JP3582161B2 - Positive electrode active material and non-aqueous electrolyte secondary battery using the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、非水電解質二次電池等で用いられる正極活物質及びそれを用いた非水電解質二次電池に関する。
【０００２】
【従来の技術】
近年、種々の電子機器の飛躍的進歩に伴い、長時間安定にかつ経済的に使用できるポータブル電源として、二次電池の研究が進められている。
【０００３】
代表的な二次電池としては、鉛蓄電池、アルカリ蓄電池、リチウム二次電池等を挙げることができる。このうちリチウム二次電池は、従来の他の二次電池に比べて高出力、高エネルギー密度を達成できることから活発に研究がなされ、種々の構成で提案がなされている。また、既に実用に供されているものもある。
【０００４】
たとえば、リチウム二次電池の負極としては、一般に、リチウムをドープ・脱ドープできる材料、金属リチウムまたはリチウム合金が使用される。リチウムをドープ・脱ドープできる材料としては、リチウムをドープした導電性高分子もしくは層状化合物（炭素材料、金属酸化物等）などが提案されている。
【０００５】
一方、正極を構成する正極活物質としては、金属酸化物、金属硫化物、特定のポリマーが使用できる。具体的には、ＴｉＳ２，ＭｏＳ２，ＮｂＳｅ２，Ｖ２Ｏ５等のリチウムを含有しない化合物や、ＬｉＭＯ２（但し、ＭはＣｏ，Ｎｉ，Ｍｎ，Ｆｅ等である）のようにリチウムを含有している複合酸化物が挙げられる。なかでも、Ｎｉを含むリチウム含有複合酸化物は、容量が大きく、比較的安価であることから期待されている。なお、これらの化合物は単独使用の他、複数種を混合して使用することもできる。
【０００６】
また、負極と正極の間に介在させるセパレータとしては、ポリプロピレン等の高分子フィルムが使用される。この場合、リチウムイオンの伝導度とエネルギー密度の点から、高分子フィルムは可能な限り薄くすることが必要とされ、実用的には５０μｍ以下である。
【０００７】
そして、電解液としては、プロピレンカーボネート等の高誘電率溶媒を主体とする非水溶媒に、ＬｉＰＦ６等のリチウム塩を電解質塩として溶解させたものが使用されている。
【０００８】
【発明が解決しようとする課題】
ところで、一般に、電池では、その内部抵抗によって内在するエネルギーの一部が消費される。したがって、充電したエネルギーを効率よく使用するためには、内部抵抗は低ければ低いほど望ましいと言える。
【０００９】
電池の内部抵抗は、主に活物質内の抵抗と、活物質粒子と電解液との界面に発生する抵抗（以下、界面分極抵抗と称する）とに由来し、これらの抵抗を合わせたものが電池全体の内部抵抗に相当する。
【００１０】
ここで、先に正極活物質として例示したリチウム含有複合酸化物では、この界面分極抵抗が経時的に増加するといった現象が見られる。なかでもＮｉを含有するリチウム含有複合酸化物は、容量が大きく比較的安価であるといった長所を有するものの、ＬｉＣｏＯ２等に比べてこの界面抵抗の経時的増加が比較的大きい傾向が短所の一つになっている。
【００１１】
そこで、本発明はこのような従来の実情に鑑みて提案されたものであり、界面分極抵抗の経時的な増加が少ない正極活物質を提供することを目的とする。また、そのような正極活物質を用いることで、内部抵抗が小さく充電エネルギーが効率良く使用される非水電解質二次電池を提供することを目的とする。
【００１２】
【課題を解決するための手段】
上述の目的を達成するために、本発明者等が鋭意検討を重ねた結果、Ｎｉを含有するリチウム含有複合酸化物の表面近傍で、固体状態としてＣｏ，ＡｌまたはＭｎのいずれかをＮｉに対して高濃度に存在せしめるようにすると、この複合酸化物における経時的な界面分極抵抗の増加が抑えられるとの知見を得るに至った。
【００１３】
本発明の正極活物質は、このような知見に基づいて完成されたものであって、ＬｉＮｉｘＭｙＯ２（但し、ＭはＡｌ，Ｍｎ，Ｆｅ，Ｎｉ，Ｃｏ，Ｃｒ，Ｔｉ，Ｚｎ，Ｐ，Ｂから選ばれる少なくとも一種の元素を表し、ｘは０＜ｘ≦１、ｙは０≦ｙ＜１である）で表される複合酸化物粒子の表面を、Ｃｏ，Ａｌ，Ｍｎの少なくともいずれかを含有する金属アルコキシドによって被覆処理したものである。
【００１５】
複合酸化物粒子表面を、これら化合物によって被覆処理すると、粒子表面にＣｏ，Ａｌ，Ｍｎを含有する化合物が付着したかたちになり、複合酸化物粒子の表面におけるｚ／（ｘ＋ｚ）（但し、ｘはＮｉの原子組成比であり、ｚはＣｏ，Ａｌ，Ｍｎの原子組成比の合計である。ここではこの値をＤ（ｓ）とする）が、複合酸化物粒子全体におけるｚ／（ｘ＋ｚ）（ここではこの値をＤ（ｂ）とする）よりも大なる値となる。なお、特に、処理用の化合物としてＣｏを含有するものを用いる場合には、Ｄ（ｓ）は１≧Ｄ（ｓ）＞０．３であるのが望ましい。
【００１６】
【発明の実施の形態】
以下、本発明の具体的な実施の形態について説明する。
【００１７】
