JP5217083B2 - Negative electrode mixture for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents

Negative electrode mixture for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery Download PDF

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JP5217083B2
JP5217083B2 JP2005330051A JP2005330051A JP5217083B2 JP 5217083 B2 JP5217083 B2 JP 5217083B2 JP 2005330051 A JP2005330051 A JP 2005330051A JP 2005330051 A JP2005330051 A JP 2005330051A JP 5217083 B2 JP5217083 B2 JP 5217083B2
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lithium ion
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康一 武井
秀秋 上原
宏一 片山
軍 揚
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Showa Denko Materials Co Ltd
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Hitachi Chemical Co Ltd
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Description

本発明は、リチウムイオン二次電池用負極合剤、それを用いた負極及びリチウムイオン二次電池に関し、特に高エネルギー密度、長サイクル寿命特性を有するリチウムイオン二次電池に関する。 The present invention includes a negative electrode mixture for lithium ion secondary batteries, its Re relates negative electrode and a lithium ion secondary battery using, in particular, high energy density, a lithium ion secondary battery having a long cycle life characteristics.

携帯電子機器の小型軽量化、多機能化に伴い、高エネルギー密度を有する電池、特に二次電池に対する要求が高くなっている。リチウムイオン二次電池は、ニッケルカドミウム電池、ニッケル水素電池と比較して高電圧、高容量を有し、しかも軽量であるため、上記携帯電子機器に多く使用されるようになってきている。   As portable electronic devices become smaller and lighter and more multifunctional, demands for batteries having a high energy density, particularly secondary batteries, are increasing. Lithium ion secondary batteries have high voltage and high capacity compared to nickel cadmium batteries and nickel metal hydride batteries, and are light in weight, and thus are increasingly used in the portable electronic devices.

リチウムイオン二次電池の負極活物質には、現在、黒鉛質負極材が一般的に使用されている。黒鉛質負極材の放電容量は、せいぜい３６０ｍＡｈ／ｇであり、より高い放電容量を有する負極材が求められている。   At present, a graphite negative electrode material is generally used as a negative electrode active material of a lithium ion secondary battery. The discharge capacity of the graphite negative electrode material is at most 360 mAh / g, and a negative electrode material having a higher discharge capacity is demanded.

高い放電容量を有する負極材として、Ｓｉ、Ｓｎ、Ａｌ、Ｐｂ等のリチウムと合金を形成する金属が検討されている。これらは、例えばＳｉは４０００ｍＡｈ/ｇという非常に大きな放電容量が得られるが、充放電（リチウムとの合金形成、分解）時に大きな体積変化を伴うため、粒子が崩壊・微粒子化し、その結果として充放電容量が大きく低下するという問題がある。この問題を解決する方策として、銅集電体表面にメッキ法によりＳｎ薄膜を形成した電極（特許文献１）、銅集電体表面にスパッタ法によりＳｉ薄膜を形成した電極が提案されている（特許文献２）。これらの方法によりサイクル特性はかなり改善されるが、前者ではＳｎ層を厚膜化した場合サイクル劣化が大きくなる、入出力特性が低いという課題があり、後者は高価な設備が必要という問題がある。   As a negative electrode material having a high discharge capacity, a metal that forms an alloy with lithium such as Si, Sn, Al, and Pb has been studied. For example, Si has a very large discharge capacity of 4000 mAh / g, but a large volume change occurs during charge / discharge (formation and decomposition of an alloy with lithium). There is a problem that the discharge capacity is greatly reduced. As measures for solving this problem, an electrode in which an Sn thin film is formed on the surface of a copper current collector by plating (Patent Document 1), and an electrode in which an Si thin film is formed on the surface of a copper current collector by sputtering are proposed ( Patent Document 2). Although the cycle characteristics are considerably improved by these methods, the former has a problem that the cycle deterioration becomes large when the Sn layer is thickened, and the input / output characteristics are low, and the latter has a problem that expensive equipment is required. .

金属Ｓｉ微粒子と炭素、黒鉛粒子を一体化した複合材粒子が提案されている（特許文献３）。金属Ｓｉを微粒子とすることにより、充放電時の粒子の崩壊を抑制し、さらに炭素、黒鉛粒子と一体化することによりリチウムイオン、電子の移動経路を確保し、結果としてサイクル劣化を抑制するものである。本手法でもサイクル劣化はかなり改善されるが、充放電サイクルにおいて複合材中の金属Ｓｉ微粒子が膨張・収縮し、その結果として複合材粒子が膨張、さらに崩壊するため、長期的な信頼性に欠けるという課題がある。   Composite particles in which metal Si fine particles, carbon, and graphite particles are integrated have been proposed (Patent Document 3). By making metal Si fine particles, particle collapse during charge and discharge is suppressed, and by integrating with carbon and graphite particles, lithium ion and electron transfer paths are secured, and as a result, cycle deterioration is suppressed. It is. Although this method can also significantly improve cycle deterioration, the metal Si fine particles in the composite material expand and contract during the charge / discharge cycle, and as a result, the composite material particles expand and further collapse, resulting in lack of long-term reliability. There is a problem.

