JPWO2015152115A1 - リチウムイオン二次電池 - Google Patents
リチウムイオン二次電池 Download PDFInfo
- Publication number
- JPWO2015152115A1 JPWO2015152115A1 JP2016511861A JP2016511861A JPWO2015152115A1 JP WO2015152115 A1 JPWO2015152115 A1 JP WO2015152115A1 JP 2016511861 A JP2016511861 A JP 2016511861A JP 2016511861 A JP2016511861 A JP 2016511861A JP WO2015152115 A1 JPWO2015152115 A1 JP WO2015152115A1
- Authority
- JP
- Japan
- Prior art keywords
- graphite particles
- active material
- graphite
- secondary battery
- ion secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 136
- 239000010439 graphite Substances 0.000 claims abstract description 136
- 239000007774 positive electrode material Substances 0.000 claims abstract description 39
- 239000007773 negative electrode material Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 24
- 239000011029 spinel Substances 0.000 claims abstract description 24
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- 239000011149 active material Substances 0.000 claims abstract description 11
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- 230000001186 cumulative effect Effects 0.000 claims description 11
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Images
Classifications
-
- 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
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Abstract
Description
前記正極活物質は、Mn系スピネル型複合酸化物と他の活物質を含み、前記正極活物質の全体に対する前記Mn系スピネル型複合酸化物の含有率が60質量%以下であり、
前記負極活物質は、天然黒鉛からなる第1の黒鉛粒子と人造黒鉛からなる第2の黒鉛粒子を含み、前記第1の黒鉛粒子と前記第2の黒鉛粒子の合計に対する該第2の黒鉛粒子の含有率が1〜30質量%の範囲にある、リチウムイオン二次電池が提供される。
本発明の実施形態によるリチウムイオン二次電池に好適な負極としては、例えば、負極集電体上に、第1及び第2の黒鉛粒子を含む前記の負極活物質と結着剤を含む負極活物質層を設けたものを用いることができる。
(式中、A:タッピングセルの質量、B:タッピングセルと黒鉛粉末の合計質量、D:充填容積)。
本発明の実施形態によるリチウムイオン二次電池に好適な正極としては、正極集電体上に、Mn系スピネル型複合酸化物を含む前記の正極活物質と結着剤を含む正極活物質層を設けたものを用いることができる。
本発明の実施形態によるリチウムイオン二次電池は、上記負極と正極と電解質を含む。
黒鉛Aとして球形化された天然黒鉛粒子を用意し、黒鉛Bとして鱗片状の人造黒鉛を用意した。前述の測定方法により、黒鉛Aの平均粒子円形度は0.86以上であり、鱗片状の黒鉛Bの平均粒子円形度より高いことを確認した。また、市販のレーザ回折・散乱方式粒子径分布測定装置を用いて、黒鉛AのD50/D5は1.36以下、D50は10〜20μmの範囲にあり、黒鉛BのD50/D5は1.52より大きく、D50は5〜30μmの範囲にあることを確認した。黒鉛Aと黒鉛Bの飽和タップ密度は、前述の測定方法により測定した結果、それぞれ1.08g/cm3、0.99g/cm3であった。黒鉛Aと黒鉛Bの混合粒子の飽和タップ密度は、1.10g/cm3であった。
負極活物質として天然黒鉛Aのみを用いた以外は実施例1と同様にしてリチウムイオン二次電池を作製した。
負極活物質として天然黒鉛Aのみを用い、正極活物質についてMn系スピネル型複合酸化物(Mnスピネル)と層状岩塩型酸化物の質量比率を70:30に変えた以外は、実施例1と同様にしてリチウムイオン二次電池を作製した。
正極活物質についてMn系スピネル型複合酸化物(スピネル酸化物)と層状岩塩型酸化物の質量比率を70:30に変えた以外は、実施例1と同様にしてリチウムイオン二次電池を作製した。
表1に示されるように、正極活物質中のMn系スピネル型複合酸化物(スピネル酸化物)の含有量が60質量%以下であり、負極活物質が天然黒鉛と人造黒鉛(含有率が1〜30質量%の範囲内)を含むことにより、サイクル特性が改善されることが分かる。
2 負極活物質層
3 正極集電体
4 負極集電体
5 セパレータ
6 ラミネート外装体
7 ラミネート外装体
8 負極タブ
9 正極タブ
Claims (12)
- リチウムイオンを吸蔵放出できる正極活物質を含む正極と、リチウムイオンを吸蔵放出できる負極活物質を含む負極と、非水電解液とを含むリチウムイオン二次電池であって、
前記正極活物質は、Mn系スピネル型複合酸化物と他の活物質を含み、前記正極活物質の全体に対する前記Mn系スピネル型複合酸化物の含有率が60質量%以下であり、
前記負極活物質は、天然黒鉛からなる第1の黒鉛粒子と人造黒鉛からなる第2の黒鉛粒子を含み、前記第1の黒鉛粒子と前記第2の黒鉛粒子の合計に対する該第2の黒鉛粒子の含有率が1〜30質量%の範囲にある、リチウムイオン二次電池。 - 前記第1の黒鉛粒子と前記第2の黒鉛粒子の合計に対する該第2の黒鉛粒子の含有率が2質量%以上10質量%未満の範囲にある、請求項2に記載のリチウムイオン二次電池。
- 前記正極活物質の全体に対する前記Mn系スピネル型複合酸化物の含有率が8質量%以上である、請求項1又は2に記載のリチウムイオン二次電池。
- 前記第1の黒鉛粒子は球形化された粒子からなり、
前記第2の黒鉛粒子は前記第1の黒鉛粒子より平均粒子円形度の低い粒子からなる、請求項1から3のいずれか一項に記載のリチウムイオン二次電池。 - 前記第1の黒鉛粒子は、平均粒子円形度が0.6〜1の範囲にある球形化された粒子からなる、請求項4に記載のリチウムイオン二次電池。
- 前記第2の黒鉛粒子は、鱗片状粒子からなる、請求項4又は5に記載のリチウムイオン二次電池。
- 前記第1の黒鉛粒子の累積分布における累積5%の粒子径(D5)に対するメジアン粒子径(D50)の比D50/D5が、前記第2の黒鉛粒子の累積分布における累積5%の粒子径(D5)に対するメジアン粒子径(D50)の比D50/D5より小さく、
前記第1の黒鉛粒子と前記第2の黒鉛粒子との混合粒子の飽和タップ密度は、前記第1の黒鉛粒子の飽和タップ密度および前記第2の黒鉛粒子の飽和タップ密度のいずれよりも大きい、請求項1から6のいずれか一項に記載のリチウムイオン二次電池。 - 前記第1の黒鉛粒子のD50/D5が1.5以下である、請求項7に記載のリチウムイオン二次電池。
- 前記第2の黒鉛粒子のD50/D5が1.5より大きい、請求項7又は8に記載のリチウムイオン二次電池。
- 前記第1の黒鉛粒子のメジアン粒子径(D50)が10〜20μmの範囲にあり、
前記第2の黒鉛粒子のメジアン粒子径(D50)が5〜30μmの範囲にある、請求項1から9のいずれか一項に記載のリチウムイオン二次電池。 - 前記第1の黒鉛粒子は、非晶質炭素で被覆されている、請求項1から10のいずれか一項に記載のリチウムイオン二次電池。
- 前記正極活物質は、前記の他の活物質として、層状岩塩型酸化物を含む、請求項1から11のいずれか一項に記載のリチウムイオン二次電池。
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