本発明の正極活物質は、ＬｉＮｉｘＭｙＯ２（但し、ＭはＡｌ，Ｍｎ，Ｆｅ，Ｎｉ，Ｃｏ，Ｃｒ，Ｔｉ，Ｚｎ，Ｐ，Ｂから選ばれる少なくとも一種の元素を表し、ｘは０＜ｘ≦１、ｙは０≦ｙ＜１である）で表される複合酸化物粒子の表面が、Ｃｏ，Ａｌ，Ｍｎの少なくともいずれかを含有する化合物によって被覆処理されてなっている。すなわち、上記正極活物質は、Ｎｉを含有するリチウム複合酸化物粒子表面に、Ｃｏ，ＡｌまたはＭｎを含有する化合物が付着し、これによって粒子が表面改質されたかたちになっている。
【００１８】
このような表面改質が施された複合酸化物粒子では、表面にＣｏ，ＡｌまたはＭｎを含有する化合物が付着した分、表面においてＮｉの占める割合が減少している。このＮｉの占める割合が減少したことで、界面分極抵抗の経時的増加が抑えられる。したがって、高容量、安価であるといったＮｉを含有する複合酸化物粒子の長所を備えながら、しかも電池の内部抵抗を増大させず、正極活物質として優れた特性が得られる。
【００１９】
処理用の化合物としては、例えばＣｏ，ＡｌまたはＭｎの金属アルコキシド等が挙げられる。このうち、例えばＣｏアルコキシドによって複合酸化物粒子の表面改質を行うには、Ｃｏアルコキシドを溶解した表面処理液に、被処理体となる複合酸化物粒子を投入、攪はん後、１日程度保存する。保存中に、複合酸化物粒子表面には−Ｏ−Ｃｏ−Ｏの結合が生成し、Ｃｏ濃度の高い層が形成される。保存後、上澄液を捨て、残存粒子を溶媒で数回洗浄する。そして、この粒子を、乾燥することによって表面改質された複合酸化物粒子が得られる。Ａｌアルコキシド、Ｍｎアルコキシドによる表面改質もこれに準じて行われる。
【００２０】
また、処理用の化合物としては、Ｌｉを含んだもの、すなわちＬｉとＭｎ，ＡｌあるいはＣｏの複合化合物であっても良い。
【００２１】
なお、処理用の化合物としてはＣｏを含有するものを用いるのが望ましい。ＡｌあるいはＭｎでは、複合酸化物粒子に固溶した場合に電池の容量を若干減少させる方向に働くが、Ｃｏの場合には電池の容量をほとんど減少させないからである。
【００２２】
このようにして表面改質が行われた複合酸化物粒子では、Ｃｏ，ＡｌあるいはＭｎの濃度が、粒子全体よりも粒子表面において大きくなる。すなわち、表面におけるｚ／（ｘ＋ｚ）（但し、ｘはＮｉの原子組成比であり、ｚはＣｏ，Ａｌ，Ｍｎの原子組成比の合計である）をＤ（ｓ）、粒子全体におけるｚ／（ｘ＋ｚ）をＤ（ｂ）としたときに、Ｄ（ｓ）の値がＤ（ｂ）の値よりも大なる値になる。なお、特に、処理用の化合物としてＣｏを含有するものを用いる場合には、Ｄ（ｓ）の値は１≧Ｄ（ｓ）＞０．３であるのが望ましい。Ｄ（ｓ）が０．３以下である場合には、複合酸化物粒子の界面抵抗の経時的増加を十分に低めることができない。
【００２３】
なお、このＤ（ｓ），Ｄ（ｂ）はそれぞれ以下のようにして求められる値である。
【００２４】
Ｄ（ｓ）の測定：
０．１ＭＨＣｌ水溶液を５０ｃｃ秤量し、常温下でこのＨＣｌ水溶液に粉体５００ｍｇを投入し、室温２３℃下、５分間浸漬する。これにより、粉体の表面が酸によって溶解される。次に、ＨＣｌ水溶液から溶解せずに残存した残査粉末を除去する。そして、上澄液として残ったＨＣｌ水溶液のみをＩＣＰ−ＡＥＳ（ｉｎｄｕｃｔｉｖｅｌｙ ｃｏｕｐｌｅｄ ｐｌａｓｍａ−ａｔｏｍｉｃ ｅｍｉｓｓｉｏｎ ｓｐｅｃｔｒｏｓｃｏｐｙ） で分析し、溶液中に存在するＮｉと、Ｃｏ，ＡｌまたはＭｎの量比を測定し、その測定量に基づいてｚ／（ｘ＋ｚ）を算出する。
【００２５】
Ｄ（ｂ）の測定：
１ＭＨＣｌ水溶液に、粉体５００ｍｇを投入し、粉体全体を溶解させる。そして、粉体を溶解させたＨＣｌ水溶液をＩＣＰ−ＡＥＳで分析し、溶液中に存在するＮｉと、Ｃｏ，ＡｌまたはＭｎの量比を測定し、その測定量に基づいてｚ／（ｘ＋ｚ）を算出する。
【００２６】
以上のような表面改質が施された複合酸化物粒子は、非水電解質二次電池の正極に用いられる。
【００２７】
上記複合酸化物粒子で正極を形成するには、この複合酸化物粒子と導電剤及結着剤を混合して正極合剤を調製し、この正極合剤を所望の電極形状に圧縮成型する。ここで、導電剤や結着剤は、この種の電池で通常用いられているものがいずれも使用可能である。
【００２８】
また、上記正極と組み合わせて用いられる負極及び非水電解液も、やはりこの種の電池で用いられているものであって良い。
【００２９】
例えば負極の活物質としては、金属リチウムまたはリチウム−アルミニウム合金等のリチウム合金の他、リチウムをドープ・脱ドープすることが可能な材料が使用される。リチウムをドープ・脱ドープすることが可能な材料としては、例えば、熱分解炭素類、コークス類（ピッチコークス、ニードルコークス、石油コークス等）、グラファイト類、ガラス状炭素類、有機高分子化合物焼成体（フェノール樹脂、フラン樹脂等を適当な温度で焼成し炭素化したもの）、炭素繊維、活性炭等の炭素質材料、あるいはポリアセチレン、ポリピロール等のポリマー等を使用することができる。
【００３０】
このような炭素質材料やポリマーで負極を形成するには、これら材料と結着剤を混合して負極合剤を調製し、この負極合剤を所望の電極形状に圧縮成型する。
【００３１】