リチウムと合金を形成する金属の酸化物を負極材として用いることが提案されている。例えば、ＳＳｉＯ２・炭素・黒鉛複合材（特許文献４）が挙げられる。これらは、金属Ｓｉを用いた複合材と比較して良好なサイクル特性を示すが、不可逆容量が大きいという課題がある。この大きな不可逆容量はそれぞれの酸化物が金属Ｓｉに還元されるために生じるものと考えられている。 It has been proposed to use an oxide of a metal that forms an alloy with lithium as the negative electrode material. For example, an SSiO 2 / carbon / graphite composite material (Patent Document 4) may be mentioned. Although these show favorable cycle characteristics as compared with composite materials using metal Si, there is a problem that the irreversible capacity is large. This large irreversible capacity is thought to occur because each oxide is reduced to metallic Si.

特開２００３−１５７８３３JP2003-157833 特開２００１−２１０３１９JP2001-210319 特開２０００−２６８８２４JP 2000-268824 特開２０００−２０３８１８JP2000-203818

本発明は、リチウムと合金を形成する金属或いはその酸化物を用いた負極材におけるサイクル劣化、大きな不可逆容量を改良したリチウムイオン二次電池用負極合剤、高容量で信頼性の高いリチウムイオン二次電池用電極及びリチウムイオン二次電池を提供する。 The present invention, cycle deterioration, a large irreversible capacity to improve the lithium-ion secondary battery negative electrode mixture, a lithium ion secondary reliable high capacity in metal or a negative electrode material using the oxide to form an alloy with lithium An electrode for a secondary battery and a lithium ion secondary battery are provided.

本発明は、下記（１）〜（６）に記載の事項をその特徴とするものである。
（１）リチウムと合金形成可能な金属（Ｍａ）と金属（Ｍｂ）の酸化物がメカニカルアロイング処理により一体化された複合材を含むリチウムイオン二次電池用負極材と、電解液中での膨潤度が７％以下である樹脂からなるバインダと、を含み、前記金属（Ｍａ）がＳｎであり、前記金属（Ｍｂ）がＡｌ或いはＭｇであるリチウムイオン二次電池用負極合剤。
（２）リチウムと合金形成可能な金属（Ｍａ）がリチウムと合金を形成しない金属（Ｍｃ）と合金を形成していることを特徴とする上記（１）に記載のリチウムイオン二次電池用負極合剤。
（３）金属（Ｍｃ）がＣｏであることを特徴とする上記（２）に記載のリチウムイオン二次電池用負極合剤。
（４）リチウムと合金形成可能な金属（Ｍａ）と金属（Ｍｂ）の酸化物がメカニカルアロイング処理により一体化された複合材がさらに炭素、或いは炭素及び黒鉛と複合化されていることを特徴とする上記（１）〜（３）のいずれか１項に記載のリチウムイオン二次電池用負極合剤。
（５）上記（１）〜（４）のいずれか１項に記載のリチウムイオン二次電池用負極合剤を用いて集電体に結着してなるリチウムイオン二次電池用負極。
（６）上記（５）に記載のリチウムイオン二次電池用負極を有してなるリチウムイオン二次電池。 The present invention is characterized by the following items (1) to ( 6 ).
(1) A negative electrode material for a lithium ion secondary battery including a composite material in which an oxide of metal (Ma) and metal (Mb) capable of forming an alloy with lithium is integrated by mechanical alloying treatment ; seen containing a binder which degree of swelling is made of a resin is 7% or less, wherein the metal (Ma) is the Sn, the metal (Mb) is a negative electrode mixture for a lithium ion secondary battery as Al or Mg.
(2) for lithium ion secondary battery according to (1), characterized in that Lithium alloy capable of forming metal (Ma) form a lithium metal alloy without the formation (Mc) and alloys Negative electrode mixture.
( 3 ) The negative electrode mixture for a lithium ion secondary battery as described in ( 2) above, wherein the metal (Mc) is Co.
( 4 ) A composite material in which a metal (Ma) alloy capable of forming an alloy with lithium and an oxide of metal (Mb) is integrated by mechanical alloying is further combined with carbon or carbon and graphite. to (1) to (3) anode mixture for lithium ion secondary battery according to any one of.
( 5 ) A negative electrode for a lithium ion secondary battery formed by binding to a current collector using the negative electrode mixture for a lithium ion secondary battery according to any one of (1) to ( 4 ) above.
( 6 ) A lithium ion secondary battery comprising the negative electrode for a lithium ion secondary battery according to (5 ) above.

本発明のリチウムイオン二次電池用負極合剤、或いは本発明のリチウムイオン二次電池用負極を用いることにより、高容量で且つ充放電サイクル性に優れたリチウムイオン二次電池を作製することができる。 Anode mixture for lithium ion secondary battery of the present invention, or by using the negative electrode for a lithium ion secondary battery of the present invention, is possible to produce a superior lithium ion secondary battery and the charge-discharge cycle characteristics at high capacity it can.

