JP4214564B2 - Spinel structure lithium manganese oxide containing other elements, method for producing the same, and use thereof - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明はＬｉおよびＭｎ以外の他種元素（Ｍ）を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物およびその製造方法並び用途に関するものである。
【０００２】
マンガン酸化物は、電池活物質として、古くから使用されている材料である。マンガンとリチウムの複合物質であるリチウムマンガン酸化物は、および該リチウムマンガン酸化物のマンガンの一部を他種元素と置換したリチウムマンガン系酸化物は、高出力、高エネルギー密度が達成できるリチウム二次電池の正極活物質として、近年注目されている材料である。
【０００３】
【従来の技術】
リチウム二次電池用の正極材料は、電圧作動領域が高いこと、高放電容量であることおよびサイクル安定性が高いことが求められ、Ｌｉと各種金属、例えば、Ｃｏ、Ｎｉ、Ｍｎ等、の複合酸化物が検討されている。
【０００４】
ＬｉとＭｎの複合酸化物の一種であるスピネル構造のＬｉＭｎ2Ｏ4は、放電時に４Ｖ付近および３Ｖ付近に平坦部部分のある二段放電を示すことが知られ、４Ｖ付近の作動領域で可逆的にサイクルさせることができれば、高いエネルギーを取り出すことが期待できるため、正極活物質として有望であると考えられている。
【０００５】
しかしながら、近年、ＬｉＭｎ2Ｏ4構造中のＭｎが、リチウム二次電池正極として充放電を行うと、有機電解液中で溶出することがわかった。さらに、本発明者らの実験では、電解液系の種類にもよるが、充放電を行わなくとも、有機電解液中でＬｉＭｎ2Ｏ4を８５℃で保存しただけでも構造中のＭｎ量が１ｍｏｌ％程度も溶出し、溶出後には正極材料としての特性が著しく低下することがわかった。
【０００６】
これは、ＬｉＭｎ2Ｏ4をリチウム二次電池用正極として使用した場合、充放電を行わなくとも、長期間保存しただけで、構造中のＭｎが有機電解液中で溶出し、リチウム二次電池用正極として作動しなくなる可能性を示している。
【０００７】
【発明が解決しようとする課題】
本発明の目的は、Ｌｉ二次電池用の正極材料として、有機電解液中でのＭｎ溶出を抑制した高性能なスピネル構造リチウムマンガン系酸化物および該リチウムマンガン系酸化物を正極に用いた高性能なリチウム二次電池を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは鋭意検討した結果、以下の組成で表され、ＬｉおよびＭｎ以外の多種元素を含有するスピネル構造リチウムマンガン系酸化物が上記目的を達成できることを見いだした。
【０００９】
｛Ｌｉ｝［Ｌｉｘ・Ｍｙ・Ｍｎ（２−ｘ−ｙ）］Ｏ４＋ｄ（ただし、｛｝内は構造中の酸素四面***置（８ａサイト），［］内は構造中の酸素八面***置（１６ｄサイト）を表す。０＜ｘ≦０．３３，０＜ｙ≦０．２，−０．５＜ｄ＜０．８）。
【００１０】
このｄ値は、焼成雰囲気が還元性雰囲気であれば、マイナスの値となり、酸化性雰囲気ではプラスの値となる。ＭはＬｉおよびＭｎ以外の元素である。
【００１１】
さらに、本発明のＬｉおよびＭｎ以外の他種元素（Ｍ）を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物の製造方法および本発明のＬｉおよびＭｎ以外の他種元素（Ｍ）を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物を正極活物質として用いた高性能なリチウム二次電池を見い出し、本発明を完成した。
【００１２】
【作用】
以下、本発明を具体的に説明をする。
【００１３】
本発明のＬｉおよびＭｎ以外の他種元素（Ｍ）を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物は以下の組成である。
【００１４】
｛Ｌｉ｝［Ｌｉｘ・Ｍｙ・Ｍｎ（２−ｘ−ｙ）］Ｏ４＋ｄ（ただし、｛｝内は構造中の酸素四面***置，［］内は構造中の酸素八面***置を表す。０＜ｘ≦０．３３，０＜ｙ≦０．２，−０．５＜ｄ＜０．８，ＭはＬｉおよびＭｎ以外の元素）
該Ｍ元素は、構造中の酸素四面***置に存在し、生成物として結晶構造が立方晶のスピネル構造であり、その格子定数ａが、８．１９オングストローム以上、８．２４オングストローム以下であるスピネル構造リチウムマンガン系酸化物を形成するものが好ましい。
【００１５】
尚、立方晶以外のスピネル構造としては、正方晶等があるが、作動電位が低くなり、Ｌｉ二次電池を構成した場合に取り出されるエネルギーが小さくなり好ましくない。
【００１６】
また、その格子定数ａが上記範囲外となると、その構造中のマンガンが不安定となるため、Ｍｎ溶出量が大きくなり好ましくない。
【００１７】
該Ｍ元素は、Ｂｅ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ，Ｓｃ，Ｙ，Ｔｉ，Ｚｒ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ，Ｍｏ，Ｗ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ａｇ，Ｚｎ，Ｂ，Ａｌ，Ｇａ，Ｉｎ，Ｓｉ，Ｇｅ，Ｓｎ，Ｐｂ，Ｐ，Ａｓ，ＳｂおよびＢｉの群から選択された少なくとも１種の元素である。
