JP5781267B2 - 非水系二次電池用負極およびそれを用いた非水系二次電池 - Google Patents
非水系二次電池用負極およびそれを用いた非水系二次電池 Download PDFInfo
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- JP5781267B2 JP5781267B2 JP2009231737A JP2009231737A JP5781267B2 JP 5781267 B2 JP5781267 B2 JP 5781267B2 JP 2009231737 A JP2009231737 A JP 2009231737A JP 2009231737 A JP2009231737 A JP 2009231737A JP 5781267 B2 JP5781267 B2 JP 5781267B2
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- 229910052744 lithium Inorganic materials 0.000 claims description 75
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- 239000011148 porous material Substances 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 238000004438 BET method Methods 0.000 claims description 19
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- 239000003575 carbonaceous material Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
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- 239000002904 solvent Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
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- 238000000034 method Methods 0.000 description 66
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 22
- 229910001416 lithium ion Inorganic materials 0.000 description 22
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- 239000004020 conductor Substances 0.000 description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 10
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
(不溶不融性基体(B−1)粉砕物の試作)
フェノール樹脂硬化体320gをステンレス製皿に入れ、この皿を角型炉(400×400×400mm)内に配置して、熱反応に供した。熱反応は、窒素雰囲気下で行い、窒素流量は5リットル/分とした。熱反応は、1℃/分の速度で、炉内温が室温から630℃となるまで昇温し、同温度で4時間保持した後、自然冷却により、60℃まで冷却し、皿を炉から取り出し、本発明の不溶不融性基体(B−1)を得た。収量は192gであった。
得られた不溶不融性基体(B−1)粉砕物10.1gをステンレススチールメッシュ製の籠に入れ、等方性ピッチ(軟化点:270 ℃)106.1gを入れたステンレス製皿の上に置き、角型炉(400×400×400mm)内に配置して、熱処理を行った。熱処理は、窒素雰囲気下で行い、窒素流量は5リットル/分とした。加熱処理は、上記ピッチを680℃ まで昇温し、同温度で4時間保持し、続いて自然冷却により60℃ まで冷却した後、炉から取り出した。若干の凝集が見られたので、乳鉢で解砕し、不溶不融性基体(A−1)を得た。収量は11.65g(15.3%の重量増加)であり、この重量増加は、上記加熱処理により、ピッチを680℃ まで加熱昇温する過程において発生した炭化水素ガスなどの炭素前駆体が、不溶不融性基体(B−1)表面および/又は細孔内で炭素質材料となることによるものである。
(不溶不融性基体(B−2)粉砕物の試作)
フェノール樹脂硬化体367gをステンレス製皿に入れ、この皿を角型炉(400×400×400mm)内に配置して、熱反応に供した。熱反応は、窒素雰囲気下で行い、窒素流量は5リットル/分とした。熱反応は、1℃/分の速度で、炉内温が室温から680℃となるまで昇温し、同温度で4時間保持した後、自然冷却により、60℃まで冷却し、皿を炉から取り出し、本発明の不溶不融性基体(B−2)を得た。収量は226gであった。
得られた不溶不融性基体(B−2)粉砕物16.0gをステンレススチールメッシュ製の籠に入れ、等方性ピッチ(軟化点:270 ℃)17.6gを入れたステンレス製皿の上に置き、角型炉(400×400×400mm)内に配置して、加熱処理を行った。加熱処理は、窒素雰囲気下で行い、窒素流量は5リットル/分とした。加熱処理は、上記ピッチを680℃ まで昇温し、同温度で4時間保持し、続いて自然冷却により60℃ まで冷却した後、炉から取り出し、不溶不融性基体(A−2)を得た。収量は17.6g(10.0%の重量増加)であった。
実施例で得られた不溶不融性基体(B−1)粉砕物を用い負極を試作した。不溶不融性基体(B−1)75重量部および導電材(アセチレンブラック)15重量部およびバインダー(ポリフッ化ビニリデン:PVDF)10重量部をNMP(N−メチル−2−ピロリドン)と混合し、負極合剤スラリーを得た。このスラリーを厚さ18μmの銅箔の片面に塗布し、乾燥した後、プレス加工して電極を得た。
(不溶不融性基体(A−3比較)の試作)
実施例1で得られた不溶不融性基体(B−2)8.21gをステンレススチールメッシュ製の籠に入れ、等方性ピッチ(軟化点:270 ℃)1.25gを入れたステンレス製皿の上に置き、角型炉(400×400×400mm)内に配置して、加熱処理を行った。加熱処理は、窒素雰囲気下で行い、窒素流量は5リットル/分とした。加熱処理は、上記ピッチを680℃ まで昇温し、同温度で4時間保持し、続いて自然冷却により60℃ まで冷却した後、炉から取り出した。若干の凝集が見られたので、乳鉢で解砕し、不溶不融性基体(A−3比較)を得た。収量は8.34g(1.6%の重量増加)であった。
1’ 正極集電体
2 負極層
2’ 負極集電体
3 正参照極
3’ 正参照極リード
4 負参照極
4’ 負参照極リード
5 セパレータ(電解液を含む)
Claims (2)
- 芳香族系縮合ポリマーを非酸化性雰囲気で熱処理し得られる不溶不融性基体を粉砕して得られる平均粒子径が2.0μm以下の不溶不融性基体(B)粉砕物を炭素前駆体の共存下熱処理することにより前記不溶不融性基体(B)粉砕物の細孔の一部あるいは全部を炭素質材料で塞いだ不溶不融性基体(A)を主成分とする非水系二次電池用負極において、前記不溶不融性基体(A)の水素原子/炭素原子比が0.60〜0.05、結晶面002面の面間隔が3.6Å以上、平均粒子径が2.0μm以下、かつBET法による比表面積が41m 2 /g以下、20Å以下の細孔が0.02cc/g以下であり、前記不溶不融性基体(A)に不溶不融性基体(A)の重量あたり500mAh/g以上のリチウムを担持させてあることを特徴とする非水系二次電池用負極。
- 正極、負極、セパレータおよびリチウム塩が非水溶媒に溶解されてなる非水系電解液を具備する非水系二次電池において、請求項1に記載の負極を用いた非水系二次電池。
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