JP6403278B2 - 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
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Description
したがって、高温下で正極活物質としてリチウム・ニッケル系複合酸化物を用いたときに、正極の劣化が防止され、かつ負極に形成された被膜による効果により電池のサイクル寿命(放電容量維持率)が向上するリチウムイオン二次電池を提供することを目的とする。
負極活物質として、負極活物質として、BET比表面積3.4m2/gの黒鉛粉末を用いた。この黒鉛粉末と、導電助剤としてBET比表面積62m2/gのカーボンブラック粉末(以下、「CB」と称する。)と、バインダー樹脂としてカルボキシメチルセルロース(以下、「CMC」と称する。)およびスチレンブタジエン共重合体ラテックス(以下、「SBR」と称する。)とを、固形分質量比でCB:CMC:SBR=0.3:1.0:2.0の割合で混合しイオン交換水に添加して撹拌し、これらの材料を水中に均一に分散させてスラリーを作製した。得られたスラリーを、負極集電体となる厚み10μmの銅箔上に塗布した。次いで、125℃にて10分間、電極を加熱し、水を蒸発させることにより負極活物質層を形成した。更に、負極活物質層をプレスすることによって、負極集電体の片面上に負極活物質層を塗布した負極を作製した。
負極活物質としてBET比表面積4.5m2/gの非晶質性炭素粉末(ハードカーボン)を使用したこと以外は、上記の負極の作製方法と同様に負極を作製した。この負極を比較例1の電池に使用した。
また、負極活物質としてBET比表面積4.5m2/gの黒鉛粉末を使用したこと以外は、上記の負極の作製方法と同様に負極を作製した。この負極を比較例2の電池に使用した。
正極活物質としてニッケル・コバルト・マンガン酸リチウム(NCM523、すなわちニッケル:コバルト:マンガン=5:2:3、リチウム/メタル比=1.04、BET比表面積0.67m2/g)とリチウム・マンガン酸化物(LiMn2O4)とを70:30(重量比)で混合した混合酸化物と、導電助剤としてBET比表面積62m2/gのCBと、BET比表面積22m2/gの黒鉛粉末(GR)と、バインダー樹脂としてポリフッ化ビニリデン(PVDF)とを、固形分質量比でCB:GR:PVDFが3:1:3の割合となるように、溶媒であるN−メチルピロリドン(以下、「NMP」と称する。)に添加した。さらに、この混合物に有機系水分捕捉剤として無水シュウ酸(分子量90)を、上記混合物からNMPを除いた固形分100質量部に対して0.03質量部添加した上で遊星方式の分散混合を30分間実施することで、これらの材料を均一に分散させてスラリーを作製した。得られたスラリーを、正極集電体となる厚み20μmのアルミニウム箔上に塗布した。次いで、125℃にて10分間、電極を加熱し、NMPを蒸発させることにより正極活物質層を形成した。さらに、正極活物質層をプレスすることによって、正極集電体の片面上に正極活物質層を塗布した正極を作製した。
耐熱微粒子としてアルミナを用いた厚さ5μmの耐熱微粒子層とポリプロピレンからなる厚さ25μmのオレフィン系樹脂層とから構成されるセラミックセパレータを使用した。
非水電解液として、非水電解液として、エチレンカーボネート(以下、「EC」と称する。)とジエチルカーボネート(以下、「DEC」と称する。)とエチルメチルカーボネート(以下、「EMC」と称する。)とをEC:DEC:EMC=30:60:10(体積比)の割合で混合した非水溶媒に、電解質塩としての六フッ化リン酸リチウム(LiPF6)を濃度が0.9mol/Lとなるように溶解させたものに対して、添加剤として環状ジスルホン酸エステル(メチレンメタンジスルホンネート(MMDS);添加剤Aと、ビニレンカーボネート(VC);添加剤Bと、フルオロエチレンカーボネート(FEC);添加剤Cとを、それぞれ各割合で溶解させたものを用いた。各実施例の電池に用いた添加剤の組成は、仕込み添加剤の総量を100%として、表1のようになる。