【００１８】
さらに本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物の平均凝集粒子径が１〜５０μｍであり、且つ、ＢＥＴ比表面積が０．１〜５ｍ２／ｇであることが好ましい。
【００１９】
平均凝集粒子径が該範囲より大きい場合、またはＢＥＴ比表面積が該範囲より小さい場合には、製造に高温が必要であり、また、電池活物質に使用した場合に高い性能が得られにくいため好ましくなく、逆に平均凝集粒子径が該範囲より小さい場合、またはＢＥＴ比表面積が該範囲より大きい場合には、電池活物質に使用する場合に充填性が悪く、また構造中からＭｎが溶出しやすい等の問題が生じやすく好ましくない。
【００２０】
また、本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物の平均一次粒子径は３μｍ以下であることが好ましい。該範囲より大きい場合、電池活物質などに使用した場合に高い性能が得られにくいため好ましくない。
【００２１】
本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物の他種元素の量を表すｙは、０＜ｙ≦０．２であり、２種以上の他種元素を含有する場合には、各他種元素の含有量をｙ１，ｙ２，ｙ３・・・ｙｎとし、０＜ｙ１＋ｙ２＋ｙ３＋・・・＋ｙｎ≦０．２である。
【００２２】
該ｙのトータル量が０．２より大きくなると充放電容量が少なくなり、好ましくない。本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物中のＬｉは構造中の酸素四面***置と酸素八面***置の両方に存在し、酸素四面***置に存在する量を１とした場合の酸素八面***置に存在する量ｘは０＜ｘ≦０．３３である。
【００２３】
Ｌｉの総量が１未満の場合、スピネル構造の単相構造が得られないか、又は、有機電解液中へのＭｎの溶出量が大きくなり好ましくなく、該範囲よりも大きい場合も、充放電容量が小さくなり好ましくない。
【００２４】
該ｘの値は０≦ｘ≦０．１５の場合、容量が大きく取れ、且つ、Ｍｎ溶出量が低く抑えられ、特に好ましい。
【００２５】
本発明のＬｉおよびＭｎ以外の元素が１種の場合にはＣｒが好ましい。
【００２６】
他種元素がＣｒの場合には、その組成式は以下のようになる。
【００２７】
｛Ｌｉ｝［Ｌｉｘ・Ｍｙ・Ｍｎ（２−ｘ−ｙ）］Ｏ４＋ｄ（ただし、｛｝内は構造中の酸素四面***置，［］内は構造中の酸素八面***置を表す。０＜ｘ≦０．３３，０＜ｙ≦０．２，−０．５＜ｄ＜０．８）
この場合、０＜ｘ≦０．１５，０．０２≦ｙ≦０．２であることが好ましい。さらに、ＬｉおよびＭｎ以外の他種元素を２種（Ｍ（１），Ｍ（２））を含有する場合は、下記の式で表される。
【００２８】
｛Ｌｉ｝［Ｌｉｘ・Ｍｎ２−ｘ−ｙ１−ｙ２・Ｍ（１）ｙ１・Ｍ（２）ｙ２］Ｏ４＋ｄ（ただし、｛｝内は構造中の酸素四面***置，［］内は構造中の酸素八面***置を表す。０＜ｘ≦０．３３，０＜ｙ１＋ｙ２≦０．２，−０．５＜ｄ＜０．８，Ｍ（１）およびＭ（２）はＬｉおよびＭｎ以外の元素）
含有する他種元素の１種Ｍ（１）がＣｒであることが好ましく、Ｍ（２）は遷移金属であることが好ましい。
【００２９】
特に含有する他種元素のうちＭ（１）がＣｒであり、Ｍ（２）がＦｅであることはより好ましく、その場合には下記の式で表される。
【００３０】
｛Ｌｉ｝［Ｌｉｘ・Ｃｒｙ１・Ｆｅｙ２・Ｍｎ２−ｘ−ｙ１−ｙ２］Ｏ４＋ｄ（ただし、｛｝内は構造中の酸素四面***置，［］内は構造中の酸素八面***置を表す。０＜ｘ≦０．３３，０＜ｙ１＜０．２，０＜ｙ２＜０．２，−０．５＜ｄ＜０．８）
該組成式において０＜ｘ≦０．１５，０＜ｙ１＜０．２，０＜ｙ２＜０．２であることが好ましい。
【００３１】
以上のように本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物は構造中の酸素四面***置にＬｉを酸素八面***置にＬｉとＭｎとさらにＬｉおよびＭｎ以外の少なくとも１種類の他種元素（Ｍ）を含有するスピネル構造リチウムマンガン系酸化物であり、さらには、電池活物質またはＬｉ吸着材などに使用した場合に高性能となる粒子構造をもつものである。
【００３２】
前述の本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物は、マンガン化合物とリチウム化合物と含有他種元素の化合物を混合、焼成することにより製造できる。
【００３３】
混合する化合物は酸化物，水酸化物，酸化水酸化物，炭酸塩，塩化物塩，硝酸塩および硫酸塩等のなかで焼成温度以下で酸化物を生成できるものであればよいが、特に、酸化物，水酸化物，酸化水酸化物，炭酸塩は反応性、廃ガスの環境へあたえる影響から好ましい。
【００３４】
原料マンガン化合物として平均凝集粒子径が０．５〜５０μｍであるマンガン酸化物を使用することが必須であり、その原料マンガン化合物の成形密度が２．７ｇ／ｃｍ3以上であるものを用いることが好ましい。
【００３５】
該範囲外のマンガン酸化物を用いることは本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物の粉体特性を満足するものを得ることが難しいため好ましくない。
【００３６】
さらに原料マンガン化合物に含まれるＮａ，Ｋ量が５００ｐｐｍ以下であるものを用いるのが好ましく、該Ｎａ，Ｋ量が多いと生成物を電池活物質に使用した場合に高性能なＬｉ二次電池を作成することが難しい。
【００３７】
