JP4368139B2

JP4368139B2 - Anode material for non-aqueous electrolyte secondary battery

Info

Publication number: JP4368139B2
Application number: JP2003129705A
Authority: JP
Inventors: 治成島村; 貴之中本; 秀明大山; 靖彦美藤
Original assignee: Panasonic Corp; Sumitomo Metal Industries Ltd; Matsushita Electric Industrial Co Ltd
Current assignee: Panasonic Corp; Sumitomo Metal Industries Ltd; Panasonic Holdings Corp
Priority date: 2003-05-08
Filing date: 2003-05-08
Publication date: 2009-11-18
Anticipated expiration: 2023-05-08
Also published as: JP2004335272A

Description

【０００１】
【発明の属する技術分野】
本発明は、改良された非水電解質二次電池用負極材料に関し、特に、充放電サイクル特性および高率放電特性に優れた非水電解質二次電池を与える負極材料に関する。本発明の非水電解質二次電池用負極材料を備えた非水電解質二次電池は、携帯情報端末、携帯電子機器、家庭用小型電力貯蔵装置、モータを動力源とする自動二輪車、電気自動車、ハイブリッド電気自動車などに好適である。
【０００２】
【従来の技術】
高起電力、高エネルギー密度などの特長を持つ非水電解質二次電池、特にリチウム二次電池は、移動体通信機器、携帯電子機器などの主電源として、従来から用いられている。負極材料としては、リチウム金属または黒鉛が主に用いられており、特に、リチウム金属を用いる場合には、最も高いエネルギー密度を得ることができる。
【０００３】
しかしながら、リチウム金属を負極材料とするリチウム二次電池には、充電時に負極に析出したデンドライトが、充放電の繰り返しにより成長して、セパレータを貫通し、内部短絡を引き起こすという欠点がある。また、黒鉛を負極材料とするリチウム二次電池には、黒鉛の理論容量（３７２ｍＡｈ／ｇ）が、リチウム金属の理論容量よりも１０％程度小さいことから、近年における高エネルギー密度化の要請に充分に応えることができないという欠点がある。
【０００４】
そこで、近年、新たな負極材料として、ケイ素（Ｓｉ）を用いることが検討されている。ケイ素は、理論上、リチウムイオンを、ケイ素原子５個あたり最大２２個まで、すなわち、Ｌｉ₂₂Ｓｉ₅の組成になるまで吸蔵することが可能である。ケイ素の理論容量は４１９９ｍＡｈ／ｇであり、黒鉛の理論容量よりも遙かに大きい。また、ケイ素を負極材料として用いた場合、通常の充電では、金属リチウムが負極の表面に析出することがないので、デンドライトの成長による内部短絡の虞もない。
【０００５】
このようなケイ素を用いた負極材料は、これまで数多く提案されている（例えば、特許文献１〜３参照。）。特許文献１では、固相Ａからなる核粒子、および前記核粒子の表面の全部または一部を覆う固相Ｂの被覆層からなる複合粒子が負極材料として提案されている。固相Ａには、ケイ素またはケイ素を含む固溶体もしくは金属間化合物が用いられている。固相Ｂには、固相Ａとは組成が異なるように、ケイ素またはケイ素を含む固溶体もしくは金属間化合物が用いられている。また、特許文献１には明記されていないが、合金溶湯を電気炉内で冷却することにより前記複合粒子を得ていることから、固相Ａも固相Ｂも結晶質相である。
【０００６】
【特許文献１】
特開２０００−３０７０３号公報（第４頁、〔００１８〕）
【特許文献２】
特開２０００−２４３３８９号公報
【特許文献３】
特開平１０−８３８１７号公報
【０００７】
【発明が解決しようとする課題】
ケイ素は、リチウムと反応すると体積が約４倍に膨張する。このため、ケイ素を負極材料とするリチウム二次電池の充放電を繰り返すと、ケイ素粒子内に大きな内部歪みが生じてクラックが発生し、粒子が微粉化しやすいという問題がある。このような微粉化は、電池の充放電サイクル特性の低下につながる。
【０００８】
特許文献１で提案されているように、ケイ素を他元素と合金化することにより、粒子の微粉化をある程度抑制することは可能である。
しかしながら、固相Ａも固相Ｂも結晶質相からなる場合、微粉化を充分に抑制することは困難である。
【０００９】
本発明は、上記を鑑みたものであり、ケイ素の微粉化を充分に抑制することにより、充放電サイクル特性および高率放電特性に優れた非水電解質二次電池を与える負極材料を提供することを目的とする。
【００１０】
【課題を解決するための手段】
すなわち、本発明は、固相Ａからなる核粒子の表面の一部または全部に、固相Ｂからなる被覆層が形成された複合粒子からなる非水電解質二次電池用負極材料であって、固相Ａは、Ｓｉと、ＳｂおよびＰよりなる群から選ばれる少なくとも１種またはＢとを含む非晶質合金相であり、固相Ｂは、Ｓｉと、Ｍｇ、Ｔｉ、Ｚｒ、Ｖ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｕ、ＣｏおよびＮｉよりなる群から選ばれる少なくとも１種とを含む結晶質合金相であり、前記固相ＡのＳｉ含有率が、９５〜９９．９９重量％であり、前記固相ＡにおけるＳｂ、ＰおよびＢの合計の含有率が、０．０１〜５重量％である、非水電解質二次電池用負極材料に関する。
【００１１】
前記核粒子と前記被覆層との重量比は、５：９５〜４０：６０であることが好ましい。
【００１２】
固相Ｂは、ＳｉとＴｉとの結晶質合金相からなることが好ましく、特に組成式がＴｉＳｉ₂で表される金属間化合物相からなることが好ましい。
【００１３】
本発明は、また、上記の非水電解質二次電池用負極材料を、リチウムイオンを吸蔵および放出する材料として備えた非水電解質二次電池用負極に関する。
【００１４】
本発明は、また、前記非水電解質二次電池用負極と、リチウムの吸蔵・放出が可能な正極と、前記負極と正極との間に介在するセパレータと、非水電解質を具備する非水電解質二次電池に関する。
【００１５】
【発明の実施の形態】
本発明の非水電解質二次電池用負極材料は、固相Ａからなる核粒子の表面の一部または全部に、固相Ｂからなる被覆層が形成された複合粒子からなり、固相Ａは、Ｓｉと、ＳｂおよびＰよりなる群から選ばれる少なくとも１種またはＢとを含む非晶質合金相であり、固相Ｂは、Ｓｉと、Ｍｇ、Ｔｉ、Ｚｒ、Ｖ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｕ、ＣｏおよびＮｉよりなる群から選ばれる少なくとも１種とを含む結晶質合金相である。
つまり、固相Ａと固相Ｂは、組成および結晶状態が異なる。
【００１６】
本発明において、非晶質合金相とは、広角Ｘ線回折法により得られる回折パターンにおいて、その合金相の結晶面に帰属されるピークが存在しないことをいう。また、結晶質合金相とは、広角Ｘ線回折法により得られる回折パターンにおいて、その合金相の結晶面に帰属されるピークが存在することをいう。「ピークが存在しない」とは、アニール（５００℃で１時間保持）後の結晶子サイズが１００ｎｍ以下、または非晶質相であることをいう。
【００１７】
