JP5404911B2 - リチウム2次電池用負極活物質、その製造方法、及びこれを含むリチウム2次電池 - Google Patents
リチウム2次電池用負極活物質、その製造方法、及びこれを含むリチウム2次電池 Download PDFInfo
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- JP5404911B2 JP5404911B2 JP2012505793A JP2012505793A JP5404911B2 JP 5404911 B2 JP5404911 B2 JP 5404911B2 JP 2012505793 A JP2012505793 A JP 2012505793A JP 2012505793 A JP2012505793 A JP 2012505793A JP 5404911 B2 JP5404911 B2 JP 5404911B2
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- active material
- negative electrode
- electrode active
- secondary battery
- lithium secondary
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- 229910052744 lithium Inorganic materials 0.000 title claims description 208
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 207
- 239000007773 negative electrode material Substances 0.000 title claims description 164
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 96
- 229910052799 carbon Inorganic materials 0.000 claims description 92
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 54
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 44
- 229910052710 silicon Inorganic materials 0.000 claims description 44
- 239000011148 porous material Substances 0.000 claims description 41
- 239000010703 silicon Substances 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 29
- 125000000524 functional group Chemical group 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- 125000000962 organic group Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
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- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
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- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910008859 Sn—Y Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
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- 229910021473 hassium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
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- 150000002641 lithium Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
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- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
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- 229910021481 rutherfordium Inorganic materials 0.000 claims description 3
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- 229910052711 selenium Inorganic materials 0.000 claims description 3