上記のように作製した各負極と正極を、各々所定サイズの矩形に切り出した。このうち、端子を接続するための未塗布部にアルミニウム製の正極リード端子を超音波溶接した。同様に、正極リード端子と同サイズのニッケル製の負極リード端子を負極板における未塗布部に超音波溶接した。厚さ25μmのポリプロピレン多孔質セパレータの両面に上記負極板と正極板とを両活物質層がセパレータを隔てて重なるように配置して電極板積層体を得た。2枚のアルミニウムラミネートフィルムの長辺の一方を除いて三辺を熱融着により接着して袋状のラミネート外装体を作製した。ラミネート外装体に上記電極積層体を挿入した。電解液を注液して真空含浸させた後、減圧下にて開口部を熱融着により封止することによって、積層型リチウムイオン電池を得た。この積層型リチウムイオン電池について高温エージングを数回行い、電池容量5Ahの積層型リチウムイオン電池を得た。
電池の残容量(以下、「SOC」と称する。)0%から100%まで、雰囲気温度55℃で、1C電流、上限電圧4.15Vでの定電流定電圧充電を行い、次いでSOC0%になるまで1C電流での定電流放電を行った。
リチウムイオン二次電池の初期充放電を行った後、電池を解体し、電解液中に残存している各添加剤の量を、核磁気共鳴法(NMR)により測定した。
リチウムイオン二次電池の初期充放電を行い、電池を解体した後、燃焼イオンクロマトグラフィ法により、各電極の硫黄含有量を測定した。
電解液中に残存する各添加剤の量を測定した後、上記と同様の手順で再度電池を封止した。作製した電池のSOC0%と100%までの間で、1C電流、4.15Vでの定電流定電圧充電(CCCV充電)と、1C電流での定電流放電(CC放電)を、55℃環境下で1ヶ月間繰り返した。これによる容量維持率を、(1ヶ月間サイクル後の電池容量)/(初期電池容量)なる計算式で計算した。
また、負極に存在する硫黄の重量が正極に存在する硫黄の重量よりも大きいことで、負極に十分な保護被膜が形成されており、負極の保護効果がより一層高くなり放電容量維持率が更に改善される。
11 負極集電体
12 正極集電体
13 負極活物質層
15 正極活物質層
17 セパレータ
25 負極リード
27 正極リード
29 外装体
31 電解液
Claims (8)
- 一般式Li x Ni y Co z Me (1−y−z) O 2 (ここでMeは、Al、Mn、Na、Fe、Cr、Cu、Zn、Ca、K、Mg、およびPbからなる群より選択される、少なくとも1種以上の金属であり、式中のxは1≦x≦1.2であり、yおよびzはy+z<1を満たす正の数であり、yの値が0.5以下であり、y>1−y−z、およびy>zである。)で表される遷移金属複合酸化物を含む正極活物質層が正極集電体に配置された正極と、
負極活物質層が負極集電体に配置された負極と、
セパレータと、
電解液と、
を含む発電要素を、外装体内部に含むリチウムイオン二次電池であって、
該セパレータが、オレフィン樹脂系樹脂層と耐熱性微粒子層とを含み、
該電解液が、
硫黄を含む添加剤Aと、
不飽和結合を有する、添加剤Aとは異なる環状カーボネート添加剤Bおよび/または
ハロゲンを有する、添加剤AおよびBとは異なる環状カーボネート添加剤Cと
を含み、
該リチウムイオン二次電池の初期充放電の後に、該添加剤Aと添加剤Bと添加剤Cの合計モル量を100としたときの該添加剤Aのモル比率が、該添加剤Bのモル比率、添加剤Cのモル比率、または添加剤Bと添加剤Cの合計モル比率の何れかよりも小さく、
該添加剤Aが、メチレンメタンジスルホン酸エステルから選択される、前記リチウムイオン二次電池。 - 該添加剤Aのモル比率が、50モル%以下である、請求項1に記載のリチウムイオン二次電池。
- 該添加剤Bおよび該添加剤Cを含む、請求項1または2に記載のリチウムイオン二次電池。
- 該添加剤Bが、ビニレンカーボネートである、請求項1〜3のいずれかに記載のリチウムイオン二次電池。
- 該添加剤Cが、4−フルオロエチレンカーボネートである、請求項1〜4のいずれかに記載のリチウムイオン二次電池。
- 該負極に存在する硫黄の重量が、該正極に存在する硫黄の重量よりも大きい、請求項1〜5のいずれかに記載のリチウムイオン二次電池。
- 該負極が、負極活物質を含む負極活物質層が負極集電体に配置された負極であり、該負極活物質が、黒鉛粒子および/または非晶質炭素粒子である、請求項1〜6のいずれかに記載のリチウムイオン二次電池。
- 該耐熱性微粒子層が、アルミナまたはベーマイトのうち少なくとも1つを含む、請求項1〜7に記載のリチウムイオン二次電池。
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