一方、非水電解液の非水溶媒としては、例えばプロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ビニレンカーボネート、γ−ブチロラクトン、スルホラン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、２−メチルテトラヒドロフラン、３−メチル−１，３−ジオキソラン、プロピオン酸メチル、酪酸メチル、ジメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート等を使用することができる。特に、電圧に安定な点から、プロピレンカーボネート，ビニレンカーボネート等の環状カーボネート類、ジメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート等の鎖状カーボネート類を使用することが好ましい。なお、これら非水溶媒はそれぞれ単独で使用しても２種類以上を組み合わせて使用しても構わない。
【００３２】
非水溶媒に溶解させる電解質塩としては、ＬｉＰＦ６，ＬＩＢＦ４，ＬｉＣｌＯ４，ＬｉＡｓＦ６，ＬｉＢＦ４，ＬｉＣＦ３ＳＯ３，ＬｉＮ（ＣＦ３ＳＯ２）２等を使用でき、このうち特にＬｉＰＦ６やＬＩＢＦ４を使用することが好ましい。
【００３３】
なお、この電池では、非水電解液の代わりに固体電解質を用いるようにしても良い。
【００３４】
また、電池の形状は特に限定されず、円筒型、角型、コイン型、ボタン型等の種々に形状にすることができる。
【００３５】
【実施例】
以下、本発明の実施例を実験結果に基づいて説明する。
【００３６】
実施例１
次のようにして正極活物質を生成した。
【００３７】
まず、以下に示す複合酸化物粒子及び表面処理液を用意した。
【００３８】
複合酸化物粒子（被処理体）：ＣｏＯ，ＮｉＯ及びＬｉＯＨ・Ｈ２Ｏを、Ｌｉ：Ｎｉ：Ｃｏ＝１：０．８：０．２（ｍｏｌ比）となるように混合し、大気中、温度７００〜８００℃で１０時間加熱処理することで得られたＬｉＮｉ０．８Ｃｏ０．２Ｏ２粉末
表面処理液：Ｃｏイソプロポキシド〔Ｃｏ（Ｏ−ｉ−Ｃ３Ｈ７）２〕を、１ｇ（５．６×１０−３ｍｏｌ相当量）秤り取り、２−エトキシエタノール（Ｃ２Ｈ５ＯＣＨ２ＣＨ２ＯＨ）１００ｃｃに溶解したＣｏアルコキシド溶液
窒素雰囲気下、上記表面処理液に複合酸化物粒子２ｇを投入し、混合攪はんした後、２４時間常温で保存した。保存後、上澄液を捨て、残存粒子を２−エトキシエタノールで数回洗浄した。そして、この粒子を、乾燥後、大気中で３００〜８００℃の温度にて加熱することによって表面改質された複合酸化物粒子（正極活物質）を得た。
【００３９】
なお、未処理の複合酸化物粒子と表面処理が施された複合酸化物粒子について、０．１ＭＨＣｌあるいは１ＭＨＣｌの溶解試験によってＤ（ｓ），Ｄ（ｂ）を測定した。その結果を表１に示す。
【００４０】
【表１】
表１に示すように、表面処理が施された複合酸化物粒子は、未処理の複合酸化物粒子よりもＤ（ｓ）の値が増加している。このことから、この表面処理によって複合酸化物粒子表面のＣｏ濃度が増加したことが確認された。
【００４２】
次に、以上のようにして表面改質がなされた複合酸化物粒子を正極活物質としてコイン型電池を作製した。
【００４３】
上記複合酸化物粒子９０重量部にグラファイト７重量部及びフッ素系高分子バインダー３重量部を加え、ジメチルホルムアミド（ＤＭＦ）とともに混合することで正極合剤を調製した。この正極合剤を十分乾燥することで溶媒であるＤＭＦを完全に揮発させた後、その約６０ｍｇを秤り取り、加圧成型することで、表面積約２ｃｍ２の円盤状の正極電極を作製した。
【００４４】
一方、負極は、Ｌｉ圧延金属を円盤状に打ち抜くことで作製した。
【００４５】
なお、この負極のＬｉ量は正極の最大充電能力の数１００倍であり、正極の電気化学的性能を制限するものではない。
【００４６】
以上のようにして作製された正極、負極をそれぞれ正極缶、負極缶に収納し、セパレータを間に挟んで積層した。そして、缶内にＬｉＰＦ６をプロピレンカーボネート（ＰＣ）に溶解させた電解液を注入し、正極缶及び負極缶をガスケットを介してかしめ密閉することでコイン型電池を作製した。そして、この電池について、充放電電流密度０．５ｍＡ／ｃｍ２なる条件でＯＣＶ（開回路電圧）が４．２Ｖになるまで充電した。
【００４７】
実施例２
複合酸化物粒子の表面処理液に溶解する金属アルコキシドとしてＡｌ（ＯＣＨ３）３を使用したこと以外は実施例１と同様にして正極活物質を生成し、コイン型電池を作製した。そして、この電池について、充放電電流密度０．５ｍＡ／ｃｍ２なる条件でＯＣＶ（開回路電圧）が４．２Ｖになるまで充電した。
【００４８】
実施例３
複合酸化物粒子の表面処理液に溶解する金属アルコキシドとしてＭｎ（Ｏ−ｉ−Ｃ３Ｈ７）２を使用したこと以外は実施例１と同様にして正極活物質を生成し、コイン型電池を作製した。そして、この電池について、充放電電流密度０．５ｍＡ／ｃｍ２なる条件でＯＣＶ（開回路電圧）が４．２Ｖになるまで充電した。
【００４９】
比較例１
表面処理を施していない複合酸化物粒子をそのまま正極活物質として使用したこと以外は実施例１と同様にしてコイン型電池を作製した。そして、この電池について、充放電電流密度０．５ｍＡ／ｃｍ２なる条件でＯＣＶ（開回路電圧）が４．２Ｖになるまで充電した。
【００５０】
以上のようにして作製された電池について、複素インピーダンス測定を１２時間毎に行い、求められるＣｏｌｅ−Ｃｏｌｅ ｐｌｏｔより正極表面における界面分極抵抗を見積もった。なお、複素インピーダンスの測定条件は以下の通りである。
【００５１】
測定使用機種：ＨＰ４１９２Ａ Ｉｍｐｅｄａｎｎｃｅ Ａｎａｌｉｚｅｒ
温度：常温（２３℃）
周波数範囲：０．５Ｈｚ〜１０００Ｈｚ