本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物の製造方法においては、原料リチウム化合物としてＢＥＴ比表面積が１ｍ2／ｇ以上であるリチウム化合物を用いることが好ましい。
【００３８】
リチウム化合物としては炭酸塩、硝酸塩、塩化物塩、水酸化物、酸化物等が例示され、特にＢＥＴ比表面積が１ｍ2／ｇ以上である炭酸リチウムを用いれば、大気中でも容易に均一な他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物が製造でき非常に好ましい。
【００３９】
本発明の他種元素を含有し、有機溶媒中でＭｎ溶出が少ないスピネル構造リチウムマンガン系酸化物の製造における焼成温度は５００〜１０００℃の範囲から所望の粉体特性が得られるように適宜選択される。
【００４０】
焼成温度が該範囲外であると、生成物のＢＥＴ比表面積および／または一次粒子径が所望の範囲となり難く好ましくない。
【００４１】
焼成時の雰囲気は、大気中及び酸素リッチ雰囲気の両方共、使用可能であるが、焼成炉の構造の容易さから、大気中が好ましい。
【００４２】
前記の製造条件において、次に示す方法を採用することが特に好ましい。
【００４３】
１．マンガン化合物とリチウム化合物及び他種元素の化合物を混合してから造粒した後、焼成する方法。
【００４４】
２．マンガン化合物とリチウム化合物とを混合、造粒、焼成した後、リチウム化合物および／または含有他種元素の化合物を混合、造粒した
後、焼成する方法。
【００４５】
３．マンガン化合物、リチウム化合物及び含有他種元素の化合物を混合、造粒、焼成した後にマンガン化合物、リチウム化合物及び含有他種
元素の化合物のいずれか１種を混合し造粒した後、焼成する。
【００４６】
さらに、原料を混合する場合均一にすることができれば、通常の方法のいかなる方法も採用でき、ロータリーキルン等のように混合しながら焼成することも好適である。
【００４７】
製造したスピネル構造リチウムマンガン系酸化物は適時、粉砕、分級を行うのが好ましい。
【００４８】
本発明では、前述のようにして製造したスピネル構造リチウムマンガン系酸化物を正極活物質として用いたＬｉ二次電池を作製した。
【００４９】
本発明のリチウム二次電池で用いる負極活物質には、金属リチウム並びにリチウムまたはリチウムイオンを吸蔵放出可能な物質を用いることができる。例えば、金属リチウム、リチウム／アルミニウム合金、リチウム／スズ合金、リチウム／鉛合金および電気化学的にリチウムイオンを挿入・脱離する炭素系材料が例示され、電気化学的にリチウムイオンを挿入・脱理する炭素系材料が安全性および電池の特性の面から特に好適である。
【００５０】
また、本発明のリチウム二次電池で用いる電解質としては、特に制限はないが、例えば、カーボネート類、スルホラン類、ラクトン類、エーテル類等の有機溶媒中にリチウム塩を溶解したものや、リチウムイオン導電性の固体電解質を用いることができる。
【００５１】
本発明のスピネル構造リチウムマンガン系酸化物を正極活物質に用いて、図１に示す電池を構成した。
【００５２】
図中において、１：正極用リード線、２：正極集電用メッシュ、３：正極、４：セパレータ、５：負極、６：負極集電用メッシュ、７：負極用リード線、８：容器を示す。
【００５３】
本発明では、以上述べてきた正極活物質、負極活物質およびリチウム塩含有非水電解質を用いて、安定な高性能なリチウム二次電池を得ることができる。
【００５４】
以下実施例を述べるが、本発明はこれに限定されるものではない。
【００５５】
【実施例】
本発明の実施例および比較例における各測定は、以下の条件で実施した。
【００５６】
・ＸＲＤパターンは以下の条件で測定した。
【００５７】
測定機種 ：マックサイエンス社 ＭＸＰ−３
照射Ｘ線 ：Ｃｕ Ｋα線
測定モード ：ステップスキャン
スキャン条件：毎秒０．０４度
計測時間 ：３秒
測定範囲 ：２θとして５度から８０度
・組成分析はＩＣＰ分光法で行った。
【００５８】
・Ｍｎ元素の酸化度はしゅう酸法で行った。
【００５９】
『スピネル構造リチウムマンガン系酸化物の合成』
実施例および比較例として、以下の方法で合成した。
【００６０】
実施例１〜４、比較例１
他種元素ＭとしてＣｒを使用し、平均凝集粒子径が２０μｍのＭｎＯ2（東ソー株式会社製電解二酸化マンガン）とＢＥＴ比表面積が３ｍ２／ｇの炭酸リチウム（Ｌｉ２ＣＯ３）と平均凝集粒子径が１μｍの酸化クロム（Ｃｒ２Ｏ３）をＣｒとＭｎの比率を変化させ、以下の組成式においてＬｉ量をｘの値が０．０６（Ｌｉ：（Ｌｉ＋Ｍｎ＋Ｃｒ）＝１．０６：３．００）で一定になるように秤量し、乳鉢でよく混合した後、４５０℃で２４時間仮焼した後、７５０℃で２４時間焼成した。
【００６１】
｛Ｌｉ｝［Ｌｉ0.06・Ｃｒy・Ｍｎ(2-0.06-y)］Ｏ4
実施例３で得られたスピネル構造リチウムマンガン系酸化物の粒子構造をＳＥＭを用い、２０、０００倍の倍率で観察した写真を図２に示す。
【００６２】
この図から、実施例３で得られたスピネル構造リチウムマンガン系酸化物の全ての粒子一次粒子径が１μｍ以下であり、平均一次粒子径が１μｍ以下であることが明らかとなった。
【００６３】
又、得られたスピネル構造リチウムマンガン系酸化物の構造が上記の化学式であることを、Ｘ線回折による格子定数値及びＲｉｅｔｖｅｌｄ分析により推定した。
【００６４】
実施例５
実施例３において、最終の焼成温度を７５０℃から９００℃に高くした以外は同一とした。
【００６５】
得られたスピネル構造リチウムマンガン系酸化物の粒子構造をＳＥＭを用い、２０、０００倍の倍率で観察した写真を図３に示す。