ＳｉをＰ、ＳｂまたはＢと非晶質合金化することにより、ケイ素とリチウムとの反応による固相Ａの体積膨張を抑制できる。また、Ｐ、ＳｂまたはＢをＳｉにドープすることにより（以下、Ｐ、ＳｂおよびＢをドープ元素ともいう。）、メカニカルアロイング法などの固相反応により、固相Ａを非晶質化するのに必要な時間を短縮することができる。また、その結果、固相Ａと固相Ｂからなる複合粒子を製造する段階で、固相Ｂの非晶質化を防止することもできる。
【００１８】
固相Ａからなる核粒子の表面の一部または全部に、固相Ｂからなる被覆層を形成することにより、核粒子の微粉化が抑制されるとともに、負極材料の電子伝導性が向上する。固相Ｂが結晶質合金相でなければならないのは、結晶粒界が多い非晶質相であると、クラックが生じて電子伝導性が低下し、高率放電特性の低下を招くからである。
【００１９】
固相ＡのＳｉ含有率は、９５〜９９．９９９重量％が好ましく、９８〜９９．９９重量％がより好ましい。固相ＡのＳｉ含有率が９５重量％未満の場合、すなわちドープ元素の含有率が５重量％を超える場合、得られる負極材料の容量が減少する。また、ドープ元素を５重量％より多くドープしても、固相Ａの非晶質化に要する時間はほとんど短縮されない。一方、固相ＡのＳｉ含有率が、９９．９９９重量％を超える場合、すなわちドープ元素の含有率が０．００１重量％未満の場合は、固相反応による製造工程において、固相Ａの非晶質化が進行しにくくなるため、負極材料を得るのに長時間を要するのみならず、固相Ｂの非晶質化を招く虞がある。
【００２０】
固相Ｂとしては、高率放電特性を改善する上で、電子伝導性の高いＳｉとＴｉとの結晶質合金相が好ましく、組成式ＴｉＳｉ₂で表される金属間化合物相が特に好ましい。ＳｉとＴｉとの結晶質合金相からなる粒子には、固相反応により、固相Ａからなる核粒子と複合粒子化することが容易であるという製造上の利点もある。
固相Ｂが固溶体の場合、二元合金については、Ｓｉと合金化元素Ｍ１との重量比が１０：９０〜４０：６０であることが好ましく、また、三元合金については、Ｓｉと合金化元素Ｍ１と合金化元素Ｍ２との重量比が１０：９０（Ｍ１とＭ２の重量比は任意）〜４０：６０（Ｍ１とＭ２の重量比は任意）であることが好ましい。
【００２１】
核粒子と被覆層との重量比は、５：９５〜４０：６０が好ましい。核粒子の割合が過少な場合は、初期放電容量が減少する。一方、被覆層の割合が過少な場合は、核粒子の被覆が充分でないためにＳｉとＬｉとの反応による固相Ａの膨張を有効に抑えることができなくなり、充放電サイクル特性が低下する。さらに、電子伝導性の低下により、高率放電特性も低下する。
【００２２】
なお、固相Ａについては０．００１重量％以下の量、また、固相Ｂについては０．１重量％以下の量であれば、それぞれ上記した各構成元素以外の元素、例えばＯ、Ｃ、Ｎ、Ｓ、Ｃａ、Ｍｇ、Ａｌなどの不純物を含んでいても構わない。
【００２３】
以下に、本発明の負極材料の製造方法について説明する。
まず、固相Ａを構成する各元素を所定の割合で溶解槽にて加熱溶融させて合金溶湯を得、この合金溶湯を急冷凝固させて第一の合金塊を製造する。また、固相Ｂを構成すべき各元素を所定の割合で溶解槽にて加熱溶融させて合金溶湯を得、この合金溶湯を急冷凝固させて第二の合金塊を製造する。それぞれの合金溶湯を得る際に溶融させる各構成元素は、単体の形態で溶解槽に投入してもよく、固溶体、金属間化合物などの合金の形態で溶解槽に投入してもよい。なお、溶融の方法としては、高周波溶解法、アーク溶解法などの従来公知の方法を用いることができる。また、急冷凝固させる方法としては、ロールスピニング法、メルトドラッグ法、直接鋳造圧延法などの従来公知の方法を用いることができる。
【００２４】
次いで、第一の合金塊と第二の合金塊とを、ボールミルを用いて、機械的に攪拌、混合し、合金粉末を作製するいわゆるメカニカルアロイングを行う。このメカニカルアロイングを適宜の時間実施することにより、非晶質合金相である固相Ａからなる核粒子の表面に、結晶質合金相である固相Ｂからなる被覆層を形成することができる。
【００２５】
本発明に係る非水電解質二次電池用負極は、上述した負極材料をリチウムイオンを吸蔵および放出する材料として用いた電極である。例えば、本発明の負極材料を、導電剤および結着剤溶液とともに混練してスラリー状の負極合剤を調製し、この負極合剤を、厚み１〜５００μｍ程度の銅箔などからなる集電体上に塗布し、乾燥後、圧延することにより、負極板を作製することができる。上記の負極合剤に代えて、本発明の負極材料の粒子表面に導電剤層を形成した後、これと結着剤溶液とを混練して得たスラリー状の負極合剤を用いてもよい。導電剤としては、人造黒鉛、膨張黒鉛などの黒鉛、アセチレンブラック、ケッチェンブラックなどの無定形炭素が例示される。導電剤の一般的な添加量は、負極材料１００重量部に対して１〜５０重量部であるが、導電剤の添加量が過多になると容量減少が顕著になるので、導電剤は、負極材料１００重量部に対して３０重量部を超えないことが好ましい。結着剤としては、スチレンブタジエンゴム、ポリフッ化ビニリデンなどが例示される。集電体材料としては、ステンレス鋼、ニッケル、銅、銅合金などが例示される。なかでも電子伝導性が極めて良好な銅および銅合金が好ましい。
【００２６】
【実施例】
本発明を実施例に基づいてさらに詳細に説明する。本発明は下記実施例に限定されるものではなく、その要旨を変更しない範囲で適宜変更して実施することが可能である。
【００２７】
［実験１］
本発明の負極材料および比較のための負極材料を作製し、各負極材料の固相Ａの結晶状態および粉体抵抗率を調べた。また、各負極材料を用いて非水電解質二次電池を作製し、各電池の高率放電特性および充放電サイクル特性を調べた。
【００２８】
《実施例１》
固相Ａには、ＳｉとＰを用い、これらを重量比１９．９：０．１の混合物とした。この混合物を高周波溶解槽に投入して溶解させ、得られた合金溶湯を、単ロール法により急冷凝固させて、核粒子の前駆体である第一の合金塊を得た。
また、固相Ｂには、ＣｏとＳｉを用い、これらを原子比１：２の混合物とした。この混合物を高周波溶解槽に投入して溶解させ、得られた合金溶湯を、単ロール法により急冷凝固させて、組成式ＣｏＳｉ₂で表される金属間化合物からなる被覆層の前駆体である第二の合金塊を得た。
次いで、第一の合金塊と第二の合金塊とを重量比２０：８０で混合した混合物を、遊星ボールミルの容器内に投入し、ミルの回転速度を２８００ｒｐｍに設定してメカニカルアロイングを１時間行った。これにより、核粒子の表面に被覆層が形成された複合粒子粉末を得た。この複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ａ１を作製した。
【００２９】
《実施例２〜８８》
Ｓｉと混合するドープ元素の種類およびＳｉとドープ元素との重量比を表１または２に示すように変えたこと以外は、実施例１と同様にして、第一の合金塊を作製した。
固相Ｂには、表１または２に示す金属間化合物または固溶体からなる第二の合金塊を用いた。
次いで、第一の合金塊と、第二の合金塊とを重量比２０：８０で混合した混合物を、遊星ボールミルの容器内に投入し、ミルの回転速度を２８００ｒｐｍに設定してメカニカルアロイングを１時間行った。これにより、核粒子の表面に金属間化合物相または固溶体相からなる被覆層が形成された複合粒子粉末を得た。この複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ａ２〜Ａ８８を作製した。
なお、被覆層を形成する固相Ｂが固溶体である負極材料Ａ４５〜Ａ８８については、第二の合金塊を作製するにあたり、二元合金についてはＳｉと合金化元素Ｍ１との原子比が９９：１の混合物を使用し、また三元合金についてはＳｉと合金化元素Ｍ１と合金化元素Ｍ２との原子比が９９：０．５：０．５の混合物を使用した。
【００３０】
【表１】

