JP5200339B2 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- JP5200339B2 JP5200339B2 JP2006167201A JP2006167201A JP5200339B2 JP 5200339 B2 JP5200339 B2 JP 5200339B2 JP 2006167201 A JP2006167201 A JP 2006167201A JP 2006167201 A JP2006167201 A JP 2006167201A JP 5200339 B2 JP5200339 B2 JP 5200339B2
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/386—Silicon or alloys based on silicon
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- H01M4/387—Tin or alloys based on tin
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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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
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- 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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Description
次に、本発明を実施例および比較例に基づいて具体的に説明する。なお、下記の実施例は本発明の好ましい形態を例示するものであり、本発明が下記の実施例に限られるものではない。本実施例では、多孔質導電性基材と各種の負極活物質と導電材を含む成型体についての検討を行った。
(1)負極活物質の作製
(TiSi2合金)
原料の金属TiはTi粉末(純度99.9%、粒径100μm〜150μm)を用い、Siは、Si粉末(純度99.9%、平均粒径3μm)を用いた。
原料のTiも上記と同じものを用い、SnはSn粉(純度99.9%、平均粒径3μm)を用いて、上記TiSi2と同様にメカニカルアロイ法にて合成した。
市販のSiO(住友チタニウム製)とSnO(高純度化学製)を粉砕し、篩によって、20μmアンダ−に分級した後に使用した。
ここでは、特に、炭素の基材について詳細に検討した。
ここでは、特にカ−ボンナノチュ−ブ(以下、CNTと称する)を用いた。
上記のようにして得られた多孔質導電性基材と負極活物質と導電材とを結着剤とを用いて、以下の要領で負極を作製した。
二酸化マンガンと、水酸化リチウムとを、モル比で2:1の割合で混合し、混合物を空気中で400℃で12時間焼成し、マンガン酸リチウムを得た。
図1に示すような外径6.8mm、厚み2.1mmの寸法を有するコイン型の非水電解質二次電池を作製した。
表1に示すとおり、実施例1のTi−Si合金に対して、多孔質導電性基材を用いない(負極活物質とCNTと結着剤のみからなる)場合と、CNTを用いない(負極活物質と多孔質導電性基材と結着剤のみからなる)場合とについて検討した。それぞれ使用した多孔質導電性基材と導電材は実施例1と同様とした。
20℃に設定した恒温槽の中で、実施例1および比較例1の各電池について定電流充放電を、充電電流2C(1Cは1時間率電流)、放電電流0.2Cで、電池電圧2.0V〜3.3Vの範囲で200サイクル繰り返した。
本実施例では、多孔質導電性基材の種類について検討した。表2に示すとおり、多孔質導電性基材がニッケル、銅、チタン、ステンレスの場合は発泡体あるいは焼結体を用いた。また、負極活物質には実施例1と同じTi−Si合金を用い、導電材としても実施例1と同じCNTを用いた。バインダ−や電極組成比率も実施例1と同じであり、電池の作成方法、評価方法も同じである。
本実施例では、導電材について、特に、粒子状、繊維状の炭素について検討した。
本実施例では、導電材について、特に、粒子状、繊維状の金属(ニッケル、銅、チタン、ステンレス)について検討した。
本実施例では、多孔質導電性基材(炭素)の平均空孔径と粒子状導電材(炭素)の平均径について詳細に検討した。
本実施例では、繊維状導電材(CNT)の平均径が1〜70nm、平均長さが0.01〜70μmについて検討した。
本実施例では、負極体の多孔度について、詳細に検討した。
2 正極缶
3 セパレ−タ
4 負極
5 ガスケット
6 負極缶
Claims (6)
- 正極と負極と非水電解質とを含む非水電解質二次電池であって、前記負極が電極の形態を保持する多孔質導電性基材と、前記多孔質導電性基材の平均空孔径より径の小さい導電材と、リチウムを可逆的に吸蔵放出可能な金属元素および半金属元素からなる群より選ばれる少なくとも1種の元素を含有した単体、合金あるいは化合物とを活物質として含む非水電解質二次電池であって、前記多孔質導電性基材が炭素であり、クロス、フェルトおよびペーパーからなる群より選ばれる少なくとも1種であることを特徴とする非水電解質二次電池。
- 前記導電材がニッケル、銅、チタン、ステンレスおよび炭素からなる群より選ばれる少なくとも1種である請求項1に記載の非水電解質二次電池。
- 前記負極の多孔度が5〜50%である請求項1に記載の非水電解質二次電池。
- 前記負極の活物質がSiまたはSnを少なくとも含むことを特徴とする請求項1記載の非水電解質二次電池。
- 前記合金が少なくとも異なる2相からなり、一方はSiを含む相であり、もう一方は、Ti、Zr、NiおよびCuからなる群より選ばれる少なくとも1種を含む相であり、かつ少なくとも一方の相が、アモルファス状態あるいは低結晶状態から選ばれる少なくとも1種の状態である請求項1に記載の非水電解質二次電池。
- 前記化合物がSiOx(0.1≦x≦2.0)およびSnOy(0.1≦y≦2.0)から選ばれる少なくとも1種である請求項1に記載の非水電解質二次電池。
Priority Applications (2)
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JP2006167201A JP5200339B2 (ja) | 2006-06-16 | 2006-06-16 | 非水電解質二次電池 |
US11/763,091 US20080096110A1 (en) | 2006-06-16 | 2007-06-14 | Negative electrode and non-aqueous electrolyte secondary battery using the same |
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JP2006167201A JP5200339B2 (ja) | 2006-06-16 | 2006-06-16 | 非水電解質二次電池 |
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JP2007335283A JP2007335283A (ja) | 2007-12-27 |
JP5200339B2 true JP5200339B2 (ja) | 2013-06-05 |
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