【００６６】
この図から、得られたスピネル構造リチウムマンガン系酸化物の一次粒子径が１μｍ以上の粒子も含まれるいるが、平均一次粒子径は３μｍ以下であることが明らかとなった。
【００６７】
実施例６
実施例４においてＬｉ量をｘの値が０．０２になるようにした以外は同一とした。
【００６８】
実施例７〜９
実施例２〜４においてＣｒのかわりにＣｏを使用した以外は同一とした。
【００６９】
なお、Ｃｏ原料は塩基性炭酸コバルトを使用した。
【００７０】
実施例１０〜１２
実施例２〜４においてＣｒのかわりにＮｉを使用した以外は同一とした。
【００７１】
なお、Ｎｉ原料は塩基性炭酸ニッケルを使用した。
【００７２】
実施例１３〜１５
実施例２〜４においてＣｒのかわりにＦｅを使用した以外は同一とした。
【００７３】
なお、Ｆｅ原料はＦｅ3Ｏ4を使用した。
【００７４】
実施例１６
第一の他種元素Ｍ１としてＣｒを、第二の他種元素Ｍ２としてＦｅ使用し、下記組成式において、Ｌｉ量をｘの値が０．０１（Ｌｉ：（Ｌｉ＋Ｍｎ＋Ｃｒ＋Ｆｅ）＝１．０１：３．００）、ｙ１の値が０．１、ｙ２の値が０．１になるように凝集粒子径が２０μｍのＭｎＯ２、ＢＥＴ比表面積が３ｍ２／ｇであるＬｉ２ＣＯ３、平均凝集粒子径１μｍのＣｒ ２ Ｏ ３ 及びＦｅ３Ｏ４を秤量し、乳鉢でよく混合した後、４５０℃で２４時間仮焼した後、７５０℃で２４時間焼成した。 ｛Ｌｉ｝［Ｌｉ０．０１・Ｃｒ０．１ ・Ｆｅ０．１ ・Ｍｎ１．７９］Ｏ４
比較例２
凝集粒子径が２０μｍのＭｎＯ２（東ソー株式会社製電解二酸化マンガン）とＢＥＴ比表面積が３ｍ２／ｇである炭酸リチウムをｘ＝０．０（Ｌｉ：Ｍｎ＝１．００：２．０）となるように秤量し、乳鉢でよく混合した後、４５０℃で２４時間仮焼した後、７５０℃で２４時間焼成した。
【００７５】
生成物はＪＣＰＤＳカード３５−７８２のＬｉＭｎ2Ｏ4と同様のパターンを示した。
【００７６】
比較例３
比較例２でｘ＝０．０６（Ｌｉ：Ｌｉ＋Ｍｎ＝１．０６：３．０）とした以外は比較例２と同一の条件で行った。
【００７７】
比較例４
比較例２でｘ＝０．１０（Ｌｉ：Ｌｉ＋Ｍｎ＝１．１０：３．０）とした以外は比較例２と同一の条件で行った。
【００７８】
比較例５
Ｌｉ：Ｃｒ：Ｍｎ＝０．９５：０．２：１．８０となるように混合し、比較例２の条件で焼成した。
【００７９】
実施例および比較例の生成物は比較例５以外は立方晶のスピネル構造単相であった。
【００８０】
『Ｍｎ溶出試験』
実施例および比較例で作製したリチウムマンガン系酸化物を各３ｇを六フッ化リン酸リチウムを１モル／ｄｍ3の濃度でエチレンカーボネートとジメチルカーボネートの混合溶媒に溶解した電解液１５ｍｌに含浸し、８５℃，１００時間保持したの後、電解液中のＭｎ量をＩＣＰ分光法により分析した。
【００８１】
結果を表１に示した。
【００８２】
【表１】
『電池の構成』
実施例および比較例で得られたリチウムマンガン系酸化物および前記Ｍｎ溶出試験後の試料を用いて電池試験を行った。電池試験は試料と導電剤のポリテトラフルオロエチレンとアセチレンブラックの混合物（商品名：ＴＡＢ−２）を、重量比で２：１の割合で混合した。混合物を１ｔｏｎ／ｃｍ2の圧力で、メッシュ（ＳＵＳ ３１６）上にペレット状に成形した後、２００℃で２４時間減圧乾燥した。
【００８４】
この様にして得られたペレットを図１の３の正極に用い、図１の５の負極にはリチウム箔（厚さ０．２ｍｍ）から切り抜いたリチウム片を用い、電解液には六フッ化リン酸リチウムを１モル／ｄｍ3の濃度でプロピレンカーボネートとジエチルカーボネートの混合溶媒に溶解した溶液を図１の４のセパレーターに含浸させ、また、負極に電気化学的にリチウムイオンを挿入・脱離する炭素系材料を使用して図１に示した電池を構成した。
【００８５】
『電池特性の評価』
実施例および比較例で作製したリチウムマンガン系酸化物を正極活物質に用いて電池を作製し、１．０ｍＡ／ｃｍ2の一定電流で、電池電圧が４．５Ｖから３．５Ｖの間で充放電を繰り返した。
【００８６】
試験温度は室温と５０℃で実施した。
【００８７】
表１に初期容量、容量維持率（１０サイクル目に対する５０サイクル目の放電容量の％）および溶出試験維持率（溶出試験後の容量の溶出試験前の初期容量に対する％）を示した。
【００８８】
【発明の効果】
本発明のスピネル構造リチウムマンガン系酸化物は、有機溶媒中でＭｎ溶出が少なく、長期保存後も安定した充放電サイクル性を発揮し、さらに高温で充放電を行っても劣化が少ない。
【図面の簡単な説明】
【図１】本発明のスピネル構造リチウムマンガン系酸化物を正極活物質に用いて構成した電池を示す。
【符号の説明】
１：正極用リード線
２：正極集電用メッシュ
３：正極
４：セパレータ
５：負極
６：負極集電用メッシュ
７：負極用リード線
８：容器
【図２】実施例３で得られたスピネル構造リチウムマンガン系酸化物の粒子構造を示す写真である。
【図３】実施例５で得られたスピネル構造リチウムマンガン系酸化物の粒子構造を示す写真である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a spinel structure lithium manganese-based oxide containing a different element (M) other than Li and Mn and having little Mn elution in an organic solvent, and a production method and use thereof.