【００３１】
【表２】

【００３２】
《比較例１》
メカニカルアロイングの時間を、１時間に代えて、３０分間としたこと以外は、実施例１と同様にして、核粒子の表面に被覆層が形成された複合粒子粉末を得た。この複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ｘ１を作製した。
【００３３】
《比較例２〜２２》
第二の合金塊として、組成式ＣｏＳｉ₂で表される金属間化合物からなる合金塊に代えて、表３に示す固相Ｂの金属間化合物または固溶体からなる合金塊を用いたこと以外は、比較例１と同様にして、核粒子の表面に金属間化合物または固溶体からなる被覆層が形成された複合粒子粉末を得た。各複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ｘ２〜Ｘ２２を作製した。なお、被覆層を形成する固相Ｂが固溶体である負極材料Ｘ１２〜Ｘ２２については、二元合金として第二の合金塊を作製するにあたり、Ｓｉと合金化元素Ｍ１との原子比が９９：１の混合物を使用した。
【００３４】
【表３】

【００３５】
（ｉ）正極板の作製
正極活物質としてのコバルト酸リチウム（ＬｉＣｏＯ₂）粉末８５重量部と、導電剤としてのアセチレンブラック１０重量部と、結着剤としてのＰＶｄＦ（ポリフッ化ビニリデン）５重量部との混合物を、ＮＭＰ（脱水Ｎ−メチル−２−ピロリドン）に分散させて、スラリー状の正極合剤を調製した。この正極合剤を厚さ２０μｍのアルミニウム箔からなる正極集電体上に、片面あたり１５０μｍ厚に塗布し、乾燥後、圧延して、正極板を作製した。
【００３６】
（ii）負極板の作製
上記の実施例または比較例で作製した各負極材料７５重量部と、導電剤としてのアセチレンブラック２０重量部と、結着剤としてのＰＶｄＦ５重量部との混合物を、ＮＭＰに分散させて、スラリー状の負極合剤を調製した。この負極合剤を厚さ１４μｍの銅箔からなる負極集電体上に、片面あたり５０μｍ厚に塗布し、乾燥後、圧延して、負極板を作製した。
【００３７】
（iii）非水電解液の調製
エチレンカーボネート（ＥＣ）とエチルメチルカーボネート（ＥＭＣ）との体積比１：１の混合溶媒に、ＬｉＰＦ₆を１モル／リットルの濃度で溶かして非水電解液を調製した。
【００３８】
（iv）非水電解質二次電池の作製
上記の正極板、負極板および非水電解液を用いて、直径１８ｍｍ、高さ６５ｍｍの円筒形の非水電解質二次電池Ａ１〜Ａ８８、Ｘ１〜Ｘ２２（電池の符号は、用いた負極材料の符号に対応する）を作製した。セパレータには、ポリエチレン製の微多孔フィルムを用いた。
【００３９】
図２は作製した非水電解質二次電池の縦断面図であり、その内部構造の一部を分解斜視図で示してある。非水電解質二次電池は、正極１、負極２、これら両電極を離間するセパレータ３、絶縁板４、電池ケース５、ガスケット７、安全弁を備える封口板８、正極リード６などからなる。正極１および負極２は、セパレータ３を間に配して渦巻き状に巻き取られた状態で電池ケース５内に収容されており、正極１は正極リード６を介して封口板８に、負極２は負極リード（図示せず）を介して電池ケース５の底部に、それぞれ接続されて、充放電可能な構成となっている。
【００４０】
［固相Ａの結晶状態］
各負極材料中の固相Ａの結晶状態を評価するために、波長１．５４０５ｎｍのＣｕＫα線を線源とする広角Ｘ線回折装置（商品コード：ＲＩＮＴ−２５００、理学電機社製）を用い、回折角２θ＝１０°〜８０°の範囲における回折強度を測定した。固相Ａの結晶面に帰属されるピークの有無を調べた。結果を表４〜６に示す。表中のピークの有無において、「無」は固相Ａの結晶面に帰属されるピークが存在せず、固相Ａが非晶質相であったことを示し、「有」は上記ピークが存在し、固相Ａが結晶質相であったことを示す。一例として、負極材料Ａ３およびＸ３の回折パターンを図１に示す。
図１において、横軸は、固相Ａおよび固相Ｂの回折角２θ（度）であり、縦軸は、回折強度である。図中◎は固相Ａの結晶面に帰属されるピークを示し、●は、固相Ｂの結晶面に帰属されるピークを示す。
【００４１】
［粉体抵抗率］
各負極材料を２ｇ秤取し、２つの電流端子と２つの電圧端子の合計４つの測定点を有するセルの中に投入し、４００ｋｇｆ／ｃｍ²の圧力を加えた状態で、電流と電圧を同時に測定して、各負極材料の粉体抵抗率（Ω・ｃｍ）を測定した（４端子法）。粉体抵抗率の低い負極材料ほど、電子伝導性が良い負極材料である。結果を表４〜６に示す。
【００４２】
［初期放電容量および高率放電特性］
各電池を、２０°Ｃに保持した恒温槽に入れ、１０００ｍＡで４．２Ｖまで充電した後、２００ｍＡで２．５Ｖまで放電して、放電容量Ｃ１（ｍＡｈ）を求めた（初期放電容量）。次いで、それらの各電池を、１０００ｍＡで４．２Ｖまで充電した後、１０００ｍＡで２．５Ｖまで放電して、放電容量Ｃ２（ｍＡｈ）を求めた。放電容量Ｃ１に対する放電容量Ｃ２の比率Ｐ（％）を下式（１）に基づいて算出して、各電池の高率放電特性Ｐを評価した。Ｐの値が大きい電池ほど、高率放電特性が良い電池である。結果を表４〜６に示す。
【００４３】
Ｐ（％）＝（Ｃ２／Ｃ１）×１００（１）
【００４４】
［充放電サイクル特性］
また、各電池を、２０°Ｃに保持した恒温槽に入れ、１０００ｍＡで４．２Ｖまで充電した後、２００ｍＡで２．５Ｖまで放電する充放電を１００サイクル行った。そして、１サイクル目の放電容量Ｃ３に対する１００サイクル目の放電容量Ｃ４の容量維持率Ｑ（％）を下式（２）に基づいて算出して、充放電サイクル特性Ｑを評価した。Ｑの値が大きい電池ほど、充放電サイクル特性が良い電池である。結果を表４〜６に示す。
【００４５】
Ｑ（％）＝（Ｃ４／Ｃ３）×１００（２）
【００４６】
【表４】

【００４７】
【表５】

【００４８】
【表６】

【００４９】
（ｖ）電池の評価
表４〜６に示すように、負極材料Ａ１〜Ａ８８の粉体抵抗率は、１×１０^-1〜９×１０^-1Ω・ｃｍと低い値を得たのに対して、負極材料Ｘ１〜Ｘ２２の粉体抵抗率は５×１０⁰〜９．５×１０⁰Ω・ｃｍと高い値であった。このことから、負極材料Ａ１〜Ａ８８は負極材料Ｘ１〜Ｘ２２に比べて電子伝導性が良いことが分かった。
【００５０】
また、図１の負極材料Ｘ３の回折パターンに見られるように、比較例の負極材料Ｘ１〜Ｘ２２については、固相Ａの結晶面に帰属される回折角（２θ＝２８°および４８°）付近にピークが認められたが、負極材料Ａ３の回折パターンに見られるように、実施例の負極材料Ａ１〜Ａ８８については、それらの回折角付近にピークが認められなかった。このことから、負極材料Ａ１〜Ａ８８は、その固相Ａが非晶質相であるのに対して、負極材料Ｘ１〜Ｘ２２は、その固相Ａが結晶質相であることが分かった。また、図１より、負極材料Ａ３の固相Ｂと、負極材料Ｘ３の固相Ｂとは、同程度の結晶性を有していることも分かった。
【００５１】
さらに、表４〜６に示すように、電池Ａ１〜Ａ８８の高率放電特性Ｐの値が９０％以上と大きいことから、これらの負極材料を用いることにより高率放電特性の良い非水電解質二次電池を得ることが分かった。
【００５２】
さらにまた、表４〜６に示すように、電池Ａ１〜Ａ８８の充放電サイクル特性Ｑの値が９０％以上であり、電池Ｘ１〜Ｘ２２の充放電サイクル特性Ｑの値が７８％以下であることから、負極材料Ａ１〜Ａ８８を用いることにより充放電サイクル特性の良い非水電解質二次電池を得ることが分かった。
【００５３】
［実験２］
固相ＡのＳｉ含有率と高率放電特性との関係を調べた。
第一の合金塊の作製において、ＳｉとＰとの重量比１９．９：０．１の混合物に代えて、表７に示す固相Ａの各Ｓｉ含有率を有する混合物を用いるとともに、第一の合金塊と第二の合金塊との重量比を２１：７９としたこと以外は、実施例１と同様にして、核粒子の表面に被覆層が形成された複合粒子粉末を得た。これらの各複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ｂ１〜Ｂ１３を作製した。
【００５４】
【表７】