本発明のリチウムイオン二次電池用負極材は、リチウムと合金形成可能な金属（Ｍａ）と金属（Ｍｂ）の酸化物が一体化された複合材を含む。このような複合材は、リチウムと合金形成可能な金属（Ｍａ）の酸化物と金属（Ｍｂ）を不活性雰囲気中でメカニカルアロイング処理して作製され、金属（Ｍａ）は極めて微細な粒子として当該複合材中に分散するため、リチウムとの合金形成時の膨張が抑制され、その結果としてサイクル性が改善されるものと推定される。また、金属（Ｍａ）の酸化物を用いた場合と比較して不可逆容量が大幅に低減でき、電池の高容量化が得られる。   The negative electrode material for a lithium ion secondary battery of the present invention includes a composite material in which an oxide of metal (Ma) and metal (Mb) capable of forming an alloy with lithium is integrated. Such a composite material is manufactured by mechanically alloying a metal (Ma) oxide capable of forming an alloy with lithium and a metal (Mb) in an inert atmosphere, and the metal (Ma) is formed as extremely fine particles. Since it is dispersed in the composite material, it is presumed that expansion during the formation of an alloy with lithium is suppressed, and as a result, the cycle performance is improved. In addition, the irreversible capacity can be significantly reduced as compared with the case where a metal (Ma) oxide is used, and the capacity of the battery can be increased.

また、上記メカニカルアロイング処理において、金属（Ｍａ）の酸化物、金属（Ｍｂ）と共にリチウムと合金を形成しない金属（Ｍｃ）の酸化物を共存させることにより、メカニカルアロイング処理における金属（Ｍａ）の酸化物の還元反応を促進することができ、また、得られる複合材において金属（Ｍａ）が金属（Ｍｃ）と合金を形成するため、リチウムとの合金形成時の膨張が抑制されると共に、導電性が向上し、サイクル性、充放電速度が改善させる。   Further, in the mechanical alloying process, the metal (Ma) in the mechanical alloying process coexists with the oxide of the metal (Ma) and the metal (Mc) oxide that does not form an alloy with lithium together with the metal (Mb). In addition, since the metal (Ma) forms an alloy with the metal (Mc) in the obtained composite material, expansion during the formation of the alloy with lithium is suppressed, Conductivity is improved, and cycle performance and charge / discharge speed are improved.

本発明のリチウムイオン二次電池用負極材は、リチウムと合金形成可能な金属（Ｍａ）と金属（Ｍｂ）の酸化物が一体化された複合材を含む。さらに、本発明のリチウムイオン二次電池用負極材は、リチウムと合金を形成しない金属（Ｍｃ）と合金化したリチウムと合金形成可能な金属（Ｍａ）と金属（Ｍｂ）が一体化した複合材を含む。本発明のこのような複合材は、リチウムと合金形成可能な金属（Ｍａ）の酸化物と金属（Ｍｂ）、又はリチウムと合金形成可能な金属（Ｍａ）の酸化物と金属（Ｍｂ）、金属（Ｍｃ）を不活性雰囲気中でメカニカルアロイング処理して作製される。   The negative electrode material for a lithium ion secondary battery of the present invention includes a composite material in which an oxide of metal (Ma) and metal (Mb) capable of forming an alloy with lithium is integrated. Furthermore, the negative electrode material for a lithium ion secondary battery of the present invention is a composite material in which a metal (Ma) and metal (Mb) capable of forming an alloy with lithium alloyed with a metal (Mc) that does not form an alloy with lithium are integrated. including. Such a composite material of the present invention includes a metal (Ma) oxide and metal (Mb) capable of forming an alloy with lithium, or a metal (Ma) oxide and metal (Mb) capable of forming an alloy with lithium, a metal (Mc) is produced by mechanical alloying treatment in an inert atmosphere.

金属（Ｍａ）としては、Ｓｎを用いることができ、金属（Ｍｂ）としてはＡｌ、Ｍｇを用いることが出来る。金属（Ｍａ）の酸化物としてはＳｎＯ２、ＳｎＯを用いることが出来る。金属（Ｍｃ）としてはＣｏ等を用いることができ、金属（Ｍａ）としてＳｎと組合せると好適である。 Sn can be used as the metal (Ma), and Al and Mg can be used as the metal (Mb). SnO 2 or SnO can be used as the metal (Ma) oxide. Co or the like can be used as the metal (Mc), and it is preferable to combine with Sn as the metal (Ma).