[0002]
Manganese oxide is a material that has been used for a long time as a battery active material. Lithium manganese oxide, which is a composite material of manganese and lithium, and lithium manganese oxide in which a part of manganese of the lithium manganese oxide is replaced with other kinds of elements are lithium manganese oxides that can achieve high output and high energy density. As a positive electrode active material for a secondary battery, it is a material that has been attracting attention in recent years.
[0003]
[Prior art]
A positive electrode material for a lithium secondary battery is required to have a high voltage operating region, a high discharge capacity, and a high cycle stability, and a composite of Li and various metals such as Co, Ni, Mn, etc. Oxides are being considered.
[0004]
It is known that LiMn 2 O 4 having a spinel structure, which is a kind of complex oxide of Li and Mn, exhibits a two-stage discharge with a flat portion near 4 V and 3 V during discharge, and is reversible in the operating region near 4 V. If it can be cycled automatically, high energy can be expected to be taken out, and it is considered promising as a positive electrode active material.
[0005]
However, in recent years, it has been found that Mn in the LiMn 2 O 4 structure elutes in an organic electrolyte when charging and discharging are performed as a lithium secondary battery positive electrode. Furthermore, in our experiments, although depending on the type of the electrolyte system, the amount of Mn in the structure can be reduced even if LiMn 2 O 4 is stored at 85 ° C. in the organic electrolyte without charging and discharging. As a result, about 1 mol% was eluted, and it was found that the characteristics as the positive electrode material were remarkably lowered after the elution.
[0006]
This is because, when LiMn 2 O 4 is used as a positive electrode for a lithium secondary battery, Mn in the structure elutes in the organic electrolyte only by storing for a long time without charging and discharging, and the lithium secondary battery This indicates the possibility that it will not work as a positive electrode for use.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a high-performance spinel structure lithium manganese oxide that suppresses Mn elution in an organic electrolyte as a positive electrode material for a Li secondary battery, and a high-performance material using the lithium manganese oxide as a positive electrode. The object is to provide a high performance lithium secondary battery.
[0008]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that a spinel structure lithium manganese oxide represented by the following composition and containing various elements other than Li and Mn can achieve the above object.
[0009]
{Li} [Li x · M y · Mn (2-xy) ] O 4 + d (where {} is the oxygen tetrahedron position in the structure (8a site), [] is the oxygen octahedron in the structure) Represents the position (16d site): 0 <x ≦ 0.33, 0 <y ≦ 0.2 , −0.5 <d <0.8.
[0010]
This d value is a negative value when the firing atmosphere is a reducing atmosphere, and a positive value when the firing atmosphere is an oxidizing atmosphere. M is an element other than Li and Mn.
[0011]
Further, the process for producing a spinel structure lithium manganese-based oxide which contains other elements (M) other than Li and Mn of the present invention and has little Mn elution in an organic solvent, and other elements other than Li and Mn of the present invention The present invention was completed by finding a high-performance lithium secondary battery containing (M) and using a spinel structure lithium manganese-based oxide containing less Mn in an organic solvent as a positive electrode active material.
[0012]
[Action]
Hereinafter, the present invention will be specifically described.
[0013]
The spinel structure lithium manganese-based oxide containing other elements (M) other than Li and Mn of the present invention and having little Mn elution in an organic solvent has the following composition.
[0014]
{Li} [Li x · M y · Mn (2-xy) ] O 4 + d (where {} represents the oxygen tetrahedron position in the structure, and [] represents the oxygen octahedron position in the structure.) 0 <x ≦ 0.33, 0 <y ≦ 0.2 , −0.5 <d <0.8, M is an element other than Li and Mn)
The element M is present at the position of the oxygen tetrahedron in the structure, the product is a cubic spinel structure, and the lattice constant a thereof is 8.19 angstrom or more and 8.24 angstrom or less. Those that form a structure lithium manganese oxide are preferred.
[0015]
As spinel structures other than cubic crystals, there are tetragonal crystals and the like, but this is not preferable because the operating potential is lowered and the energy taken out when a Li secondary battery is configured is reduced.
[0016]
On the other hand, if the lattice constant a is outside the above range, manganese in the structure becomes unstable.
[0017]
The M element is Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, B, Al. , Ga, In, Si, Ge, Sn, Pb, P, As, Sb, and Bi.
[0018]
Furthermore, the average aggregate particle diameter of the spinel structure lithium manganese-based oxide containing other elements of the present invention and less Mn elution in an organic solvent is 1 to 50 μm, and the BET specific surface area is 0.1 to 5 m 2. / G is preferable.
[0019]
When the average agglomerated particle diameter is larger than the above range, or when the BET specific surface area is smaller than the above range, it is preferable because high temperature is required for production, and it is difficult to obtain high performance when used as a battery active material. On the contrary, when the average aggregated particle size is smaller than the above range, or when the BET specific surface area is larger than the above range, the filling property is poor when used for the battery active material, and Mn is easily eluted from the structure. Such problems are likely to occur, which is not preferable.
[0020]
Moreover, it is preferable that the average primary particle diameter of the spinel structure lithium manganese-type oxide which contains the other kind element of this invention and has little Mn elution in an organic solvent is 3 micrometers or less. When it is larger than this range, it is difficult to obtain high performance when used for a battery active material or the like, which is not preferable.