【００５５】
また、第一の合金塊の作製において、ＳｉとＰとの重量比１９．９：０．１の混合物に代えて、表８に示す固相Ａの各Ｓｉ含有率を有する混合物を用いるとともに、第一の合金塊と第二の合金塊との重量比を２１：７９としたこと以外は、実施例４５と同様にして、核粒子の表面に被覆層が形成された複合粒子粉末を得た。これらの各複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ｂ１４〜Ｂ２６を作製した。
【００５６】
【表８】

【００５７】
上記各負極材料（Ｂ１〜Ｂ２６）の固相Ａの結晶状態および粉体抵抗率を調べた。また、上記各負極材料を用いて非水電解質二次電池を作製し、各電池の高率放電特性および充放電サイクル特性を調べた。結果を表９および１０に示す。
【００５８】
【表９】

【００５９】
【表１０】

【００６０】
負極材料Ｂ１〜Ｂ２６のいずれの回折パターンにも、固相Ａの結晶面に帰属されるピークが認められなかった。このことから、それらの固相Ａが全て非晶質相であることが分かった。また、表９および１０より、固相ＡのＳｉ含有率が低くなるにつれて高率放電特性Ｐは向上するものの、初期放電容量は減少することが分かった。初期放電容量と高率放電特性との特性バランスを考慮すると、電池Ｂ４〜Ｂ１１および電池Ｂ１７〜Ｂ２４が特に優れていた。このことから、固相ＡのＳｉ含有率として、９５〜９９．９９９重量％が好ましいことが分かった。なお、表９および１０には示さなかったが、電池Ｂ１〜Ｂ２６の容量維持率Ｑは８６％〜９３％であった。
【００６１】
［実験３］
核粒子と被覆層との重量比と高率放電特性との関係を調べた。
第一の合金塊と第二の合金塊との重量比を、表１１に示す重量比としたこと以外は、実施例２と同様にして、基体粒子の表面に被覆層が形成された複合粒子粉末を得た。これらの各複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ｄ１〜Ｄ１０を作製した。
【００６２】
【表１１】

【００６３】
また、第一の合金塊と第二の合金塊との重量比を、表１２に示す重量比としたこと以外は、実施例４６と同様にして、基体粒子の表面に被覆層が形成された複合粒子粉末を得た。これらの各複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ｄ１１〜Ｄ１９を作製した。
【００６４】
【表１２】

【００６５】
上記各負極材料Ｄ１〜Ｄ１９の固相Ａの結晶状態および粉体抵抗率を調べた。また、各負極材料を用いて非水電解質二次電池を作製し、各電池の高率放電特性および充放電サイクル特性を調べた。結果を表１３および１４に示す。
【００６６】
【表１３】

【００６７】
【表１４】

【００６８】
負極材料Ｄ１〜Ｄ１９のいずれの回折パターンにも、固相Ａの結晶面に帰属されるピークは認められなかった。このことから、それらの固相Ａが全て非晶質相であることが分かった。また、表１３および１４より、核粒子に対する被覆層の割合が大きくなるにつれて高率放電特性Ｐは向上するものの、初期放電容量は減少することが分かった。初期放電容量と高率放電特性との特性バランスを考慮すると、電池Ｄ３〜Ｄ７および電池Ｄ１２〜Ｄ１６が特に優れていた。このことから、基体粒子と被覆層との重量比は、５：９５〜４０：６０が好ましいことが分かった。なお、表１３および１４には示さなかったが、電池Ｄ１〜Ｄ１９の容量維持率Ｑは８６％〜９３％であった。
【００６９】
［実験４］
固相Ｂの種類と高率放電特性との関係を調べた。
実施例１と同様にして、第一の合金塊を得た。この第一の合金塊と表１５に示す固相Ｂの第二の合金塊との重量比２２：７８の混合物を、遊星ボールミルの容器内に投入し、ミルの回転速度を２８００ｒｐｍに設定してメカニカルアロイングを１時間行い、核粒子の表面に金属間化合物相からなる被覆層が形成された複合粒子粉末を得た。これらの複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ｅ１〜Ｅ１１を作製した。
【００７０】
【表１５】

【００７１】
実施例４５と同様にして、第一の合金塊を得た。この第一の合金塊と表１６に示す固相Ｂの第二の合金塊との重量比２２：７８の混合物を、遊星ボールミルの容器内に投入し、ミルの回転速度を２８００ｒｐｍに設定してメカニカルアロイングを１時間行い、核粒子の表面に固溶体相からなる被覆層が形成された複合粒子粉末を得た。これらの複合粒子粉末を篩で分級して、平均粒径４５μｍの負極材料Ｅ１２〜Ｅ２２を作製した。
【００７２】
【表１６】

【００７３】
各負極材料の固相Ａの結晶状態および粉体抵抗率を調べた。また、各負極材料を用いて非水電解質二次電池を作製し、各電池の高率放電特性および充放電サイクル特性を調べた。結果を表１７および１８に示す。
【００７４】
【表１７】