これらの金属酸化物及び金属を不活性雰囲気中でメカニカルアロイング処理すると、金属（Ｍａ）の酸化物は金属（Ｍｂ）によって還元され、金属（Ｍｂ）の酸化物と金属（Ｍａ）が一体化した複合材、或いは金属（Ｍｂ）の酸化物と金属（Ｍｃ）と合金化した金属（Ｍａ）が一体化した複合材が得られる。これらの存在は、複合材の広角Ｘ線回折図より確認することが出来る。当複合材中で金属（Ｍａ）は非常に小さな微粒子として存在していると考えられ、複合材の広角Ｘ線回折線の半値幅より求められた結晶子サイズは数ｎｍ〜数十ｎｍである。得られる複合材の粒子径は１〜２０μｍである。   When these metal oxides and metal are mechanically alloyed in an inert atmosphere, the metal (Ma) oxide is reduced by the metal (Mb), and the metal (Mb) oxide and the metal (Ma) are integrated. Or a composite material in which an oxide of metal (Mb) and a metal (Ma) alloyed with metal (Mc) are integrated. The presence of these can be confirmed from the wide-angle X-ray diffraction diagram of the composite material. The metal (Ma) is considered to exist as very small fine particles in the composite material, and the crystallite size obtained from the half-value width of the wide-angle X-ray diffraction line of the composite material is several nm to several tens of nm. . The resulting composite material has a particle size of 1 to 20 μm.

メカニカルアロイング処理における金属（Ｍａ）の酸化物に対する金属（Ｍｂ）の比率は、金属（Ｍａ）の酸化物をすべて還元するのに必要な量（化学量論比）、若しくは若干過剰とすることが好ましい。化学量論比よりも少ない場合、得られる複合材中には金属（Ｍａ）の酸化物が残留し、リチウムイオン二次電池用負極材として用いた場合、不可逆容量が大きくなる。一方、過剰に多い場合には得られる複合材中に非常に活性な金属（Ｍｂ）が残留するため、取扱いに危険が伴うようになるため好ましくない。好ましい比率は１．０〜１．６である。   The ratio of the metal (Mb) to the metal (Ma) oxide in the mechanical alloying process is an amount (stoichiometry) necessary to reduce all the metal (Ma) oxide (stoichiometric ratio) or slightly excessive. Is preferred. When the ratio is less than the stoichiometric ratio, metal (Ma) oxide remains in the obtained composite material, and when used as a negative electrode material for a lithium ion secondary battery, the irreversible capacity increases. On the other hand, when the amount is excessively large, a very active metal (Mb) remains in the obtained composite material. A preferred ratio is 1.0 to 1.6.

メカニカルアロイング処理には、強い圧縮、せん断力が発生する公知の設備を使用することができ、例えば遊星ボールミル、振動ボールミル、ロッドミル、ボールミル等を用いることが出来る。   For the mechanical alloying treatment, known equipment that generates strong compression and shearing force can be used. For example, a planetary ball mill, a vibration ball mill, a rod mill, a ball mill, or the like can be used.

メカニカルアロイング処理において、処理環境（処理容器内）の雰囲気は、金属（Ｍｂ）及び生成する金属（Ｍａ）の酸化を抑制するため、不活性雰囲気とすることが好ましい。窒素、アルゴン、ヘリウム等が使用できる。   In the mechanical alloying process, the atmosphere of the processing environment (in the processing container) is preferably an inert atmosphere in order to suppress the oxidation of the metal (Mb) and the generated metal (Ma). Nitrogen, argon, helium, etc. can be used.

メカニカルアロイング処理の時間は、処理によって生じる反応の進み具合を観察することによって決定されるべきものであり、１時間〜数十時間の範囲である。   The mechanical alloying time should be determined by observing the progress of the reaction caused by the treatment, and is in the range of 1 hour to several tens of hours.

本発明のリチウムイオン二次電池用負極材において、リチウムと合金形成可能な金属（Ｍａ）がリチウムと合金を形成しない金属（Ｍｃ）と合金を形成していても良い。金属（Ｍａ）としてＳｎ、金属（Ｍｃ）としてＣｏを用いることが好適である。金属（Ｍａ）が金属（Ｍｃ）との合金となることにより、リチウムとの合金形成（充電時）の膨張が更に抑制されると共に、導電性が向上し、リチウムイオン二次電池用負極材として用いた場合、サイクル性、充放電速度が向上する。   In the negative electrode material for a lithium ion secondary battery of the present invention, the metal (Ma) capable of forming an alloy with lithium may form an alloy with a metal (Mc) that does not form an alloy with lithium. It is preferable to use Sn as the metal (Ma) and Co as the metal (Mc). As the metal (Ma) becomes an alloy with the metal (Mc), the expansion of the alloy formation with lithium (during charging) is further suppressed, the conductivity is improved, and the anode material for the lithium ion secondary battery When used, cycleability and charge / discharge speed are improved.