[0021]
The y representing the amount of other elements of the spinel structure lithium manganese oxide containing other elements of the present invention and less Mn elution in an organic solvent is 0 <y ≦ 0.2 , and two or more elements when containing other species element, the content of each other species element and y1, y2, y3 · · · yn, is 0 <y1 + y2 + y3 + ··· + yn ≦ 0.2.
[0022]
If the total amount of y is larger than 0.2, the charge / discharge capacity decreases, which is not preferable. Li in the spinel structure lithium manganese-based oxide containing other elements of the present invention and less Mn elution in an organic solvent is present in both the oxygen tetrahedron position and the oxygen octahedron position in the structure, and the oxygen tetrahedron. The amount x existing at the oxygen octahedron position when the amount existing at the position is 1 is 0 <x ≦ 0.33.
[0023]
When the total amount of Li is less than 1, the spinel single-phase structure cannot be obtained, or the elution amount of Mn into the organic electrolyte is undesirably large. Becomes smaller, which is not preferable.
[0024]
When the value of x is 0 ≦ x ≦ 0.15, it is particularly preferable because the capacity can be increased and the elution amount of Mn can be kept low.
[0025]
Cr is preferred when there is only one element other than Li and Mn of the present invention.
[0026]
When the other element is Cr, the composition formula is as follows.
[0027]
{Li} [Li x · M y · Mn (2-xy) ] O 4 + d (where {} represents the oxygen tetrahedron position in the structure, and [] represents the oxygen octahedron position in the structure.) 0 <x ≦ 0.33, 0 <y ≦ 0.2 , −0.5 <d <0.8)
In this case, it is preferable that 0 <x ≦ 0.15, 0.02 ≦ y ≦ 0.2. Further, when two kinds of elements other than Li and Mn (M (1), M (2)) are contained, they are represented by the following formula.
[0028]
{Li} [Li x · Mn 2−x−y 1 −y 2 · M (1) y 1 · M (2) y 2] O 4 + d (where {} is the oxygen tetrahedral position in the structure, [] is the structure Represents the oxygen octahedron position in which 0 <x ≦ 0.33, 0 <y1 + y2 ≦ 0.2 , −0.5 <d <0.8, M (1) and M (2) are other than Li and Mn Elements)
It is preferable that 1 type M (1) of the other kind element to contain is Cr, and it is preferable that M (2) is a transition metal.
[0029]
In particular, it is more preferable that M (1) is Cr and M (2) is Fe among other kinds of elements to be contained. In this case, it is represented by the following formula.
[0030]
{Li} [Li x · Cr y 1 · Fe y 2 · Mn 2−x−y 1 −y 2 ] O 4 + d (where {} is the oxygen tetrahedron position in the structure, and [] is the oxygen octahedron position in the structure) 0 <x ≦ 0.33, 0 <y1 <0.2 , 0 <y2 <0.2 , −0.5 <d <0.8)
It is preferred in the composition formula is 0 <x ≦ 0.15,0 <y1 < 0.2,0 <y2 <0.2.
[0031]
As described above, the spinel-structure lithium-manganese oxide containing other elements of the present invention and having little Mn elution in an organic solvent has Li at the oxygen tetrahedron position in the structure and Li and Mn at the oxygen octahedron position. A spinel-structure lithium-manganese oxide containing at least one other element (M) other than Li and Mn, and further having a high-performance particle structure when used as a battery active material or Li adsorbent It has something.
[0032]
Contain other species element of the invention described above, Mn elution less spinel-type lithium-manganese oxide in an organic solvent, manufacture mixing a compound of another type element-containing manganese compound and a lithium compound and fired kill at.
[0033]
The compound to be mixed may be any oxide, hydroxide, oxide hydroxide, carbonate, chloride salt, nitrate, sulfate, etc., as long as it can generate an oxide at a temperature lower than the firing temperature. Substances, hydroxides, oxide hydroxides and carbonates are preferred because of their reactivity and the effect of waste gas on the environment.
[0034]
It is essential to use a manganese oxide having an average agglomerated particle size of 0.5 to 50 μm as a raw material manganese compound, and use of a raw material manganese compound having a molding density of 2.7 g / cm 3 or more. preferable.
[0035]
It is difficult to obtain a manganese oxide outside the above range that contains the other elements of the present invention and satisfies the powder characteristics of the spinel structure lithium manganese oxide with less Mn elution in an organic solvent. It is not preferable.
[0036]
Furthermore, it is preferable to use a material in which the amount of Na and K contained in the raw material manganese compound is 500 ppm or less. If the amount of Na and K is large, a high performance Li secondary battery can be obtained when the product is used as a battery active material. Difficult to create.
[0037]
In the method for producing a spinel structure lithium manganese oxide containing other elements of the present invention and having little Mn elution in an organic solvent , a lithium compound having a BET specific surface area of 1 m 2 / g or more is used as a raw material lithium compound. It is preferable.
[0038]
Examples of the lithium compound include carbonates, nitrates, chloride salts, hydroxides, oxides, and the like. Particularly, when lithium carbonate having a BET specific surface area of 1 m 2 / g or more is used, other types that are easily and uniformly distributed in the atmosphere. A spinel structure lithium manganese-based oxide containing an element and having little Mn elution in an organic solvent can be produced, which is very preferable.
[0039]
The firing temperature in the production of the spinel structure lithium manganese oxide containing other elements of the present invention and less Mn elution in an organic solvent is appropriately selected so that desired powder characteristics can be obtained from the range of 500 to 1000 ° C. Is done.
[0040]
If the calcination temperature is outside this range, the BET specific surface area and / or the primary particle diameter of the product are not easily in the desired range, which is not preferable.
[0041]
The atmosphere at the time of firing can be used both in the air and in an oxygen-rich atmosphere, but the air is preferable because of the ease of the structure of the firing furnace.
[0042]
In the above manufacturing conditions, it is particularly preferable to employ the following method.
[0043]
1. A method in which a manganese compound, a lithium compound, and a compound of another element are mixed and then granulated and then fired.