印加バイアス電圧：４．２Ｖ
最大電流：１０ｍＡ
測定間隔：１２時間毎
求められた界面分極抵抗の経時変化を図１に示す。なお、図１において、縦軸は、測定開始からｔ時間後の界面分極抵抗Ｒｔを、測定開始時の界面分極抵抗Ｒｔ＝０で規格化した値である。
【００５２】
図１からわかるように、Ｃｏ，ＡｌまたはＭｎの金属アルコキシドによって表面処理が施された複合酸化物粒子を正極に用いた実施例１〜実施例３の電池は、未処理の複合酸化物粒子を正極に用いた比較例１の電池に比べて、正極表面における界面分極抵抗の経時的な増加が抑制されている。
【００５３】
このことから、Ｎｉを含有する複合酸化物粒子をＣｏ，Ａｌ，Ｍｎを含む化合物で処理することは、非水電解質二次電池において、当該複合酸化物粒子と電解液との間の界面分極抵抗が増大し難いものとする上で有効であることがわかった。
【００５４】
【発明の効果】
以上の説明からも明らかなように、本発明の正極活物質は、ＬｉＮｉｘＭｙＯ２（但し、ＭはＡｌ，Ｍｎ，Ｆｅ，Ｎｉ，Ｃｏ，Ｃｒ，Ｔｉ，Ｚｎ，Ｐ，Ｂから選ばれる少なくとも一種の元素を表し、ｘは０＜ｘ≦１、ｙは０≦ｙ＜１である）で表される複合酸化物粒子の表面を、Ｃｏ，Ａｌ，Ｍｎの少なくともいずれかを含有する金属アルコキシドによって被覆処理したものであるので、高容量，安価であるとともに界面分極抵抗の経時的な増加が少ない。したがって、このような正極活物質を用いることで、内部抵抗が小さく、充電エネルギーが効率良く使用される非水電解質二次電池が実現できる。
【図面の簡単な説明】
【図１】正極表面における界面分極抵抗の経時変化を示す特性図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a positive electrode active material used in a non-aqueous electrolyte secondary battery and the like, and a non-aqueous electrolyte secondary battery using the same.
[0002]
[Prior art]
2. Description of the Related Art In recent years, with the dramatic progress of various electronic devices, research on a secondary battery has been promoted as a portable power source that can be used stably and economically for a long time.
[0003]
Representative secondary batteries include a lead storage battery, an alkaline storage battery, a lithium secondary battery, and the like. Among these, lithium secondary batteries are being actively studied because they can achieve higher output and higher energy density than other conventional secondary batteries, and proposals are made in various configurations. Some are already in practical use.
[0004]
For example, as a negative electrode of a lithium secondary battery, a material capable of doping and undoping lithium, metallic lithium or a lithium alloy is generally used. As a material capable of doping and undoping lithium, a conductive polymer or a layered compound (carbon material, metal oxide, or the like) doped with lithium has been proposed.
[0005]
On the other hand, as the positive electrode active material constituting the positive electrode, metal oxides, metal sulfides, and specific polymers can be used. Specifically, lithium-free compounds such as TiS 2 , MoS 2 , NbSe 2 , and V 2 O 5 , and lithium such as LiMO 2 (where M is Co, Ni, Mn, Fe, etc.) Complex oxides contained therein. Above all, lithium-containing composite oxides containing Ni are expected to be large in capacity and relatively inexpensive. These compounds can be used alone or in combination of two or more.
