JP4191281B2 - Negative electrode active material, negative electrode and method for producing the same, and non-aqueous secondary battery - Google Patents
Negative electrode active material, negative electrode and method for producing the same, and non-aqueous secondary battery Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
【０００１】
【発明の属する技術分野】
本発明は、高作動電圧、高容量及び良好な充放電サイクル特性を有する主としてケイ化銅を負極活物質とする非水系二次電池に関するものである。
【０００２】
【従来の技術】
３Ｖ級の電圧を持つ非水系二次電池においては、負極活物質としてリチウム金属、正極活物質としてＣｏ，Ｍｎ，Ｎｉに代表される遷移金属の酸化物を用いる方法が代表的である。しかし、負極にリチウム金属を用いると充電中にリチウム金属が樹枝状のデンドライトに成長し、内部ショートしたり、そのデンドライトの活性が高く、発火する危険性を持つ。そのため、これに代わる活物質としてリチウムを挿入放出できる焼成炭素質材料負極が実用化されている。しかし、炭素質材料は、体積当りの充放電容量が低いという欠点を持っている。そこで、３〜４Ｖ級のさらに高い電圧を持ち、高容量の二次電池を開発するため、より容量の大きい負極活物質が必要とされている。
【０００３】
リチウムを挿入放出する負極活物質としては、遷移金属カルコゲン化合物、ルチル構造の遷移金属酸化物、例えば、ＷＯ2（米国特許第４１９８４７６号公報）、ＬｉxＦｅ（Ｆｅ2）Ｏ4などのスピネル化合物（特開昭５８−２２０３６２号公報）、電気化学的に合成されたＦｅ2Ｏ3のリチウム化合物（米国特許第４４６４４４７号公報）、Ｆｅ2Ｏ3のリチウム化合物（特開平３−１１２０７０号公報）、Ｎｂ2Ｏ5（特開昭６２−５９４１２号公報、特開平２−８２４４７号公報）、酸化鉄及び酸化コバルト（ＦｅＯ，Ｆｅ2Ｏ3，Ｆｅ3Ｏ4，ＣｏＯ，Ｃｏ2Ｏ3，Ｃｏ3Ｏ4）（特開平３−２９１８６２号公報）が知られている。一方、リチウムと合金を形成することが知られているＳｎ，Ｃｄ（Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ ｔｈｅ Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ，８７−１，１９８７），Ａｌ（Ｓｏｌｉｄ Ｓｔａｔｅ Ｉｏｎｉｃｓ，２０，１９８６），Ｓｉ，Ｐｂ，Ｂｉ，Ｓｂ（Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ ｔｈｅ Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ，８７−１，１９８７）及びこれらのリチウムとの合金を負極活物質として用いることも検討されている（例えば、特開平７−２９６０２号公報）。
【０００４】
【発明が解決しようとする課題】
しかし、上記遷移金属カルコゲン化合物やルチル構造の遷移金属酸化物、スピネル化合物及び遷移金属酸化物の電極電位は、金属リチウムの電極電位に対して貴に大であり、これら負極活物質を負極とし、正極と組み合わせて電池を構成しても、３〜４Ｖの高電圧が得られないという問題がある。また、Ｓｎ，Ｃｄ，Ａｌ，Ｓｉ，Ｐｂ，Ｂｉ，Ｓｂ及びこれらのリチウムとの合金は、高電流密度（例えば、１ｍＡ／ｃｍ2）において容量が小さく、さらに充放電のサイクル寿命が短いという問題がある。また、Ｓｉを活物質とした場合、高容量が期待できるが、充放電の繰り返しに伴い、電極の体積が大きく変化するため、電極の割れによる容量の低下や内部短絡が起き易いという問題がある。
【０００５】