上記のリチウムと合金形成可能な金属（Ｍａ）がリチウムと合金を形成しない金属（Ｍｃ）との合金となっている複合材は、メカニカルアロイング処理において、金属（Ｍａ）の酸化物、金属（Ｍｂ）と共に金属（Ｍｃ）を処理に供することによって作製することができる。メカニカルアロイング処理において金属（Ｍｃ）を共存させると、上記の複合材特性の改善が図れると共に、金属（Ｍａ）の酸化物の還元反応が促進されるため、メカニカルアロイング処理時間の短縮、或いは金属（Ｍａ）の酸化物の残留が抑制され、不可逆容量の低減ができる。金属（Ｍａ）としてはＳｎ、その酸化物としてはＳｎＯ、ＳｎＯ２を用いることができ、金属（Ｍｃ）としてはＣｏが好適である。 In the mechanical alloying process, the composite material in which the metal (Ma) capable of forming an alloy with lithium is an alloy of a metal (Mc) that does not form an alloy with lithium is an oxide of a metal (Ma), a metal ( It can be produced by subjecting the metal (Mc) to the treatment together with Mb). When the metal (Mc) is allowed to coexist in the mechanical alloying process, the above composite material characteristics can be improved and the reduction reaction of the metal (Ma) oxide is promoted. Residue of metal (Ma) oxide is suppressed, and irreversible capacity can be reduced. Sn can be used as the metal (Ma), SnO or SnO 2 can be used as its oxide, and Co is preferable as the metal (Mc).

本発明のリチウムイオン二次電池用負極材では、リチウムと合金形成可能な金属（Ｍａ）と金属（Ｍｂ）の酸化物が一体化された複合材を更に炭素、或いは炭素及び黒鉛粒子と複合化することが出来る。複合材をさらに炭素、或いは炭素及び黒鉛粒子と複合化することにより、充放電時の複合材粒子の膨張収縮が抑制され、その結果としてサイクル性が改善され、また、導電性が向上するため充放電速度が向上する。 In the negative electrode material for a lithium ion secondary battery of the present invention, a composite material in which an oxide of metal (Ma) and metal (Mb) capable of forming an alloy with lithium is integrated with carbon or carbon and graphite particles. I can do it . The double cause material further carbon, or by complexing with carbon and graphite particles, it is suppressed expansion and contraction of composite particles during charging and discharging, resulting cyclability are improved as also for conductivity is improved Charge / discharge speed is improved.

本発明のリチウムイオン二次電池用負極材は、電解液中での膨潤度が７％以下、好ましくは５％以下の樹脂からなるバインダを用いて集電体に結着して負極とすることにより、リチウムイオン二次電池として更に優れた特性を発揮することが出来る。電解液中での膨潤度は、以下のようにして求めることができる。バインダーを含む溶液をテフロン（登録商標）コーティングしたステンレス板上に塗布、８０℃で１時間、乾燥し、形成されたバインダ樹脂フィルムを剥離し、１２０℃、真空中、５時間乾燥する。得られたバインダ樹脂フィルムを電解液｛１Ｍ ＬｉＰＦ６、ＥＣ／ＤＭＣ／ＤＥＣ（１／１／１）｝に浸漬し、５０℃で２４時間放置する。膨潤度は、この電解液浸漬前後での重量変化より算出される。膨潤度が大きな樹脂からなるバインダを用いた場合、電池内でバインダが膨潤、結着力が低下し、負極材の充放電時の膨張収縮によって負極材粒子間、負極材／集電体間の接合が破壊され、容量低下が生じる。上記のような樹脂からなるバインダは、例えば、ＬＳＲ７（日立化成工業株式会社製）、ＬＡ１３２（Chengdu Indigo Power Sources Co., LtD製）として入手可能である。
本発明のリチウムイオン二次電池用負極は、本発明のリチウムイオン二次電池用負極材と前記バインダ樹脂、溶剤、導電助材を十分混練し、銅箔等の集電体に塗布、乾燥、プレスして作製することができる。導電助材としては、アセチレンブラック、ケッチェンブラック等のカーボンブラック、黒鉛粉を用いることができる。また、本発明のリチウムイオン二次電池用負極は、本発明のリチウムイオン二次電池用負極材と黒鉛質リチウムイオン二次電池用負極材と前記バインダ樹脂、溶剤を十分混練し、銅箔等の集電体に塗布、乾燥、プレスして作製することができる。 The negative electrode material for a lithium ion secondary battery of the present invention is formed into a negative electrode by binding to a current collector using a binder made of a resin having a degree of swelling of 7% or less, preferably 5% or less in an electrolytic solution. Therefore, it is possible to exhibit further excellent characteristics as a lithium ion secondary battery. The degree of swelling in the electrolytic solution can be determined as follows. A solution containing a binder is applied onto a Teflon (registered trademark) -coated stainless steel plate, dried at 80 ° C. for 1 hour, the formed binder resin film is peeled off, and dried in a vacuum at 120 ° C. for 5 hours. The obtained binder resin film is immersed in an electrolytic solution {1M LiPF 6 , EC / DMC / DEC (1/1/1)} and left at 50 ° C. for 24 hours. The degree of swelling is calculated from the weight change before and after immersion in the electrolyte solution. When a binder made of a resin with a high degree of swelling is used, the binder swells in the battery, the binding force decreases, and the negative electrode material is bonded between the negative electrode material particles and the negative electrode material / current collector due to expansion and contraction during charge / discharge of the negative electrode material. Is destroyed and the capacity is reduced. The binder made of the resin as described above is available as, for example, LSR7 (manufactured by Hitachi Chemical Co., Ltd.) or LA132 (manufactured by Chengdu Indigo Power Sources Co., LtD).
The negative electrode for a lithium ion secondary battery of the present invention is sufficiently kneaded with the negative electrode material for a lithium ion secondary battery of the present invention and the binder resin, solvent, and conductive additive, applied to a current collector such as a copper foil, dried, It can be made by pressing. As the conductive aid, carbon black such as acetylene black and ketjen black, and graphite powder can be used. The negative electrode for a lithium ion secondary battery of the present invention is a mixture of a negative electrode material for a lithium ion secondary battery of the present invention, a negative electrode material for a graphite lithium ion secondary battery, the binder resin, and a solvent, and a copper foil or the like. The current collector can be applied, dried and pressed.