【００７５】
【表１８】

【００７６】
負極材料Ｅ１〜Ｅ２２のいずれの回折パターンにも、固相Ａの結晶面に帰属されるピークが認められなかった。このことから、これらの固相Ａが全て非晶質相であることが分かった。また、表１７および１８に示すように、電池Ｅ８およびＥ１９の初期放電容量が特に大きく、また高率放電特性の値が特に良かった。このことから、固相ＢがＴｉとＳｉとの結晶質合金相である場合、特に固相Ｂが組成式ＴｉＳｉ₂で表される金属間化合物相である場合に、高率放電特性が極めて良く、しかも初期放電容量の大きい非水電解質二次電池が得られることが分かった。なお、表１７および１８には示さなかったが、電池Ｅ１〜Ｅ２２の容量維持率Ｑは８６％〜９３％であった。
【００７７】
上記実施例では、負極材料を円筒形の非水電解質二次電池の負極材料として用いる場合について述べたが、本発明負極材料は、円筒形のほか、コイン型、ボタン型、シート型、積層型、偏平型、角型など、種々の形状の非水電解質二次電池の負極材料として用いることができる。
【００７８】
【発明の効果】
本発明によれば、Ｓｉと、ＳｂおよびＰよりなる群から選ばれる少なくとも１種またはＢとを含む核粒子の表面の一部または全部に、Ｓｉと、金属元素とを含む被覆層が形成された複合粒子からなる非水電解質二次電池用負極材料を作製し、これを非水電解質二次電池に備えることにより、優れた充放電サイクル特性および高率放電特性を有することができる。
【図面の簡単な説明】
【図１】実施例及び比較例で作製した負極材料のＸ線回折によるパターン図である。
【図２】実施例で作製した円筒形の非水電解質二次電池の縦断面図であり、その内部構造の一部を分解斜視図で示したものである。
【符号の説明】
１正極
２負極
３セパレータ
４絶縁板
５電池ケース
６正極リード
７ガスケット
８封口板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improved negative electrode material for a non-aqueous electrolyte secondary battery, and more particularly, to a negative electrode material that provides a non-aqueous electrolyte secondary battery excellent in charge / discharge cycle characteristics and high rate discharge characteristics. A non-aqueous electrolyte secondary battery comprising the negative electrode material for a non-aqueous electrolyte secondary battery of the present invention is a portable information terminal, a portable electronic device, a small electric power storage device for home use, a motorcycle powered by a motor, an electric vehicle, It is suitable for a hybrid electric vehicle.
[0002]
[Prior art]
Nonaqueous electrolyte secondary batteries, particularly lithium secondary batteries, having features such as high electromotive force and high energy density, have been conventionally used as main power sources for mobile communication devices and portable electronic devices. As the negative electrode material, lithium metal or graphite is mainly used. In particular, when lithium metal is used, the highest energy density can be obtained.
[0003]
However, a lithium secondary battery using lithium metal as a negative electrode material has a drawback that dendrites deposited on the negative electrode during charging grow by repeated charge and discharge, penetrate the separator, and cause an internal short circuit. In addition, for a lithium secondary battery using graphite as a negative electrode material, the theoretical capacity of graphite (372 mAh / g) is about 10% smaller than the theoretical capacity of lithium metal, which is sufficient for the recent demand for higher energy density. There is a drawback that it cannot respond to.
[0004]
Therefore, in recent years, the use of silicon (Si) as a new negative electrode material has been studied. Silicon theoretically contains up to 22 lithium ions per 5 silicon atoms, ie Li _{twenty two} Si _Five It is possible to occlude until the composition becomes. The theoretical capacity of silicon is 4199 mAh / g, which is much larger than the theoretical capacity of graphite. In addition, when silicon is used as the negative electrode material, metal lithium does not precipitate on the surface of the negative electrode during normal charging, so there is no risk of an internal short circuit due to dendrite growth.
[0005]
Many negative electrode materials using such silicon have been proposed so far (see, for example, Patent Documents 1 to 3). In Patent Document 1, a core particle composed of a solid phase A and a composite particle composed of a coating layer of a solid phase B that covers all or part of the surface of the core particle is proposed as a negative electrode material. For the solid phase A, silicon, a solid solution containing silicon, or an intermetallic compound is used. For the solid phase B, silicon, a solid solution containing silicon, or an intermetallic compound is used so that the composition differs from that of the solid phase A. Although not specified in Patent Document 1, since the composite particles are obtained by cooling the molten alloy in an electric furnace, both the solid phase A and the solid phase B are crystalline phases.
[0006]
[Patent Document 1]
JP 2000-30703 A (page 4, [0018])
[Patent Document 2]
JP 2000-243389 A
[Patent Document 3]
JP-A-10-83817
[0007]
[Problems to be solved by the invention]
Silicon expands about four times in volume when it reacts with lithium. For this reason, when charging / discharging of a lithium secondary battery using silicon as a negative electrode material is repeated, there is a problem that a large internal strain is generated in the silicon particles, cracks are generated, and the particles are easily pulverized. Such pulverization leads to deterioration of charge / discharge cycle characteristics of the battery.
[0008]
As proposed in Patent Document 1, it is possible to suppress the pulverization of particles to some extent by alloying silicon with other elements.
However, when both solid phase A and solid phase B are composed of a crystalline phase, it is difficult to sufficiently suppress pulverization.
[0009]
The present invention has been made in view of the above, and provides a negative electrode material that provides a non-aqueous electrolyte secondary battery excellent in charge / discharge cycle characteristics and high-rate discharge characteristics by sufficiently suppressing silicon pulverization. With the goal.
[0010]
[Means for Solving the Problems]
That is, the present invention is a negative electrode material for a non-aqueous electrolyte secondary battery comprising composite particles in which a coating layer comprising a solid phase B is formed on part or all of the surface of a core particle comprising a solid phase A, The solid phase A is an amorphous alloy phase containing Si and at least one selected from the group consisting of Sb and P or B, and the solid phase B is Si, Mg, Ti, Zr, V, Mo , W, Mn, Fe, Cu, Co and a crystalline alloy phase containing at least one selected from the group consisting of Ni The solid phase A has a Si content of 95 to 99.99% by weight, and the total content of Sb, P and B in the solid phase A is 0.01 to 5% by weight. The present invention relates to a negative electrode material for a non-aqueous electrolyte secondary battery.
[0011]
in front The weight ratio of the nucleus particles to the coating layer is preferably 5:95 to 40:60.
[0012]
The solid phase B is preferably composed of a crystalline alloy phase of Si and Ti, and in particular the composition formula is TiSi. ₂ It is preferable to consist of the intermetallic compound phase represented by these.
[0013]
The present invention also relates to a negative electrode for a nonaqueous electrolyte secondary battery provided with the above negative electrode material for a nonaqueous electrolyte secondary battery as a material that absorbs and releases lithium ions.
[0014]
The present invention also provides a non-aqueous electrolyte comprising the non-aqueous electrolyte secondary battery negative electrode, a positive electrode capable of occluding and releasing lithium, a separator interposed between the negative electrode and the positive electrode, and a non-aqueous electrolyte. The present invention relates to a secondary battery.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The negative electrode material for a non-aqueous electrolyte secondary battery of the present invention is composed of composite particles in which a coating layer composed of a solid phase B is formed on a part or all of the surface of a core particle composed of a solid phase A. , Si and at least one selected from the group consisting of Sb and P, or B, which is an amorphous alloy phase, where the solid phase B is Si, Mg, Ti, Zr, V, Mo, W, Mn A crystalline alloy phase containing at least one selected from the group consisting of Fe, Cu, Co and Ni.
That is, the solid phase A and the solid phase B are different in composition and crystal state.
[0016]
In the present invention, the amorphous alloy phase means that there is no peak attributed to the crystal plane of the alloy phase in the diffraction pattern obtained by the wide-angle X-ray diffraction method. The crystalline alloy phase means that there is a peak attributed to the crystal plane of the alloy phase in a diffraction pattern obtained by a wide-angle X-ray diffraction method. “No peak” means that the crystallite size after annealing (held at 500 ° C. for 1 hour) is 100 nm or less, or is in an amorphous phase.
[0017]
By making Si amorphous with P, Sb or B, volume expansion of the solid phase A due to the reaction between silicon and lithium can be suppressed. Further, by doping P, Sb or B into Si (hereinafter, P, Sb and B are also referred to as doping elements), the solid phase A is made amorphous by a solid phase reaction such as a mechanical alloying method. The time required for this can be shortened. As a result, it is possible to prevent the solid phase B from becoming amorphous at the stage of producing composite particles composed of the solid phase A and the solid phase B.
[0018]
By forming the coating layer made of the solid phase B on part or all of the surface of the core particle made of the solid phase A, the pulverization of the core particles is suppressed and the electron conductivity of the negative electrode material is improved. The reason why the solid phase B must be a crystalline alloy phase is that if it is an amorphous phase with many crystal grain boundaries, cracks are generated, the electron conductivity is lowered, and the high rate discharge characteristics are lowered. .