[0006]
As a separator interposed between the negative electrode and the positive electrode, a polymer film such as polypropylene is used. In this case, from the viewpoint of lithium ion conductivity and energy density, the polymer film needs to be as thin as possible, and is practically 50 μm or less.
[0007]
As the electrolytic solution, a solution obtained by dissolving a lithium salt such as LiPF 6 as an electrolyte salt in a nonaqueous solvent mainly containing a high dielectric constant solvent such as propylene carbonate is used.
[0008]
[Problems to be solved by the invention]
By the way, in general, in a battery, a part of the inherent energy is consumed by its internal resistance. Therefore, in order to use the charged energy efficiently, it can be said that the lower the internal resistance, the better.
[0009]
The internal resistance of a battery is mainly derived from the resistance in the active material and the resistance generated at the interface between the active material particles and the electrolyte (hereinafter referred to as interfacial polarization resistance). It corresponds to the internal resistance of the whole battery.
[0010]
Here, in the lithium-containing composite oxide exemplified above as the positive electrode active material, a phenomenon such that the interfacial polarization resistance increases with time is observed. Among them, the lithium-containing composite oxide containing Ni has an advantage that it has a large capacity and is relatively inexpensive, but one of its disadvantages is that the increase in interface resistance with time tends to be relatively large as compared with LiCoO 2 or the like. It has become.
[0011]
Therefore, the present invention has been proposed in view of such a conventional situation, and an object of the present invention is to provide a positive electrode active material having a small increase in interfacial polarization resistance with time. Another object of the present invention is to provide a nonaqueous electrolyte secondary battery having a low internal resistance and using charging energy efficiently by using such a positive electrode active material.