本発明のリチウムイオン二次電池用負極材或いは負極を用いてリチウムイオン二次電池を作製する場合、正極材料は特に限定されず、公知の材料、例えばＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４等のリチウム含有酸化物を使用することができる。正極は、粉末状のこれら正極材料にバインダの他、必要であれば導電材、溶剤等を添加して十分混練後、アルミニウム箔等の集電体に塗布、乾燥、プレスして作製することができる。 When producing a lithium ion secondary battery using the negative electrode material for lithium ion secondary batteries or the negative electrode of the present invention, the positive electrode material is not particularly limited, and known materials such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4, etc. Lithium-containing oxides can be used. A positive electrode can be prepared by adding a conductive material, a solvent, etc., if necessary, to a powdered positive electrode material, kneading and applying, drying and pressing on a current collector such as an aluminum foil. it can.

また、セパレータについても特に限定はなく、公知の材料を使用することが可能である。
電解質用溶媒としては、公知のリチウム塩を溶解できる非プロトン性、低誘電率の溶媒を使用することができる。例えば、エチレンカーボネート、プロピレンカーボネート、ジエチレンカーボネート、ジメチルカーボネート、メチル・エチルカーボネート、アセトニトリル、プロピオニトリル、テトラヒドロフラン、γ―ブチロラクトン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、４−メチル−１，３−ジオキソラン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、ジエチルエーテル、スルホラン、メチルスルホラン、ニトロメタン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の溶媒を単独、或いは複数混合して使用することができる。 Moreover, there is no limitation in particular also about a separator, It is possible to use a well-known material.
As the electrolyte solvent, an aprotic solvent having a low dielectric constant capable of dissolving a known lithium salt can be used. For example, ethylene carbonate, propylene carbonate, diethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, acetonitrile, propionitrile, tetrahydrofuran, γ-butyrolactone, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3- Use a solvent such as dioxolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether, sulfolane, methyl sulfolane, nitromethane, N, N-dimethylformamide, dimethyl sulfoxide alone or in combination. Can do.

電解質として用いるリチウム塩としては、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＢ（Ｃ６Ｈ５）４、ＬｉＣｌ、ＣＨ３ＳＯ３Ｌｉ、ＣＦ３ＳＯ３Ｌｉ等があり、これらの塩を単独、或いは複数混合して使用することができる。 Examples of the lithium salt used as the electrolyte include LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiB (C 6 H 5 ) 4 , LiCl, CH 3 SO 3 Li, CF 3 SO 3 Li, and the like. It can be used alone or in combination.

また、リチウム固体二次電池、ポリマーリチウム二次電池を作成する場合においては、公知の正極、ポリマー電解質、固体電解質と共に、本発明のリチウムイオン二次電池用負極材或いは負極を用いることにより、安全性が高く、高容量の二次電池を作製することができる。   In addition, when making a lithium solid secondary battery or a polymer lithium secondary battery, the negative electrode material for a lithium ion secondary battery or the negative electrode of the present invention can be used together with a known positive electrode, polymer electrolyte, and solid electrolyte. A high-capacity secondary battery with high capacity can be manufactured.

〔実施例１〕
遊星ボールミル｛Planetary Mono Mill P-6（Fritsch Germany）、容器：ステンレス製、容積８０ｍｌ、ステンレス製ボール（φ１０ｍｍ、１０個）｝の容器にＳｎＯ２、Ａｌ（２００ｍｅｓｈ以下）、Ｃｏを重量比１：０．２７：０．１６で秤量、投入した。 容器内をアルゴンガスでパージした後、密閉し、４５０ｒｐｍで１０時間、メカニカルアロイング処理を行った。得られた複合材の広角Ｘ線回折図にはＣｏＳｎ３、Ａｌ２Ｏ３及び少量の未反応のＣｏが観察された。 [Example 1]
Planetary Mono Mill P-6 (Planetary Mono Mill P-6 (Fritsch Germany), container: made of stainless steel, volume 80 ml, stainless steel balls (10 mm diameter, 10 pieces)) SnO 2 , Al (200 mesh or less), Co in weight ratio 1: 0.27: Weighed and charged at 0.16. After purging the inside of the container with argon gas, it was sealed and subjected to mechanical alloying at 450 rpm for 10 hours. CoSn 3 , Al 2 O 3 and a small amount of unreacted Co were observed in the wide-angle X-ray diffraction pattern of the obtained composite material.