[0019]
The Si content of the solid phase A is preferably 95 to 99.999% by weight, and more preferably 98 to 99.99% by weight. When the Si content of the solid phase A is less than 95% by weight, that is, when the content of the doping element exceeds 5% by weight, the capacity of the obtained negative electrode material decreases. Further, even if the doping element is doped more than 5% by weight, the time required for making the solid phase A amorphous is hardly shortened. On the other hand, when the Si content of the solid phase A exceeds 99.999% by weight, that is, when the content of the dope element is less than 0.001% by weight, the non-solid phase A is not produced in the production process by solid phase reaction. Since crystallization hardly proceeds, not only a long time is required to obtain the negative electrode material, but also the solid phase B may become amorphous.
[0020]
As the solid phase B, in order to improve the high rate discharge characteristics, a crystalline alloy phase of Si and Ti having high electron conductivity is preferable. ₂ An intermetallic compound phase represented by is particularly preferred. Particles made of a crystalline alloy phase of Si and Ti also have a manufacturing advantage that it is easy to form composite particles with core particles made of solid phase A by a solid phase reaction.
When the solid phase B is a solid solution, the binary alloy preferably has a weight ratio of Si to the alloying element M1 of 10:90 to 40:60, and the ternary alloy is alloyed with Si. The weight ratio of the element M1 and the alloying element M2 is preferably 10:90 (the weight ratio of M1 and M2 is arbitrary) to 40:60 (the weight ratio of M1 and M2 is arbitrary).
[0021]
The weight ratio between the core particles and the coating layer is preferably 5:95 to 40:60. When the ratio of the core particles is too small, the initial discharge capacity decreases. On the other hand, when the ratio of the coating layer is too small, the coating of the core particles is not sufficient, so that the expansion of the solid phase A due to the reaction between Si and Li cannot be effectively suppressed, and the charge / discharge cycle characteristics are deteriorated. Furthermore, the high-rate discharge characteristics are also reduced due to the decrease in electron conductivity.
[0022]
In addition, as long as it is an amount of 0.001% by weight or less for the solid phase A and 0.1% by weight or less for the solid phase B, elements other than the above-described constituent elements, for example, O, C, Impurities such as N, S, Ca, Mg, and Al may be included.
[0023]
Below, the manufacturing method of the negative electrode material of this invention is demonstrated.
First, each element constituting the solid phase A is heated and melted at a predetermined ratio in a melting tank to obtain a molten alloy, and the molten alloy is rapidly solidified to produce a first alloy lump. In addition, each element constituting the solid phase B is heated and melted in a melting tank at a predetermined ratio to obtain a molten alloy, and the molten alloy is rapidly solidified to produce a second alloy lump. Each constituent element to be melted when each molten alloy is obtained may be put into the melting tank in the form of a simple substance, or may be put into the melting tank in the form of an alloy such as a solid solution or an intermetallic compound. As a melting method, a conventionally known method such as a high frequency melting method or an arc melting method can be used. In addition, as a method of rapid solidification, a conventionally known method such as a roll spinning method, a melt drag method, a direct casting rolling method, or the like can be used.
[0024]
Next, the first alloy lump and the second alloy lump are mechanically stirred and mixed using a ball mill to perform so-called mechanical alloying to produce alloy powder. By performing this mechanical alloying for an appropriate period of time, a coating layer made of the solid phase B that is the crystalline alloy phase can be formed on the surface of the core particle made of the solid phase A that is the amorphous alloy phase. .
[0025]
The negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is an electrode using the negative electrode material described above as a material that absorbs and releases lithium ions. For example, the negative electrode material of the present invention is kneaded with a conductive agent and a binder solution to prepare a slurry-like negative electrode mixture, and the negative electrode mixture is made from a copper foil having a thickness of about 1 to 500 μm. A negative electrode plate can be produced by applying the coating onto the substrate, drying it, and rolling it. Instead of the above-mentioned negative electrode mixture, a slurry-like negative electrode mixture obtained by kneading this and a binder solution after forming a conductive agent layer on the particle surface of the negative electrode material of the present invention may be used. . Examples of the conductive agent include graphite such as artificial graphite and expanded graphite, and amorphous carbon such as acetylene black and ketjen black. The general addition amount of the conductive agent is 1 to 50 parts by weight with respect to 100 parts by weight of the negative electrode material. However, when the addition amount of the conductive agent is excessive, the capacity decrease becomes significant. It is preferable not to exceed 30 parts by weight with respect to 100 parts by weight. Examples of the binder include styrene butadiene rubber and polyvinylidene fluoride. Examples of the current collector material include stainless steel, nickel, copper, and copper alloy. Of these, copper and copper alloys having very good electronic conductivity are preferred.
[0026]
【Example】
The present invention will be described in more detail based on examples. The present invention is not limited to the following examples, and can be implemented with appropriate modifications without departing from the scope of the invention.
[0027]
[Experiment 1]
A negative electrode material of the present invention and a negative electrode material for comparison were prepared, and the crystal state and powder resistivity of the solid phase A of each negative electrode material were examined. Moreover, a non-aqueous electrolyte secondary battery was produced using each negative electrode material, and the high rate discharge characteristics and charge / discharge cycle characteristics of each battery were examined.
[0028]
Example 1
As the solid phase A, Si and P were used, and these were used as a mixture having a weight ratio of 19.9: 0.1. This mixture was put into a high-frequency melting tank to be melted, and the obtained molten alloy was rapidly cooled and solidified by a single roll method to obtain a first alloy lump that is a precursor of core particles.
Moreover, Co and Si were used for the solid phase B, and these were used as a mixture having an atomic ratio of 1: 2. This mixture is put into a high-frequency melting tank to be melted, and the obtained molten alloy is rapidly solidified by a single roll method to obtain a composition formula CoSi. ₂ The 2nd alloy lump which is a precursor of the coating layer which consists of intermetallic compounds represented by these was obtained.
Next, a mixture obtained by mixing the first alloy lump and the second alloy lump at a weight ratio of 20:80 is put into a container of a planetary ball mill, the rotational speed of the mill is set to 2800 rpm, and mechanical alloying is performed at 1 Went for hours. As a result, a composite particle powder having a coating layer formed on the surface of the core particle was obtained. The composite particle powder was classified with a sieve to prepare a negative electrode material A1 having an average particle diameter of 45 μm.
[0029]
<< Examples 2-88 >>
A first alloy lump was produced in the same manner as in Example 1 except that the type of the doping element mixed with Si and the weight ratio of Si to the doping element were changed as shown in Table 1 or 2.
As the solid phase B, a second alloy lump made of an intermetallic compound or a solid solution shown in Table 1 or 2 was used.
Next, a mixture obtained by mixing the first alloy lump and the second alloy lump at a weight ratio of 20:80 is put into a container of a planetary ball mill, the rotational speed of the mill is set to 2800 rpm, and mechanical alloying is performed. It went for 1 hour. As a result, a composite particle powder in which a coating layer composed of an intermetallic compound phase or a solid solution phase was formed on the surface of the core particle was obtained. The composite particle powder was classified with a sieve to prepare negative electrode materials A2 to A88 having an average particle diameter of 45 μm.
In addition, for the negative electrode materials A45 to A88 in which the solid phase B forming the coating layer is a solid solution, the atomic ratio between Si and the alloying element M1 is 99 for the binary alloy in producing the second alloy lump. 1 was used, and for the ternary alloy, a mixture in which the atomic ratio of Si, alloying element M1, and alloying element M2 was 99: 0.5: 0.5 was used.
[0030]
[Table 1]

