び530ないし534eVの結合エネルギーを有する酸素ピークを示し、前記ピークそれぞれの面積から計算された窒素:酸素の組成比が1:100〜2.44:69.66であることを特徴とする正極活物質。 - 前記コアで、窒素原子がドーピングされた領域が結晶相として存在することを特徴とする請求項1に記載の正極活物質。
- 前記コアが酸化数+3である金属を含み、
前記コアに存在する酸化数+3である金属の含有量が、酸化数+2である金属及び酸化数+3である金属の総含有量の5重量%以下であることを特徴とする請求項1に記載の正極活物質。 - 前記コアが窒素及びリン(P)を含み、前記コアが、X線光電スペクトルで、398ないし400eVの結合エネルギーを有する窒素ピーク、及び132ないし136eVの結合エネルギーを有するリン(P)ピークを示し、前記ピークそれぞれの面積から計算された窒素:リンの組成比が1:100以上であることを特徴とする請求項1に記載の正極活物質。
- 前記窒素:リンの組成比が1:100ないし30:100であることを特徴とする請求項4に記載の正極活物質。
- 前記コアが、X線光電スペクトルで、396ないし398未満eVの結合エネルギーを有する窒素ピークをさらに示すことを特徴とする請求項1に記載の正極活物質。
- 前記コアの平均粒径が1nmないし1,000μmであることを特徴とする請求項1に記載の正極活物質。
- 前記オリビン構造を有する材料が、下記化学式1で表示されることを特徴とする請求項1に記載の正極活物質:
[化1]
LixMeyMzPO4−dXd
前記化学式1で、0.9≦x≦1.1、0.9≦y≦1.1、0≦z≦0.2、0≦d≦0.2であり、
Meは、Fe、Mn、Ni及びCoからなる群から選択される一つ以上であり、
Mは、Mg、Ca、Sr、Ba、Ti、Zr、Nb、Mo、W、Zn、Al及びSiからなる群から選択される一つ以上であり、
Xは、S及びFからなる群から選択される一つ以上である。 - 前記オリビン構造を有する材料が、LiFePO4、LiFe1−aMnaPO4(0<a<1)、及びLiMnPO4からなる群から選択された一つ以上であることを特徴とする請求項1に記載の正極活物質。
- 前記コア上に形成された伝導性炭素を含むコーティング層をさらに含むことを特徴とする請求項1に記載の正極活物質。
- 請求項1から10のいずれか一項に記載の正極活物質の製造方法において、
オリビン構造を有する材料と、窒素前駆体ガスと、を接触させる段階を含む正極活物質の製造方法。 - 前記接触段階で、
前記オリビン構造を有する材料の少なくとも一部に、窒素がドーピングされることを特徴とする請求項11に記載の正極活物質の製造方法。 - 前記窒素前駆体ガスが、アンモニアを含むことを特徴とすることを特徴とする請求項11に記載の正極活物質の製造方法。
- 前記オリビン構造を有する材料が、下記化学式1で表示されることを特徴とする請求項11に記載の正極活物質の製造方法:
[化1]
LixMeyMzPO4−dXd
前記化学式1で、0.9≦x≦1.1、0.9≦y≦1.1、0≦z≦0.2、0≦d≦0.2であり、
Meは、Fe、Mn、Ni及びCoからなる群から選択される一つ以上であり、
Mは、Mg、Ca、Sr、Ba、Ti、Zr、Nb、Mo、W、Zn、Al及びSiからなる群から選択される一つ以上であり、
Xは、S及びFからなる群から選択される一つ以上である。 - 前記オリビン構造を有する材料が、LiFePO4、LiFe1−aMnaPO4(0<a<1)、及びLiMnPO4からなる群から選択された一つ以上であることを特徴とする請求項11に記載の正極活物質の製造方法。
- 前記接触が行われる温度が、300℃ないし400℃であることを特徴とする請求項11に記載の正極活物質の製造方法。
- 前記接触が持続する時間が、1分ないし600分であることを特徴とする請求項11に記載の正極活物質の製造方法。
- 前記オリビン構造を有する材料が、
前記材料上に形成された伝導性炭素を含むコーティング層をさらに含むことを特徴とする請求項11に記載の正極活物質の製造方法。 - 請求項1ないし請求項10のうち、いずれか1項に記載の正極活物質を含む正極。
- 請求項19に記載の正極を採用したリチウム電池。
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