[0012]
[Means for Solving the Problems]
In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, in the vicinity of the surface of the lithium-containing composite oxide containing Ni, any one of Co, Al, and Mn has been added to Ni as a solid state. It has been found that if the compound oxide is present at a high concentration, the increase in interfacial polarization resistance of this composite oxide over time can be suppressed.
[0013]
The positive electrode active material of the present invention has been completed based on such findings, and includes LiNi x MyO 2 (where M is Al, Mn, Fe, Ni, Co, Cr, Ti, Zn, P, B represents at least one element selected from the group consisting of B, where x is 0 <x ≦ 1 and y is 0 ≦ y <1). Coated with a metal alkoxide containing
[0015]
When the surface of the composite oxide particle is coated with these compounds, a compound containing Co, Al, and Mn adheres to the particle surface, and z / (x + z) on the surface of the composite oxide particle (where x is This is the atomic composition ratio of Ni, and z is the sum of the atomic composition ratios of Co, Al, and Mn. Here, this value is D (s), but z / (x + z) ( Here, this value is assumed to be larger than D (b). In particular, when a compound containing Co is used as the treatment compound, D (s) preferably satisfies 1 ≧ D (s)> 0.3.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, specific embodiments of the present invention will be described.
[0017]
The positive electrode active material of the present invention, LiNi x M y O 2 (where, M represents Al, Mn, Fe, Ni, Co, Cr, Ti, Zn, P, at least one element selected from B, x is The surface of the composite oxide particles represented by 0 <x ≦ 1, y is 0 ≦ y <1) is coated with a compound containing at least one of Co, Al, and Mn. That is, in the positive electrode active material, a compound containing Co, Al, or Mn adheres to the surface of the lithium composite oxide particles containing Ni, whereby the particles are surface-modified.
[0018]
In the composite oxide particles subjected to such surface modification, the proportion of Ni occupied on the surface is reduced by the amount of the compound containing Co, Al or Mn attached to the surface. The decrease in the proportion occupied by Ni suppresses an increase in interfacial polarization resistance with time. Therefore, excellent characteristics as a positive electrode active material can be obtained while having the advantages of high-capacity and inexpensive composite oxide particles containing Ni without increasing the internal resistance of the battery.
[0019]
Examples of the compound for treatment include metal alkoxides of Co, Al or Mn. Of these, for example, in order to perform surface modification of the composite oxide particles with a Co alkoxide, the composite oxide particles to be treated are added to a surface treatment solution in which the Co alkoxide is dissolved, and after stirring, about one day. save. During storage, a bond of -O-Co-O is generated on the surface of the composite oxide particle, and a layer having a high Co concentration is formed. After storage, the supernatant is discarded and the remaining particles are washed several times with a solvent. Then, the particles are dried to obtain surface-modified composite oxide particles. The surface modification with Al alkoxide and Mn alkoxide is performed according to this.
[0020]
Further, the compound for treatment may be a compound containing Li, that is, a composite compound of Li and Mn, Al or Co.
[0021]
Note that it is desirable to use a compound containing Co as the treatment compound. This is because Al or Mn works in the direction of slightly reducing the capacity of the battery when dissolved in the composite oxide particles, but hardly reduces the capacity of the battery in the case of Co.
[0022]
In the composite oxide particles subjected to the surface modification as described above, the concentration of Co, Al, or Mn is higher on the particle surface than on the entire particle. That is, z / (x + z) on the surface (where x is the atomic composition ratio of Ni and z is the sum of the atomic composition ratios of Co, Al, and Mn) is D (s), and z / ( When (x + z) is D (b), the value of D (s) is larger than the value of D (b). In particular, when a compound containing Co is used as the treatment compound, the value of D (s) is desirably 1 ≧ D (s)> 0.3. When D (s) is 0.3 or less, it is not possible to sufficiently decrease the interfacial resistance of the composite oxide particles over time.
[0023]
Note that D (s) and D (b) are values obtained as follows.
[0024]
Measurement of D (s):
50 cc of 0.1 M HCl aqueous solution is weighed, 500 mg of powder is put into this HCl aqueous solution at room temperature, and immersed at room temperature 23 ° C. for 5 minutes. Thereby, the surface of the powder is dissolved by the acid. Next, the residual powder remaining without being dissolved is removed from the aqueous HCl solution. Then, only the aqueous HCl solution remaining as the supernatant is analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and the quantitative ratio of Ni and Co, Al, or Mn present in the solution is measured. Calculate z / (x + z) based on the quantity.
[0025]
Measurement of D (b):
500 mg of powder is put into a 1M aqueous HCl solution to dissolve the whole powder. Then, the aqueous HCl solution in which the powder is dissolved is analyzed by ICP-AES, and the quantitative ratio of Ni and Co, Al or Mn present in the solution is measured, and z / (x + z) is calculated based on the measured amount. calculate.