[0031]
[Table 2]

[0032]
<< Comparative Example 1 >>
A composite particle powder in which a coating layer was formed on the surface of the core particle was obtained in the same manner as in Example 1 except that the mechanical alloying time was changed to 30 minutes instead of 1 hour. The composite particle powder was classified with a sieve to produce a negative electrode material X1 having an average particle diameter of 45 μm.
[0033]
<< Comparative Examples 2-22 >>
As the second alloy mass, the composition formula CoSi ₂ In the same manner as in Comparative Example 1 except that an alloy lump composed of an intermetallic compound of solid phase B shown in Table 3 or a solid solution was used instead of the alloy lump composed of an intermetallic compound represented by A composite particle powder having a coating layer made of an intermetallic compound or solid solution formed on the surface was obtained. Each composite particle powder was classified with a sieve to prepare negative electrode materials X2 to X22 having an average particle diameter of 45 μm. For the negative electrode materials X12 to X22 in which the solid phase B forming the coating layer is a solid solution, the atomic ratio between Si and the alloying element M1 is 99: 1 in producing the second alloy mass as a binary alloy. A mixture of was used.
[0034]
[Table 3]

[0035]
(I) Preparation of positive electrode plate
Lithium cobaltate (LiCoO) as positive electrode active material ₂ ) A mixture of 85 parts by weight of powder, 10 parts by weight of acetylene black as a conductive agent, and 5 parts by weight of PVdF (polyvinylidene fluoride) as a binder is dispersed in NMP (dehydrated N-methyl-2-pyrrolidone). Thus, a slurry-like positive electrode mixture was prepared. This positive electrode mixture was applied onto a positive electrode current collector made of an aluminum foil having a thickness of 20 μm so as to have a thickness of 150 μm per side, dried and rolled to produce a positive electrode plate.
[0036]
(Ii) Production of negative electrode plate
A mixture of 75 parts by weight of each negative electrode material prepared in the above examples or comparative examples, 20 parts by weight of acetylene black as a conductive agent, and 5 parts by weight of PVdF as a binder is dispersed in NMP to form a slurry. A negative electrode mixture was prepared. This negative electrode mixture was applied to a negative electrode current collector made of a copper foil having a thickness of 14 μm so as to have a thickness of 50 μm per side, dried and rolled to prepare a negative electrode plate.
[0037]
(Iii) Preparation of non-aqueous electrolyte
In a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in a volume ratio of 1: 1, LiPF ₆ Was dissolved at a concentration of 1 mol / liter to prepare a non-aqueous electrolyte.
[0038]
(Iv) Fabrication of non-aqueous electrolyte secondary battery
Cylindrical nonaqueous electrolyte secondary batteries A1 to A88, X1 to X22 having a diameter of 18 mm and a height of 65 mm using the positive electrode plate, the negative electrode plate, and the nonaqueous electrolyte solution (the symbols of the batteries are the same as those of the negative electrode material used). Corresponding to the code). As the separator, a microporous film made of polyethylene was used.
[0039]
FIG. 2 is a longitudinal sectional view of the produced nonaqueous electrolyte secondary battery, and a part of its internal structure is shown in an exploded perspective view. The nonaqueous electrolyte secondary battery includes a positive electrode 1, a negative electrode 2, a separator 3 that separates both electrodes, an insulating plate 4, a battery case 5, a gasket 7, a sealing plate 8 having a safety valve, a positive electrode lead 6, and the like. The positive electrode 1 and the negative electrode 2 are accommodated in the battery case 5 with the separator 3 interposed therebetween and wound in a spiral shape. The positive electrode 1 is connected to the sealing plate 8 via the positive electrode lead 6 and the negative electrode 2. Are connected to the bottom of the battery case 5 via a negative electrode lead (not shown), respectively, so that they can be charged and discharged.
[0040]
[Crystal state of solid phase A]
In order to evaluate the crystalline state of the solid phase A in each negative electrode material, a wide-angle X-ray diffractometer (product code: RINT-2500, manufactured by Rigaku Corporation) using a CuKα ray having a wavelength of 1.5405 nm as a radiation source was used. The diffraction intensity in the range of diffraction angle 2θ = 10 ° to 80 ° was measured. The presence or absence of a peak attributed to the crystal plane of the solid phase A was examined. The results are shown in Tables 4-6. In the presence or absence of a peak in the table, “None” indicates that there is no peak attributed to the crystal plane of the solid phase A, indicating that the solid phase A was an amorphous phase, and “Yes” indicates that the above peak is present. Present, indicating that solid phase A was a crystalline phase. As an example, the diffraction patterns of the negative electrode materials A3 and X3 are shown in FIG.
In FIG. 1, the horizontal axis represents the diffraction angle 2θ (degrees) of the solid phase A and the solid phase B, and the vertical axis represents the diffraction intensity. In the figure, ◎ indicates a peak attributed to the crystal plane of the solid phase A, and ● indicates a peak attributed to the crystal plane of the solid phase B.
[0041]
[Powder resistivity]
2 g of each negative electrode material was weighed and put into a cell having a total of four measurement points of two current terminals and two voltage terminals, and 400 kgf / cm ² In the state where the pressure was applied, the current and voltage were measured simultaneously to measure the powder resistivity (Ω · cm) of each negative electrode material (4-terminal method). A negative electrode material having a lower powder resistivity is a negative electrode material having better electron conductivity. The results are shown in Tables 4-6.
[0042]
[Initial discharge capacity and high rate discharge characteristics]
Each battery was put in a thermostat kept at 20 ° C., charged to 4.2 V at 1000 mA, and then discharged to 2.5 V at 200 mA to obtain a discharge capacity C1 (mAh) (initial discharge capacity). Next, each of these batteries was charged at 1000 mA to 4.2 V, and then discharged at 1000 mA to 2.5 V to obtain a discharge capacity C2 (mAh). The ratio P (%) of the discharge capacity C2 to the discharge capacity C1 was calculated based on the following formula (1) to evaluate the high rate discharge characteristics P of each battery. A battery having a larger value of P is a battery having better high rate discharge characteristics. The results are shown in Tables 4-6.
[0043]
P (%) = (C2 / C1) × 100 (1)
[0044]
[Charge / discharge cycle characteristics]
Each battery was placed in a thermostat kept at 20 ° C., charged at 1000 mA to 4.2 V, and then charged and discharged at 200 mA to 2.5 V for 100 cycles. Then, the capacity maintenance rate Q (%) of the discharge capacity C4 of the 100th cycle with respect to the discharge capacity C3 of the first cycle was calculated based on the following formula (2), and the charge / discharge cycle characteristics Q were evaluated. A battery having a larger Q value has better charge / discharge cycle characteristics. The results are shown in Tables 4-6.
[0045]
Q (%) = (C4 / C3) × 100 (2)
[0046]
[Table 4]

[0047]
[Table 5]

[0048]
[Table 6]

[0049]
(V) Battery evaluation
As shown in Tables 4-6, the negative electrode materials A1-A88 have a powder resistivity of 1 × 10 ^-1 ~ 9x10 ^-1 While the low value of Ω · cm was obtained, the powder resistivity of the negative electrode materials X1 to X22 was 5 × 10 ⁰ ~ 9.5 × 10 ⁰ The value was as high as Ω · cm. From this, it was found that the negative electrode materials A1 to A88 had better electron conductivity than the negative electrode materials X1 to X22.
[0050]
Further, as seen in the diffraction pattern of the negative electrode material X3 in FIG. 1, for the negative electrode materials X1 to X22 of the comparative example, near the diffraction angles (2θ = 28 ° and 48 °) attributed to the crystal plane of the solid phase A However, as can be seen in the diffraction pattern of the negative electrode material A3, no peak was observed in the vicinity of the diffraction angles of the negative electrode materials A1 to A88 of the example. From this, it was found that the solid phase A of the negative electrode materials A1 to A88 is an amorphous phase, whereas the solid phase A of the negative electrode materials X1 to X22 is a crystalline phase. Further, FIG. 1 also shows that the solid phase B of the negative electrode material A3 and the solid phase B of the negative electrode material X3 have the same degree of crystallinity.
[0051]
Further, as shown in Tables 4 to 6, since the value of the high rate discharge characteristic P of the batteries A1 to A88 is as large as 90% or more, the use of these negative electrode materials makes it possible to obtain a non-aqueous electrolyte with good high rate discharge characteristics. It turns out that the next battery is obtained.
[0052]
Furthermore, as shown in Tables 4 to 6, the values of the charge / discharge cycle characteristics Q of the batteries A1 to A88 are 90% or more, and the values of the charge / discharge cycle characteristics Q of the batteries X1 to X22 are 78% or less. Thus, it was found that by using the negative electrode materials A1 to A88, a nonaqueous electrolyte secondary battery having good charge / discharge cycle characteristics was obtained.
[0053]
[Experiment 2]
The relationship between the Si content of the solid phase A and the high rate discharge characteristics was investigated.
In the production of the first alloy lump, instead of the mixture of Si and P having a weight ratio of 19.9: 0.1, a mixture having each Si content of solid phase A shown in Table 7 was used. A composite particle powder having a coating layer formed on the surface of the core particle was obtained in the same manner as in Example 1 except that the weight ratio of the alloy lump and the second alloy lump was 21:79. Each of these composite particle powders was classified with a sieve to prepare negative electrode materials B1 to B13 having an average particle diameter of 45 μm.
[0054]
[Table 7]

[0055]
Further, in the production of the first alloy lump, instead of a mixture of Si and P in a weight ratio of 19.9: 0.1, a mixture having each Si content of solid phase A shown in Table 8 was used, A composite particle powder having a coating layer formed on the surface of the core particle was obtained in the same manner as in Example 45 except that the weight ratio of the first alloy lump to the second alloy lump was 21:79. . Each of these composite particle powders was classified with a sieve to prepare negative electrode materials B14 to B26 having an average particle diameter of 45 μm.
[0056]
[Table 8]

[0057]
The crystal state and powder resistivity of the solid phase A of each of the negative electrode materials (B1 to B26) were examined. In addition, a non-aqueous electrolyte secondary battery was produced using each of the negative electrode materials, and the high rate discharge characteristics and charge / discharge cycle characteristics of each battery were examined. The results are shown in Tables 9 and 10.
[0058]
[Table 9]