そこで、本発明は、高電流密度でも、高電圧、高容量で、かつ良好な充放電サイクル特性を有する非水系二次電池を提供することを目的とした。
【０００６】
【課題を解決するための手段】
上記の目的を達成するため、本発明は主にケイ化銅からなる負極活物質を用いて電池を構成すれば、上記課題を解決できることを見出して完成されたものである。本発明の非水系二次電池は、主にケイ化銅からなる負極活物質を含む負極と、遷移金属を構成元素として含む金属酸化物からなる正極活物質を含む正極と、リチウムイオン導電性の非水媒体とからなることを特徴とするものである。ケイ化銅を負極活物質に用いることにより、ケイ素を用いた場合に比べ充放電時における負極の体積変化が抑制され、充放電のサイクル特性が向上する。ここで、ケイ化銅とは、ケイ素と銅の化合物であり、ＣｕＳｉ，Ｃｕ2Ｓｉ，Ｃｕ3Ｓｉ，Ｃｕ5Ｓｉ等の組成をいう。また、結晶性でも非晶性でも、特に限定されない。
【０００８】
また、ケイ化銅は、例えば、後で述べる真空成膜法で作製したものを用いることができる。
【００１１】
また、上記負極活物質として、銅基板の表面に真空成膜法により形成されたケイ素薄膜を非酸化雰囲気下で熱処理してなるケイ化銅薄膜を用いても良い。熱処理により、ケイ素薄膜と基板である銅との間の反応が進行し、ケイ化銅の薄膜が形成される。そして銅基板を集電体とすることにより、負極活物質の作製と負極の作製を同時に行うことができる。さらに銅基板との反応により、集電体である銅基板と負極活物質との界面の抵抗が低くなるため、電池の内部抵抗を低減できる。
【００１６】
【発明の実施の形態】
本発明に用いる負極の製造方法として、蒸着法、スパッタリング法、イオンプレーティング法、ＣＶＤ法等の真空製膜法と熱処理を組み合わせても良い。真空製膜法を用いる望ましい製造方法としては、例えば、銅基板にスパッタリング法によりケイ素薄膜を製膜後、基板ごと、非酸化雰囲気下で熱処理する方法がある。熱処理温度は、３００〜９００℃が好ましい。
【００１７】
本発明の正極活物質として用いられる正極材料は、従来公知の何れの材料も使用でき、例えば、ＬｉxＣｏＯ2，ＬｉxＮｉＯ2，ＭｎＯ2，ＬｉＭｎＯ2，ＬｉxＭｎ2Ｏ4，ＬｉxＭｎ2-yＯ4，α−Ｖ2Ｏ5，ＴｉＳ2等が挙げられる。
【００１８】
本発明に使用されるリチウムイオン導電性の非水媒体としては、有機溶媒にリチウム化合物を溶解させた非水電解液、又は高分子にリチウム化合物を固溶或いはリチウム化合物を溶解させた有機溶媒を保持させた高分子固体電解質を用いることができる。非水電解液は、有機溶媒と電解質とを適宜組み合わせて調製されるが、これら有機溶媒や電解質はこの種の電池に用いられるものであればいずれも使用可能である。有機溶媒としては、例えばプロピレンカーボネート、エチレンカーボネート、ビニレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、１，２−ジメトキシエタン、１，２−ジエトキシエタンメチルフォルメイト、ブチロラクトン、テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソフラン、４−メチル−１，３−ジオキソフラン、ジエチルエーテル、スルホラン、メチルスルホラン、アセトニトリル、プロピオニトリル、ブチロニトリル、バレロニトリル、ベンゾニトリル、１，２−ジクロロエタン、４−メチル−２−ペンタノン、１，４−ジオキサン、アニソール、ジグライム、ジメチルホルムアミド、ジメチルスルホキシド等である。これらの溶媒を２種以上併用することもできる。
【００１９】
電解質としては、例えばＬｉＣｌＯ4，ＬｉＡｓＦ6，ＬｉＰＦ6，ＬｉＢＦ4，ＬｉＢ（Ｃ6Ｈ5）4，ＬｉＣｌ，ＬｉＢｒ，ＬｉＩ，ＬｉＣＨ3ＳＯ3，ＬｉＣＦ3ＳＯ3，ＬｉＡｌＣｌ4等が挙げられ、これらを単独でも、２種以上を併用することもできる。
【００２０】