[0044]
2. A method in which a manganese compound and a lithium compound are mixed, granulated, and fired, and then a lithium compound and / or a compound of another kind of contained element is mixed and granulated, followed by firing.
[0045]
3. After mixing, granulating, and firing a manganese compound, a lithium compound, and a compound of another contained element, any one of a manganese compound, a lithium compound, and a compound of another contained element is mixed, granulated, and fired.
[0046]
Furthermore, if the raw materials can be made uniform, any ordinary method can be adopted, and it is also preferable to perform firing while mixing such as a rotary kiln.
[0047]
The manufactured spinel lithium manganese oxide is preferably pulverized and classified in a timely manner.
[0048]
In the present invention, a Li secondary battery using the spinel structure lithium manganese oxide produced as described above as a positive electrode active material was produced.
[0049]
As the negative electrode active material used in the lithium secondary battery of the present invention, metallic lithium and a material capable of occluding and releasing lithium or lithium ions can be used. Examples include lithium metal, lithium / aluminum alloy, lithium / tin alloy, lithium / lead alloy, and carbon-based materials that electrochemically insert and desorb lithium ions, and electrochemically insert and desorb lithium ions. The carbon-based material to be used is particularly suitable from the viewpoints of safety and battery characteristics.
[0050]
The electrolyte used in the lithium secondary battery of the present invention is not particularly limited. For example, an electrolyte obtained by dissolving a lithium salt in an organic solvent such as carbonates, sulfolanes, lactones, and ethers, or lithium ions A conductive solid electrolyte can be used.
[0051]
The battery shown in FIG. 1 was constructed using the spinel structure lithium manganese oxide of the present invention as the positive electrode active material.
[0052]
In the drawing, 1: lead wire for positive electrode, 2: mesh for positive electrode current collection, 3: positive electrode, 4: separator, 5: negative electrode, 6: mesh for negative electrode current collection, 7: lead wire for negative electrode, 8: container Show.
[0053]
In the present invention, a stable high-performance lithium secondary battery can be obtained by using the positive electrode active material, the negative electrode active material, and the lithium salt-containing nonaqueous electrolyte described above.
[0054]
Examples will be described below, but the present invention is not limited thereto.
[0055]
【Example】
Each measurement in Examples and Comparative Examples of the present invention was performed under the following conditions.
[0056]
-The XRD pattern was measured under the following conditions.
[0057]
Measurement model: MXP-3
Irradiation X-ray: Cu Kα ray measurement mode: Step scan scan condition: 0.04 degrees per second Measurement time: 3 seconds Measurement range: 5 degrees to 80 degrees as 2θ. Composition analysis was performed by ICP spectroscopy.
[0058]
-The oxidation degree of Mn element was performed by the oxalic acid method.
[0059]
"Synthesis of spinel lithium manganese oxide"
Examples and Comparative Examples were synthesized by the following method.
[0060]
Examples 1-4, Comparative Example 1
MnO 2 (electrolytic manganese dioxide manufactured by Tosoh Corporation) having an average aggregate particle size of 20 μm, lithium carbonate (Li 2 CO 3 ) having a BET specific surface area of 3 m 2 / g, and average aggregate particles Chromium oxide (Cr 2 O 3 ) having a diameter of 1 μm is changed in the ratio of Cr and Mn, and the amount of Li in the following composition formula is 0.06 (Li: (Li + Mn + Cr) = 1.06: 3. 00) and was mixed well in a mortar, calcined at 450 ° C. for 24 hours, and then calcined at 750 ° C. for 24 hours.
[0061]
{Li} [Li 0.06 · Cr y · Mn (2-0.06-y)] O 4
FIG. 2 shows a photograph of the particle structure of the spinel structure lithium manganese oxide obtained in Example 3 observed using a SEM at a magnification of 20,000 times.
[0062]
From this figure, it was revealed that the primary particle diameter of all the particles of the spinel structure lithium manganese oxide obtained in Example 3 is 1 μm or less, and the average primary particle diameter is 1 μm or less.
[0063]
Moreover, it was estimated by the lattice constant value by X-ray diffraction and Rietveld analysis that the structure of the obtained spinel structure lithium manganese oxide was the above chemical formula.
[0064]
Example 5
In Example 3, it was the same except that the final baking temperature was increased from 750 ° C. to 900 ° C.
[0065]
The photograph which observed the particle | grain structure of the obtained spinel structure lithium manganese type oxide by 20,000 times using SEM is shown in FIG.
[0066]
From this figure, it was clarified that although the primary particle diameter of the obtained spinel structure lithium manganese oxide was 1 μm or more, the average primary particle diameter was 3 μm or less.
[0067]
Example 6
In Example 4, the amount of Li was the same except that the value of x was 0.02.
[0068]
Examples 7-9
In Examples 2 to 4, it was the same except that Co was used instead of Cr.
[0069]
Co raw material used was basic cobalt carbonate.
[0070]
Example 1 0-1 2
In Examples 2 to 4, it was the same except that Ni was used instead of Cr.
[0071]
The nickel raw material used was basic nickel carbonate.
[0072]
Examples 1 3 to 15
In Examples 2 to 4, it was the same except that Fe was used instead of Cr.
[0073]
Note that Fe 3 O 4 was used as the Fe raw material.