[0059]
[Table 10]

[0060]
In any of the diffraction patterns of the negative electrode materials B1 to B26, no peak attributed to the crystal plane of the solid phase A was observed. From this, it was found that those solid phases A were all amorphous phases. Further, from Tables 9 and 10, it was found that, as the Si content of the solid phase A decreases, the high rate discharge characteristic P improves, but the initial discharge capacity decreases. Considering the characteristic balance between the initial discharge capacity and the high rate discharge characteristics, the batteries B4 to B11 and the batteries B17 to B24 were particularly excellent. From this, it was found that the Si content of the solid phase A is preferably 95 to 99.999% by weight. Although not shown in Tables 9 and 10, the capacity maintenance rates Q of the batteries B1 to B26 were 86% to 93%.
[0061]
[Experiment 3]
The relationship between the weight ratio between the core particles and the coating layer and the high rate discharge characteristics was investigated.
A composite particle in which a coating layer is formed on the surface of the base particle in the same manner as in Example 2 except that the weight ratio of the first alloy lump to the second alloy lump was changed to the weight ratio shown in Table 11. A powder was obtained. These composite particle powders were classified with a sieve to prepare negative electrode materials D1 to D10 having an average particle diameter of 45 μm.
[0062]
[Table 11]

[0063]
Further, a coating layer was formed on the surface of the base particle in the same manner as in Example 46 except that the weight ratio of the first alloy lump and the second alloy lump was changed to the weight ratio shown in Table 12. A composite particle powder was obtained. These composite particle powders were classified with a sieve to prepare negative electrode materials D11 to D19 having an average particle diameter of 45 μm.
[0064]
[Table 12]

[0065]
The crystal state and powder resistivity of the solid phase A of each of the negative electrode materials D1 to D19 were examined. Moreover, a non-aqueous electrolyte secondary battery was produced using each negative electrode material, and the high rate discharge characteristics and charge / discharge cycle characteristics of each battery were examined. The results are shown in Tables 13 and 14.
[0066]
[Table 13]

[0067]
[Table 14]

[0068]
No peak attributed to the crystal plane of the solid phase A was observed in any of the diffraction patterns of the negative electrode materials D1 to D19. From this, it was found that those solid phases A were all amorphous phases. Further, from Tables 13 and 14, it was found that, as the ratio of the coating layer to the core particles increases, the high rate discharge characteristic P improves, but the initial discharge capacity decreases. In consideration of the balance between the initial discharge capacity and the high rate discharge characteristics, the batteries D3 to D7 and the batteries D12 to D16 were particularly excellent. From this, it was found that the weight ratio of the base particles to the coating layer is preferably 5:95 to 40:60. Although not shown in Tables 13 and 14, the capacity maintenance rates Q of the batteries D1 to D19 were 86% to 93%.
[0069]
[Experiment 4]
The relationship between the type of solid phase B and high rate discharge characteristics was investigated.
In the same manner as in Example 1, a first alloy lump was obtained. A mixture of the first alloy lump and the second alloy lump of solid phase B shown in Table 15 in a weight ratio of 22:78 was put into a container of a planetary ball mill, and the rotation speed of the mill was set to 2800 rpm. Mechanical alloying was performed for 1 hour to obtain a composite particle powder in which a coating layer composed of an intermetallic compound phase was formed on the surface of the core particle. These composite particle powders were classified with a sieve to prepare negative electrode materials E1 to E11 having an average particle diameter of 45 μm.
[0070]
[Table 15]

[0071]
In the same manner as in Example 45, a first alloy ingot was obtained. A mixture of the first alloy lump and the second alloy lump of solid phase B shown in Table 16 in a weight ratio of 22:78 was put into a container of a planetary ball mill, and the rotation speed of the mill was set to 2800 rpm. Mechanical alloying was performed for 1 hour to obtain a composite particle powder in which a coating layer composed of a solid solution phase was formed on the surface of the core particle. These composite particle powders were classified with a sieve to prepare negative electrode materials E12 to E22 having an average particle diameter of 45 μm.
[0072]
[Table 16]

[0073]
The crystal state of the solid phase A and the powder resistivity of each negative electrode material were examined. Moreover, a non-aqueous electrolyte secondary battery was produced using each negative electrode material, and the high rate discharge characteristics and charge / discharge cycle characteristics of each battery were examined. The results are shown in Tables 17 and 18.
[0074]
[Table 17]

[0075]
[Table 18]

[0076]
No peak attributed to the crystal plane of the solid phase A was observed in any diffraction pattern of the negative electrode materials E1 to E22. From this, it was found that these solid phases A were all amorphous. Further, as shown in Tables 17 and 18, the initial discharge capacities of the batteries E8 and E19 were particularly large, and the value of the high rate discharge characteristic was particularly good. From this, when the solid phase B is a crystalline alloy phase of Ti and Si, the solid phase B particularly has the composition formula TiSi. ₂ It was found that a non-aqueous electrolyte secondary battery having a very good high rate discharge characteristic and a large initial discharge capacity can be obtained when the intermetallic compound phase represented by Although not shown in Tables 17 and 18, the capacity maintenance rates Q of the batteries E1 to E22 were 86% to 93%.
[0077]
In the above embodiment, the case where the negative electrode material is used as the negative electrode material of the cylindrical non-aqueous electrolyte secondary battery is described. However, the negative electrode material of the present invention is not only cylindrical but also coin type, button type, sheet type, laminated type In addition, it can be used as a negative electrode material for non-aqueous electrolyte secondary batteries having various shapes such as flat type and square type.
[0078]
【The invention's effect】
According to the present invention, a coating layer containing Si and a metal element is formed on part or all of the surface of a core particle containing Si and at least one selected from the group consisting of Sb and P or B. By preparing a negative electrode material for a non-aqueous electrolyte secondary battery composed of the composite particles and providing it in a non-aqueous electrolyte secondary battery, it is possible to have excellent charge / discharge cycle characteristics and high rate discharge characteristics.
[Brief description of the drawings]
FIG. 1 is a pattern diagram by X-ray diffraction of negative electrode materials prepared in Examples and Comparative Examples.
FIG. 2 is a longitudinal sectional view of a cylindrical non-aqueous electrolyte secondary battery manufactured in an example, showing a part of its internal structure in an exploded perspective view.
[Explanation of symbols]
1 Positive electrode
2 Negative electrode
3 Separator
4 Insulation plate
5 Battery case
6 Positive lead
7 Gasket
8 Sealing plate

Claims

A negative electrode material for a non-aqueous electrolyte secondary battery comprising composite particles in which a coating layer comprising a solid phase B is formed on part or all of the surface of a core particle comprising a solid phase A,
The solid phase A is an amorphous alloy phase containing Si and at least one selected from the group consisting of Sb and P or B,
Solid Phase B, Si and, Mg, Ti, Zr, V , Mo, W, Mn, Ri crystalline alloy phase der containing at least one kind Fe, Cu, selected from the group consisting of Co and Ni,
The Si content of the solid phase A is 95-99.99 wt%,
A negative electrode material for a non-aqueous electrolyte secondary battery, wherein the total content of Sb, P and B in the solid phase A is 0.01 to 5% by weight .

2. The negative electrode material for a non-aqueous electrolyte secondary battery according to claim 1, wherein a weight ratio of the core particles to the coating layer is 5:95 to 40:60.

The solid phase B is a negative electrode material for a non-aqueous electrolyte secondary battery according to claim 1 or 2 , comprising a crystalline alloy phase of Si and Ti.

The negative electrode material for a nonaqueous electrolyte secondary battery according to claim 3, wherein the crystalline alloy phase of Si and Ti is an intermetallic compound phase represented by a composition formula TiSi ₂ .

A negative electrode for a non-aqueous electrolyte secondary battery comprising the negative electrode material for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 4 as a material that absorbs and releases lithium ions.

A nonaqueous electrolyte secondary battery comprising: a negative electrode for a nonaqueous electrolyte secondary battery according to claim 5; a positive electrode capable of inserting and extracting lithium; a separator interposed between the negative electrode and the positive electrode; and a nonaqueous electrolyte. battery.