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- 229910052713 technetium Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
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- 229910008326 Si-Y Inorganic materials 0.000 claims description 2
- 229910006773 Si—Y Inorganic materials 0.000 claims description 2
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- 239000010410 layer Substances 0.000 description 64
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 18
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- 239000011230 binding agent Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
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- 239000002002 slurry Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Description
(ブチル基に改質されたシリコンの製造)
SiCl4(純度99.999%、アルドリッチ社)30g及び1,2−ジメトキシエタン100gを完全に混合した後、この混合液をナトリウムナフタレニド(sodium naphthalenide)溶液でデカントして、400℃で1時間還流させた。得られた溶液をグリニャール試薬であるn−ブチルリチウム40mlと混合して、一晩攪拌した。この時、グリニャール試薬であるn−ブチルリチウムがSiCl4と反応してブチル基に改質されたシリコンが形成された。溶媒及びナフタレンを、回転蒸発器を使用して真空下120℃で加熱することによって除去し、NaCl及びLiCl副産物を過量のn−ヘキサン及び水を使用して除去した。最終的に得られた生成物であるブチル基に改質されたシリコンは、淡い黄色の粘性があるゲルであった。
前記工程により製造されたゲル形態のブチル基に改質されたシリコンを、平均粒子直径が200nmの球形シリカナノ粒子と混合した。この時、前記製造されたブチル基に改質されたシリコン及び前記球形シリカナノ粒子は70:30(ブチル基に改質されたシリコン:球形シリカナノ粒子)の重量比になるように混合した。
(リチウム2次電池用負極活物質の製造)
粒子直径が200nmである球形シリカナノ粒子を使用して、実施例1と同様な方法で製造されたブチル基に改質されたシリコン及び前記球形シリカナノ粒子を70:30(ブチル基に改質されたシリコン:球形シリカナノ粒子)の重量比になるように混合した。
(リチウム2次電池用負極活物質の製造)
粒子直径が200nmである球形シリカナノ粒子を使用して、実施例1と同様な方法で製造されたブチル基に改質されたシリコン及び前記球形シリカナノ粒子を70:30(ブチル基に改質されたシリコン:球形シリカナノ粒子)の重量比になるように混合した。
(リチウム2次電池用負極活物質の製造)
粒子直径が300nmである球形シリカナノ粒子を使用して、実施例1と同様な方法で製造されたブチル基に改質されたシリコン及び前記球形シリカナノ粒子を70:30(ブチル基に改質されたシリコン:球形シリカナノ粒子)の重量比になるように混合した。
(リチウム2次電池用負極活物質の製造)
粒子直径が300nmである球形シリカナノ粒子を使用して、実施例1と同様な方法で製造されたブチル基に改質されたシリコン及び前記球形シリカナノ粒子を70:30(ブチル基に改質されたシリコン:球形シリカナノ粒子)の重量比になるように混合した。
(リチウム2次電池用負極活物質の製造)
粒子直径が200nmである球形シリカナノ粒子を使用して、実施例1と同様な方法で製造されたブチル基に改質されたシリコン及び前記球形シリカナノ粒子を70:30(ブチル基に改質されたシリコン:球形シリカナノ粒子)の重量比になるように混合した。
(リチウム2次電池用負極活物質の製造)
粒子直径が200nmである球形シリカナノ粒子を使用して、実施例1と同様な方法で製造されたブチル基に改質されたシリコン及び前記球形シリカナノ粒子を70:30(ブチル基に改質されたシリコン:球形シリカナノ粒子)の重量比になるように混合した。
シリコン粉末(シグマアルドリッチ社、20ミクロン)及び天然黒鉛を利用して、800rpmで8時間ボールミリングして、炭素コーティングされたシリコン粒子を製造し、後にこれをリチウム2次電池用負極活物質として使用した。この時、前記炭素コーティングされたシリコン粒子において、炭素:シリコンの重量比は44:56であった。