[0074]
Example 1 6
Cr is used as the first other element M1, and Fe is used as the second other element M2. In the following composition formula, the value of x is 0.01 (Li: (Li + Mn + Cr + Fe) = 1.01: 3 .00), MnO 2 with an aggregated particle diameter of 20 μm so that the value of y1 is 0.1 and the value of y2 is 0.1, Li 2 CO 3 with a BET specific surface area of 3 m 2 / g, average aggregated particles Cr 2 O 3 and Fe 3 O 4 having a diameter of 1 μm were weighed, mixed well in a mortar, calcined at 450 ° C. for 24 hours, and then calcined at 750 ° C. for 24 hours. {Li} [Li 0.01 · Cr 0.1 · Fe 0.1 · Mn 1.79 ] O 4
Comparative Example 2
MnO 2 (electrolytic manganese dioxide manufactured by Tosoh Corporation) having an aggregated particle size of 20 μm and lithium carbonate having a BET specific surface area of 3 m 2 / g are x = 0.0 (Li: Mn = 1.00: 2.0) After being weighed and mixed well in a mortar, it was calcined at 450 ° C. for 24 hours and then calcined at 750 ° C. for 24 hours.
[0075]
The product showed a pattern similar to LiMn 2 O 4 of JCPDS card 35-782.
[0076]
Comparative Example 3
In Comparative Example 2 x = 0.06 (Li: Li + Mn = 1.06: 3.0) and then other than the was performed under the same conditions as Comparative Example 2.
[0077]
Comparative Example 4
In Comparative Example 2 x = 0.10 (Li: Li + Mn = 1.10: 3.0) and then other than the was performed under the same conditions as Comparative Example 2.
[0078]
Comparative Example 5
The mixture was mixed so that Li: Cr: Mn = 0.95: 0.2: 1.80, and fired under the conditions of Comparative Example 2 .
[0079]
Except for Comparative Example 5 , the products of Examples and Comparative Examples were cubic spinel structure single phase.
[0080]
"Mn dissolution test"
3 g of each of the lithium manganese oxides prepared in Examples and Comparative Examples were impregnated in 15 ml of an electrolytic solution in which lithium hexafluorophosphate was dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate at a concentration of 1 mol / dm 3 , After holding at 85 ° C. for 100 hours, the amount of Mn in the electrolytic solution was analyzed by ICP spectroscopy.
[0081]
The results are shown in Table 1.
[0082]
[Table 1]
Battery configuration
A battery test was conducted using the lithium manganese oxides obtained in Examples and Comparative Examples and the sample after the Mn elution test. In the battery test, a mixture of a sample and a conductive agent polytetrafluoroethylene and acetylene black (trade name: TAB-2) was mixed at a weight ratio of 2: 1. The mixture was formed into a pellet on a mesh (SUS 316) at a pressure of 1 ton / cm 2 and then dried under reduced pressure at 200 ° C. for 24 hours.
[0084]
The pellets thus obtained were used for the
[0085]
"Evaluation of battery characteristics"
A battery was prepared using the lithium manganese oxide prepared in Examples and Comparative Examples as a positive electrode active material, and charged at a constant current of 1.0 mA / cm 2 between 4.5 V and 3.5 V. The discharge was repeated.
[0086]
The test temperature was room temperature and 50 ° C.
[0087]
Table 1 shows the initial capacity, the capacity retention ratio (% of the discharge capacity at the 50th cycle with respect to the 10th cycle), and the dissolution test retention ratio (% of the capacity after the dissolution test with respect to the initial capacity before the dissolution test).
[0088]
【The invention's effect】
The spinel structure lithium manganese-based oxide of the present invention has little Mn elution in an organic solvent, exhibits stable charge / discharge cycle characteristics even after long-term storage, and has little deterioration even when charged / discharged at a high temperature.
[Brief description of the drawings]
FIG. 1 shows a battery constructed using the spinel structure lithium manganese oxide of the present invention as a positive electrode active material.
[Explanation of symbols]
1: Positive electrode lead wire 2: Positive electrode current collecting mesh 3: Positive electrode 4: Separator 5: Negative electrode 6: Negative electrode current collecting mesh 7: Negative electrode lead wire 8: Container [FIG. 2] Spinel obtained in Example 3 It is a photograph which shows the particle structure of a structure lithium manganese type oxide.
3 is a photograph showing the particle structure of a spinel structure lithium manganese oxide obtained in Example 5. FIG.
Claims (21)
｛Ｌｉ｝［Ｌｉｘ・Ｍｙ・Ｍｎ( ２−ｘ−ｙ )］Ｏ４＋ｄ（ただし、｛｝内は構造中の酸素四面***置，［］内は構造中の酸素八面***置を表す。０＜ｘ≦０．３３，０＜ｙ≦０．２，−０．５＜ｄ＜０．８，ＭはＬｉおよびＭｎ以外の元素）A spinel structure lithium manganese oxide represented by the following composition, containing at least one other kind of element (M) other than Li and Mn, and having little Mn elution in an organic solvent .
{Li} [Li x · M y · Mn ( 2-xy ) ] O 4 + d (where {} represents the oxygen tetrahedron position in the structure, and [] represents the oxygen octahedron position in the structure.) 0 <x ≦ 0.33, 0 <y ≦ 0.2 , −0.5 <d <0.8, M is an element other than Li and Mn)
｛Ｌｉ｝［Ｌｉｘ・Ｍｎ２―ｘ―ｙ１−ｙ２・Ｍ（１）ｙ１・Ｍ（２）ｙ２］Ｏ４＋ｄ（ただし、｛｝内は構造中の酸素四面***置，［］内は構造中の酸素八面***置を表す。０＜ｘ≦０．３３，０＜ｙ１＋ｙ２≦０．２，−０．５＜ｄ＜０．８）The spinel structure lithium manganese oxide containing the other elements according to claim 1, wherein the other elements M other than Li and Mn are two kinds of elements (M (1), M (2)). A spinel structure lithium manganese oxide containing other species represented by the following formula.
{Li} [Li x · Mn 2−x−y 1 −y 2 · M (1) y 1 · M (2) y 2] O 4 + d (where {} is the oxygen tetrahedron position in the structure, and [] is the structure The oxygen octahedron position is represented by 0 <x ≦ 0.33, 0 <y1 + y2 ≦ 0.2 , −0.5 <d <0.8)
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