〔実施例２〕
遊星ボールミルの容器にＳｎＯ、Ａｌ、Ｃｏを重量比で１：０．１７６：０．１４８で秤量し、実施例１と同様にしてメカニカルアロイング処理を行った。得られた複合材の広角Ｘ線回折図にはＣｏＳｎ３とＡｌ２Ｏ３が観察された。 [Example 2]
SnO, Al, and Co were weighed at a weight ratio of 1: 0.176: 0.148 in a container of a planetary ball mill, and mechanical alloying was performed in the same manner as in Example 1. CoSn 3 and Al 2 O 3 were observed in the wide-angle X-ray diffraction pattern of the obtained composite material.

〔実施例３〕
遊星ボールミルの容器にＳｎＯ２、Ａｌを重量比で１：０．２７で秤量し、実施例１と同様にしてメカニカルアロイング処理を行った。得られた複合材の広角Ｘ線回折図にはＳｎ、Ａｌ２Ｏ３の他、少量の未反応のＳｎＯ２、Ａｌが観察された。 Example 3
SnO 2 and Al were weighed at a weight ratio of 1: 0.27 in a planetary ball mill container and subjected to mechanical alloying in the same manner as in Example 1. In addition to Sn and Al 2 O 3 , a small amount of unreacted SnO 2 and Al were observed in the wide-angle X-ray diffraction pattern of the obtained composite material.

〔実施例４〕
遊星ボールミルの容器にＳｎＯ、Ｍｇ、Ｃｏを重量比で１：０．２３５：０．１４８で秤量し、実施例１と同様にしてメカニカルアロイング処理を行った。得られた複合材の広角Ｘ線回折図にはＣｏＳｎ３とＭｇＯが観察された。 Example 4
SnO, Mg, and Co were weighed at a weight ratio of 1: 0.235: 0.148 in a planetary ball mill container, and mechanical alloying was performed in the same manner as in Example 1. CoSn 3 and MgO were observed in the wide-angle X-ray diffraction pattern of the obtained composite material.

〔比較例１〕
遊星ボールミルの容器にＳｎＯ、Ａｌ、Ｓｂを重量比で１：０．１７６：０．９で秤量し、実施例１と同様にしてメカニカルアロイング処理を行った。得られた複合材の広角Ｘ線回折図にはＳｎ、ＳｎＳｂ、Ａｌ２Ｏ３、Ｓｂ、Ａｌが観察された。 [Comparative Example 1]
SnO, Al, and Sb were weighed at a weight ratio of 1: 0.176: 0.9 in a planetary ball mill container, and mechanical alloying was performed in the same manner as in Example 1. Sn, SnSb, Al 2 O 3 , Sb, and Al were observed in the wide-angle X-ray diffraction pattern of the obtained composite material.

＜参考例＞
〔充放電特性評価〕
実施例１〜４で作製した複合材について、複合材８７％に対し、５％のアセチレンブラック、及びバインダーとして８％のポリ弗化ビニリデン（呉羽化学製、ＫＦ１１２０）、及び溶媒としてＮ−メチル−ピロリドンを添加、混練しスラリーとした。得られたスラリーを銅箔に塗布、乾燥後、プレスして負極を作製した。 <Reference example>
[Charge / discharge characteristics evaluation]
About the composite material produced in Examples 1-4, 5% of acetylene black, 8% of polyvinylidene fluoride (manufactured by Kureha Chemical, KF1120) as a binder, and N-methyl- as a solvent with respect to 87% of the composite material Pyrrolidone was added and kneaded to form a slurry. The obtained slurry was applied to a copper foil, dried, and then pressed to prepare a negative electrode.

得られた負極を打ち抜き、対極として金属リチウム、電解液として１Ｍ ＬｉＰＦ６／ＥＣ＋ＤＭＣ（容積比１：１）を用い、コインセル（ＣＲ２０１６型）を用いて電池を組みたてた。電流密度０．３ｍＡ／ｃｍ２、カットオフ電圧を金属リチウム電位に対して充電時０．０Ｖ、放電時１．４Ｖとして充放電を行った。表１に各複合材の充放電評価結果を示す。同表には、比較例としてＳｎＯ２（比較例２）、及びＳｎＯ（比較例３）について、同様にして測定した充放電評価結果を示す。 The obtained negative electrode was punched out, and a battery was assembled using a coin cell (CR2016 type) using metallic lithium as a counter electrode, 1M LiPF 6 / EC + DMC (volume ratio 1: 1) as an electrolyte. Charging / discharging was performed with a current density of 0.3 mA / cm 2 and a cut-off voltage of 0.0 V during charging and 1.4 V during discharging with respect to the metal lithium potential. Table 1 shows the charge / discharge evaluation results of each composite material. The table shows the charge / discharge evaluation results measured in the same manner for SnO 2 (Comparative Example 2) and SnO (Comparative Example 3) as comparative examples.