Si0.7B0.3金属固溶体粉末(BET比表面積:16m2/g、平均粒径:0.2ミクロン)、繊維状炭素(BET比表面積:35m2/g、平均長さ:2ミクロン、平均直径:0.08ミクロン)、及びポリビニルピロリドン10gをエタノール1リットルに混合して、湿式ジェットミルで追加混合して、スラリーを製造した。スラリーの製造に利用したSi0.7B0.3金属固溶体粉末及び繊維状炭素(CF)の総重量は100gとし、重量比は70:30とした。次に、スラリーに対してスプレードライ法(2000℃の雰囲気温度)を適用して複合粒子を形成した。複合粒子の平均粒径は10μmであった。
実施例1で製造されたリチウム2次電池用負極活物質をX線光電子分光器で分析した。その結果を図2に示した。X線光電子分光器によれば、シリカの場合、110eV及び105eVで2つの支配的なピークを示す。しかし、図2によれば、前記110eV及び105eVでのピークは観察されず、SiOx(0<x<2)を示す104eVでの弱いピークが観察され、且つSiを示す100eVでの強いピークが観察された。これによって、実施例1の負極活物質では、炭素層の表面のシリカ粒子が全て除去されたことが確認された。前記100eVでの強いピークは、コアに含まれているシリコンを示すものであり、104eVでの弱いピークは、前記コアに一部のSiOx(0<x<2)が存在することを示すものである。
実施例1で、熱処理段階直後のシリコンを含むコアの表面に形成された炭素層にシリカナノ粒子が導入されている複合体のSEM写真を撮影して確認した。その結果を図3aないし図3cに示した。図3aないし図3cによれば、前記炭素層の表面に互いに連結されたシリカナノ粒子が導入されていることが確認された。
実施例1により製造されたリチウム2次電池用負極活物質を炭素コーティングされた銅グリッド上に蒸着させることによって試料を製造し、その断面のTEM写真を撮影した。その結果を図6aに示した。また、SADP(selected area diffraction pattern)の結果を図6bに示した。
実施例1で前記コアの表面に形成された炭素層の配列程度(ordering)を調べるために、前記リチウム2次電池用負極活物質のSERS(surface enhanced Raman spectra)を分析した。ラマンスペクトル分析は、Renishaw 2000 Raman microscope system及び632.8nmレーザー励起(laser excitation)を使用して測定し、レーザー熱効果を避けるために、低いレーザー出力密度及び30秒の露出時間で50倍光学レンズを使用して測定した。その結果を図8に示した。
実施例1で製造されたリチウム2次電池用負極活物質のX線回折分析を実施した。その結果を図9に示した。
実施例1で製造されたリチウム2次電池用負極活物質の表面積を調べるために、Micrometrics ASAP 2020 systemで窒素等温吸着実験を実施した。その結果を図11に示した。図11で、下側の線は窒素気体の吸着曲線であり、上側の線は窒素気体の脱着曲線である。
実施例1〜5により製造されたリチウム2次電池用負極活物質、スーパーPカーボンブラック、及びポリ(ビニリデンフルオライド)バインダーを80:10:10の重量比でN−メチルピロリドン溶媒中で混合して、負極活物質スラリーを製造した。前記製造された負極活物質スラリーを50μmの厚さの銅ホイルにコーティングして、150℃で20分乾燥した後、ロールプレスして、負極を製造した。
前記参考例1〜2により製造されたリチウム2次電池用負極活物質を使用したことを除いては、実施例6〜10と同様な方法で参考例3〜4の半電池を製造した。
前記比較例1〜2により製造されたリチウム2次電池用負極活物質を使用したことを除いては、実施例6〜10と同様な方法で比較例3〜4の半電池を製造した。
実施例6〜10、参考例3及び4、比較例3及び4で製造された半電池を1.5ないし0Vで且つ0.2C(400mA/g)で100回充放電を実施して、1回、30回、70回、及び100回充放電時の特性を測定した。その結果を表1ないし表3に示した。
実施例6〜10、参考例3及び4、比較例3及び4で製造された半電池を1.5ないし0Vで且つ0.2C(400mA/g)、1C(2000mA/g)で100回充放電を実施して、その結果を図12a〜12iに順次に示した。
実施例6〜10の半電池を1.5ないし0Vで、且つ0.2C、1C、2C、及び3Cで各々1回充放電を実施して、率別特性を測定した。その結果、充電容量は各々0.2Cで2600〜2774mAh/gであり、1Cで2430〜2600mAh/gであり、2Cで2150〜2373mAh/gであり、3Cで1875〜2015mAh/gであり、0.2C充電容量に対する3C充電容量比は73%であった。
Claims (28)
- リチウムをドープ及び脱ドープすることができる物質を含むコアと、
前記コアの表面に形成された炭素層と、を含み、
前記炭素層は、厚さが40ないし150nmの気孔壁を間において前記炭素層上に規則的に配列された平均直径100ないし300nmのナノ気孔を含む3次元多孔性構造からなる、リチウム2次電池用負極活物質。 - 100eVまたは104eVで特徴的なピークが示され、105eVまたは110eVで実質的なピークが示されないX線光電子分光スペクトル(XPS)で表示される、請求項1に記載のリチウム2次電池用負極活物質。
- 充放電実施後の前記ナノ気孔の平均直径は30ないし150nmである、請求項1に記載のリチウム2次電池用負極活物質。