[0026]
The composite oxide particles subjected to the surface modification as described above are used for a positive electrode of a nonaqueous electrolyte secondary battery.
[0027]
To form a positive electrode from the composite oxide particles, the composite oxide particles, a conductive agent and a binder are mixed to prepare a positive electrode mixture, and the positive electrode mixture is compression-molded into a desired electrode shape. Here, as the conductive agent and the binder, any of those commonly used in this type of battery can be used.
[0028]
Further, the negative electrode and the non-aqueous electrolyte used in combination with the positive electrode may also be those used in this type of battery.
[0029]
For example, as the active material of the negative electrode, a material capable of doping and undoping lithium is used in addition to lithium metal such as lithium metal or a lithium-aluminum alloy. Materials capable of doping / dedoping lithium include, for example, pyrolytic carbons, cokes (pitch coke, needle coke, petroleum coke, etc.), graphites, glassy carbons, and organic polymer compound fired bodies (A phenol resin, a furan resin or the like, which is calcined at an appropriate temperature and carbonized), a carbonaceous material such as carbon fiber or activated carbon, or a polymer such as polyacetylene or polypyrrole can be used.
[0030]
To form a negative electrode using such a carbonaceous material or polymer, a negative electrode mixture is prepared by mixing these materials with a binder, and the negative electrode mixture is compression-molded into a desired electrode shape.
[0031]
On the other hand, examples of the non-aqueous solvent of the non-aqueous electrolyte include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, γ-butyrolactone, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 2-methyl Tetrahydrofuran, 3-methyl-1,3-dioxolan, methyl propionate, methyl butyrate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate and the like can be used. In particular, it is preferable to use cyclic carbonates such as propylene carbonate and vinylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate and dipropyl carbonate, from the viewpoint of voltage stability. These non-aqueous solvents may be used alone or in combination of two or more.
[0032]
As an electrolyte salt dissolved in the nonaqueous solvent, LiPF 6, LIBF 4, LiClO 4, LiAsF 6, LiBF 4, LiCF 3 SO 3, LiN (CF 3 SO 2) can be used 2 or the like, Ya Among especially LiPF 6 it is preferred to use LiBF 4.
[0033]
In this battery, a solid electrolyte may be used instead of the non-aqueous electrolyte.
[0034]
Further, the shape of the battery is not particularly limited, and may be various shapes such as a cylindrical shape, a square shape, a coin shape, and a button shape.
[0035]
【Example】
Hereinafter, examples of the present invention will be described based on experimental results.
[0036]
Example 1
A positive electrode active material was produced as follows.
[0037]
First, the following composite oxide particles and a surface treatment liquid were prepared.
[0038]
Composite oxide particles (object to be treated): CoO, NiO and LiOH.H 2 O are mixed so that Li: Ni: Co = 1: 0.8: 0.2 (molar ratio), LiNi 0.8 Co 0.2 O 2 powder surface treatment solution obtained by heat treatment at a temperature of 700 to 800 ° C. for 10 hours: Co isopropoxide [Co (OiC 3 H 7 ) 2 ] 1 g (equivalent to 5.6 × 10 −3 mol) was weighed, and a Co alkoxide solution dissolved in 100 cc of 2 -ethoxyethanol (C 2 H 5 OCH 2 CH 2 OH) was combined with the above surface treatment solution under a nitrogen atmosphere. 2 g of the oxide particles were charged, mixed and stirred, and then stored at room temperature for 24 hours. After storage, the supernatant was discarded, and the remaining particles were washed several times with 2-ethoxyethanol. After drying the particles, the particles were heated at a temperature of 300 to 800 ° C. in the atmosphere to obtain surface-modified composite oxide particles (positive electrode active material).
[0039]
D (s) and D (b) of the untreated composite oxide particles and the surface-treated composite oxide particles were measured by a dissolution test of 0.1 M HCl or 1 M HCl. Table 1 shows the results.
[0040]
[Table 1]
As shown in Table 1, the value of D (s) is larger in the surface-treated composite oxide particles than in the untreated composite oxide particles. From this, it was confirmed that the surface treatment increased the Co concentration on the surface of the composite oxide particles.
[0042]
Next, a coin-type battery was manufactured using the composite oxide particles whose surface was modified as described above as a positive electrode active material.
[0043]
7 parts by weight of graphite and 3 parts by weight of a fluoropolymer binder were added to 90 parts by weight of the composite oxide particles, and mixed with dimethylformamide (DMF) to prepare a positive electrode mixture. After sufficiently drying the positive electrode mixture to completely volatilize DMF as a solvent, about 60 mg of the solvent was weighed and molded under pressure to produce a disk-shaped positive electrode having a surface area of about 2 cm 2 . .