本発明のリチウムイオン二次電池は、金属酸化物を負極材として用いた場合（比較例３、４）と比較し、初回充放電効率が高く、また３サイクル後での容量維持率が大きいことが分かる。
また、メカニカルアロイング処理時、リチウムと合金形成可能な金属（Ｍａ）の酸化物、金属（Ｍｂ）と共にリチウムと合金を形成しない金属（Ｍｃ）を共存、且つＭｃをＣｏとすることにより、初回充放電効率が高く、３サイクル後での容量維持率が大きくなることが分かる。 The lithium ion secondary battery of the present invention has a high initial charge / discharge efficiency and a large capacity retention rate after 3 cycles compared to the case where a metal oxide is used as a negative electrode material (Comparative Examples 3 and 4). I understand.
Further, at the time of mechanical alloying, the metal (Ma) oxide that can form an alloy with lithium, the metal (Mb) that does not form an alloy with lithium (Mc), and Mc as Co are used for the first time. It can be seen that the charge / discharge efficiency is high, and the capacity retention rate after 3 cycles is increased.

Figure 0005217083
Figure 0005217083

〔実施例７、８〕
実施例２で作製した複合材について、バインダーをＰＶｄＦからＬＡ１３２（Chengdu Indigo Power Sources Co., Ltd.製）（実施例７）、ＬＳＲ７（日立化成工業株式会社製）（実施例８）に替え、実施例２と同様にして充放電特性の評価を行った。結果を表３に示す。 [Examples 7 and 8]
About the composite material produced in Example 2, the binder is changed from PVdF to LA132 (manufactured by Chengdu Indigo Power Sources Co., Ltd.) (Example 7), LSR7 (manufactured by Hitachi Chemical Co., Ltd.) (Example 8), The charge / discharge characteristics were evaluated in the same manner as in Example 2. The results are shown in Table 3 .

Figure 0005217083
バインダ添加量：固形分濃度
Figure 0005217083
 Binder addition amount: solid content concentration

Claims (6)

リチウムと合金形成可能な金属（Ｍａ）と金属（Ｍｂ）の酸化物がメカニカルアロイング処理により一体化された複合材を含むリチウムイオン二次電池用負極材と、電解液中での膨潤度が７％以下である樹脂からなるバインダと、を含み、
前記金属（Ｍａ）がＳｎであり、前記金属（Ｍｂ）がＡｌ或いはＭｇであるリチウムイオン二次電池用負極合剤。 A negative electrode material for a lithium ion secondary battery including a composite material in which an oxide of metal (Ma) and metal (Mb) capable of forming an alloy with lithium is integrated by mechanical alloying , and a degree of swelling in an electrolyte solution and a binder consisting of a 7% or less is resin, only including,
A negative electrode mixture for a lithium ion secondary battery, wherein the metal (Ma) is Sn and the metal (Mb) is Al or Mg . リチウムと合金形成可能な金属（Ｍａ）がリチウムと合金を形成しない金属（Ｍｃ）と合金を形成していることを特徴とする請求項１に記載のリチウムイオン二次電池用負極合剤。 2. The negative electrode mixture for a lithium ion secondary battery according to claim 1 , wherein the metal (Ma) capable of forming an alloy with lithium forms an alloy with a metal (Mc) that does not form an alloy with lithium. 金属（Ｍｃ）がＣｏであることを特徴とする請求項２に記載のリチウムイオン二次電池用負極合剤。 Metals (Mc) is a negative electrode mixture for a lithium ion secondary battery according to claim 2, characterized in that the Co. リチウムと合金形成可能な金属（Ｍａ）と金属（Ｍｂ）の酸化物がメカニカルアロイング処理により一体化された複合材がさらに炭素、或いは炭素及び黒鉛と複合化されていることを特徴とする請求項１〜３のいずれか１項に記載のリチウムイオン二次電池用負極合剤。 A composite material in which an oxide of metal (Ma) and metal (Mb) capable of forming an alloy with lithium is integrated by mechanical alloying is further combined with carbon or carbon and graphite. anode mixture for lithium ion secondary battery according to any one of clauses 1-3. 請求項１〜４のいずれか１項に記載のリチウムイオン二次電池用負極合剤を用いて集電体に結着してなるリチウムイオン二次電池用負極。 The negative electrode for lithium ion secondary batteries formed by binding to the current collector using the negative electrode mixture for lithium ion secondary batteries according to any one of claims 1 to 4 . 請求項５に記載のリチウムイオン二次電池用負極を有してなるリチウムイオン二次電池。 A lithium ion secondary battery comprising the negative electrode for a lithium ion secondary battery according to claim 5 .
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