- 充放電実施後の前記ナノ気孔の間の気孔壁の厚さは40ないし120nmである、請求項1に記載のリチウム2次電池用負極活物質。
- 前記リチウムをドープ及び脱ドープすることができる物質は、Si、SiOx(0<x<2)、Si−Y1合金、Sn、SnO2、Sn−Y2、Sb、及びGeからなる群より選択される1種以上の第14族または第15族元素含有物質を含み、前記Y1及びY2は、アルカリ金属、アルカリ土類金属、第13族元素、第14族元素、遷移金属、及び希土類元素からなる群より選択される1種以上の元素であり、前記Y1はSiではなく、前記Y2はSnではないことを特徴とする、請求項1に記載のリチウム2次電池用負極活物質。
- 前記元素Y1及びY2は、Mg、Ca、Sr、Ba、Ra、Sc、Y、Ti、Zr、Hf、Rf、V、Nb、Ta、Db、Cr、Mo、W、Sg、Tc、Re、Bh、Fe、Pb、Ru、Os、Hs、Rh、Ir、Pd、Pt、Cu、Ag、Au、Zn、Cd、B、Al、Ga、Si、Sn、In、Ti、Ge、P、As、Sb、Bi、S、Se、Te、及びPoからなる群より選択される1種以上のシリコンまたは錫と結合可能な元素である、請求項5に記載のリチウム2次電池用負極活物質。
- 前記コアに含まれる、リチウムをドープ及び脱ドープすることができる物質は、複数の粒子で存在し、前記複数の粒子の間に炭素物質がさらに含まれる、請求項1に記載のリチウム2次電池用負極活物質。
- 前記コアは、前記リチウムをドープ及び脱ドープすることができる物質の酸化物をさらに含む、請求項1に記載のリチウム2次電池用負極活物質。
- 前記コアに含まれる、リチウムをドープ及び脱ドープすることができる物質は、結晶性構造からなり、前記結晶性構造を形成する結晶性グレインの平均直径は20ないし100nmである、請求項1に記載のリチウム2次電池用負極活物質。
- 充放電実施後の前記コアに含まれる、リチウムをドープ及び脱ドープすることができる物質は、無定形マトリックスに結晶性グレインが分散している構造からなる、請求項1に記載のリチウム2次電池用負極活物質。
- 前記分散している結晶性グレインの平均直径は2ないし5nmである、請求項10に記載のリチウム2次電池用負極活物質。
- 前記炭素層の厚さは1ないし30nmである、請求項1に記載のリチウム2次電池用負極活物質。
- 前記炭素層は、不規則に配列された炭素を含む、請求項1に記載のリチウム2次電池用負極活物質。
- 前記炭素層のラマンスペクトルの積分強度比であるD/G(I(1360)/I(1580))は0.1ないし2である、請求項13に記載のリチウム2次電池用負極活物質。
- 前記リチウム2次電池用負極活物質の総量に対して5ないし40重量%の炭素を含む、請求項1に記載のリチウム2次電池用負極活物質。
- 前記リチウム2次電池用負極活物質の比表面積は50ないし200m2/gである、請求項1に記載のリチウム2次電池用負極活物質。
- リチウムをドープ及び脱ドープすることができる物質を有機作用基に改質する段階と、
前記有機作用基に改質されたリチウムをドープ及び脱ドープすることができる物質を無機酸化物と混合する段階と、
前記混合物を熱処理する段階と、
前記無機酸化物を除去する段階と、を含むリチウム2次電池用負極活物質の製造方法。 - 前記熱処理段階後に、前記リチウムをドープ及び脱ドープすることができる物質の表面に炭素層が形成され、このような炭素層上に無機酸化物粒子が導入されている構造が形成される、請求項17に記載のリチウム2次電池用負極活物質の製造方法。
- 前記有機作用基はCnHmで示される有機基であり、前記n及びmは1以上の整数である、請求項17に記載のリチウム2次電池用負極活物質の製造方法。
- 前記有機作用基は、炭素数1ないし30の脂肪族有機基、炭素数3ないし30の脂環族有機基、及び炭素数6ないし30の芳香族有機基からなる群より選択される、請求項19に記載のリチウム2次電池用負極活物質の製造方法。
- 前記無機酸化物は、シリカ、アルミナ、チタン、セリア、及びジルコニアからなる群より選択される1種以上の不活性無機酸化物を含む、請求項17に記載のリチウム2次電池用負極活物質の製造方法。
- 前記無機酸化物は、前記有機作用基に改質されたリチウムをドープ及び脱ドープすることができる物質100重量部に対して10ないし80重量部で添加される、請求項17に記載のリチウム2次電池用負極活物質の製造方法。
- 前記有機作用基に改質されたリチウムをドープ及び脱ドープすることができる物質は、ゲル形態を帯びている、請求項17に記載のリチウム2次電池用負極活物質の製造方法。
- 前記熱処理段階は、真空または不活性雰囲気下で実施する、請求項17に記載のリチウム2次電池用負極活物質の製造方法。
- 前記熱処理段階は700ないし1200℃で実施される、請求項17に記載のリチウム2次電池用負極活物質の製造方法。
- 前記無機酸化物を除去する段階は塩基性または酸性物質を使用して実施される、請求項17に記載のリチウム2次電池用負極活物質の製造方法。
- 正極活物質を含む正極と、
負極活物質を含む負極と、
電解質と、を含み、
前記負極活物質は、請求項1ないし請求項16のうちのいずれか一項によるリチウム2次電池用負極活物質である、リチウム2次電池。 - 30回以上充放電したとき、94%以上のクーロン効率を有する請求項27に記載のリチウム2次電池。
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