[0044]
On the other hand, the negative electrode was produced by punching a rolled Li metal into a disk shape.
[0045]
The amount of Li in the negative electrode is several hundred times the maximum charging capacity of the positive electrode, and does not limit the electrochemical performance of the positive electrode.
[0046]
The positive electrode and the negative electrode produced as described above were accommodated in a positive electrode can and a negative electrode can, respectively, and laminated with a separator interposed therebetween. Then, an electrolytic solution obtained by dissolving LiPF 6 in propylene carbonate (PC) was injected into the can, and the positive electrode can and the negative electrode can were caulked via a gasket and sealed to produce a coin-type battery. Then, the battery was charged until the OCV (open circuit voltage) became 4.2 V under the condition of a charge / discharge current density of 0.5 mA / cm 2 .
[0047]
Example 2
A positive electrode active material was produced in the same manner as in Example 1 except that Al (OCH 3 ) 3 was used as a metal alkoxide dissolved in the surface treatment solution of the composite oxide particles, to produce a coin-type battery. Then, the battery was charged until the OCV (open circuit voltage) became 4.2 V under the condition of a charge / discharge current density of 0.5 mA / cm 2 .
[0048]
Example 3
A positive electrode active material was produced in the same manner as in Example 1 except that Mn (OiC 3 H 7 ) 2 was used as a metal alkoxide dissolved in the surface treatment solution of the composite oxide particles, and a coin-type battery was manufactured. Produced. Then, the battery was charged until the OCV (open circuit voltage) became 4.2 V under the condition of a charge / discharge current density of 0.5 mA / cm 2 .
[0049]
Comparative Example 1
A coin-type battery was produced in the same manner as in Example 1, except that the composite oxide particles not subjected to the surface treatment were used as the positive electrode active material. Then, the battery was charged until the OCV (open circuit voltage) became 4.2 V under the condition of a charge / discharge current density of 0.5 mA / cm 2 .
[0050]
With respect to the battery manufactured as described above, the complex impedance was measured every 12 hours, and the interfacial polarization resistance on the positive electrode surface was estimated from the obtained Cole-Cole plot. The measurement conditions of the complex impedance are as follows.
[0051]
Model used for measurement: HP4192A Impedance Analyzer
Temperature: room temperature (23 ° C)
Frequency range: 0.5Hz to 1000Hz
Applied bias voltage: 4.2V
Maximum current: 10mA
FIG. 1 shows the time-dependent change of the interfacial polarization resistance determined every 12 hours. In FIG. 1, the vertical axis represents a value obtained by normalizing the interfacial polarization resistance R t after t hours from the start of the measurement by the interfacial polarization resistance R t = 0 at the start of the measurement.
[0052]
As can be seen from FIG. 1, the batteries of Examples 1 to 3 using the composite oxide particles surface-treated with the metal alkoxide of Co, Al or Mn for the positive electrode were obtained by using untreated composite oxide particles. Compared with the battery of Comparative Example 1 used for the positive electrode, the increase in interfacial polarization resistance on the positive electrode surface over time is suppressed.
[0053]
For this reason, treating the Ni-containing composite oxide particles with a compound containing Co, Al, and Mn makes it possible to reduce the interfacial polarization resistance between the composite oxide particles and the electrolyte in a non-aqueous electrolyte secondary battery. Has been found to be effective in making it difficult to increase.
[0054]
【The invention's effect】
As is clear from the above description, the cathode active material of the present invention is LiNi x MyO 2 (where M is at least one selected from Al, Mn, Fe, Ni, Co, Cr, Ti, Zn, P, and B). X represents 0 <x ≦ 1 and y represents 0 ≦ y <1). The surface of the composite oxide particle represented by x is a metal alkoxide containing at least one of Co, Al and Mn. Since it has been coated with a coating , it has a high capacity, is inexpensive, and has little increase in interfacial polarization resistance with time. Therefore, by using such a positive electrode active material, a non-aqueous electrolyte secondary battery having a small internal resistance and efficiently using charging energy can be realized.
[Brief description of the drawings]
FIG. 1 is a characteristic diagram showing a change with time of interfacial polarization resistance on a positive electrode surface.
Claims (8)
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| JP20608395A JP3582161B2 (en) | 1995-08-11 | 1995-08-11 | Positive electrode active material and non-aqueous electrolyte secondary battery using the same |
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| JP20608395A JP3582161B2 (en) | 1995-08-11 | 1995-08-11 | Positive electrode active material and non-aqueous electrolyte secondary battery using the same |
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| WO2019164313A1 (en) * | 2018-02-23 | 2019-08-29 | 주식회사 엘지화학 | Positive electrode active material for secondary battery, preparation method therefor, and lithium secondary battery comprising same |
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