本発明に使用される他の媒体としては、上記の電解質から選ばれる電解質を以下に示す高分子に固溶させたものを用いることができる。例えば、ポリエチレンオキサイドやポリプロピレンオキサイドのようなポリエーテル鎖を有する高分子、ポリエチレンサクシネート、ポリカプロラクタムのようなポリエステル鎖を有する高分子、ポリエチレンイミンのようなポリアミン鎖を有する高分子、ポリアルキレンスルフィドのようなポリスルフィド鎖を有する高分子が挙げられる。
【００２１】
また、本発明に使用されるさらに他の媒体としては、ポリフッ化ビニリデン、フッ化ビニリデン-テトラフルオロエチレン共重合体、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリアクリロニトリル、ポリメタクリル酸メチル等の高分子に上記電解質及び非水電解液を保持させ上記高分子を可塑化させたものを用いることもできる。
【００２２】
以下、実施例を用いて本発明をさらに詳細に説明する。
【実施例】
〈実施例１〉
銅基板にスパッタ蒸着装置を用いてケイ素を蒸着した後、基板ごと窒素雰囲気中で８００℃で１時間熱処理を行った。熱処理後のＸ線回折測定から、ケイ素はケイ化銅を形成していることを確認した。
【００２３】
正極は次の様にして作製した。炭酸リチウムＬｉ2ＣＯ3と炭酸コバルトＣｏＣＯ3をモル比でＬｉ／Ｃｏが１：１となるように、秤量し、イソプロピルアルコールを用いてボールミルで湿式混合した後、溶媒を蒸発させて８００℃で１時間仮焼した。仮焼粉を振動ミルで再粉砕した後、８００℃で１０時間焼成し、ＬｉＣｏＯ2の粉末を得た。ＬｉＣｏＯ2の粉末１００部に導電剤として黒鉛粉末を６部、結着剤としてポリビニリデンジフルオライド8部を溶媒n−メチル−２−ピロリドンに溶解し、攪拌混合したスラリーをアルミニウム箔上に塗布し、１４０℃で乾燥して溶媒を除去した。乾燥した塗膜は、ロールプレス機で圧着後、所定の大きさに切断して正極とした。
【００２４】
電解液はエチレンカーボネートとジメチルカーボネートの体積比１：１混合溶媒にＬｉＰＦ6を１ｍｏｌ／ｌ溶解したものを用いた。ボタン型電池を作製し、室温で一昼夜放置してエージングした後、２００ｍＡ／ｇの電流密度で充放電試験を行った。結果を表１に示す。
【００２５】
〈比較例１〉
ケイ素粉末と銅粉末をモル比１：２になるように秤量し、振動ミルで乾式混合した後、窒素雰囲気下９００℃で１０時間焼成した。焼成粉末を結着剤であるポリフッ化ビニリデンとｎ−メチル−２−ピロリドンとを用いてスラリー状にし、銅箔に塗布後１４０℃にて乾燥した後、所定の大きさに切り抜きロールプレス機で圧着した。この塗膜を窒素雰囲気下８００℃で３時間加熱し、負極として使用した。正極、電解液は実施例１と同様の方法で製造した。以下、実施例１と同様の条件により電池を作製し、充放電試験を行った。結果を表１に示す。
【００２６】
〈比較例２〉
黒鉛９０部とポリビニリデンジフルオライド１０部とをｎ−メチル−２−ピロリドン中でスラリーとし、銅箔上に塗布乾燥して得られた塗膜を所定の大きさに切り抜き、ロールプレス機で圧着した。これを負極として用いた以外は、実施例１と同様にしてボタン型電池を作製し、充放電試験を行った。結果を表１に示す。
【００２７】
【表１】
【発明の効果】
本発明においては、主にケイ化銅からなる負極活物質を用いることにより、充放電時においても負極の体積変化を抑制できるため、充放電のサイクル特性が向上した高容量で高作動電圧の非水系二次電池を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-aqueous secondary battery mainly having copper silicide as a negative electrode active material having a high operating voltage, a high capacity, and good charge / discharge cycle characteristics.
[0002]
[Prior art]
In a non-aqueous secondary battery having a voltage of 3V class, a method using a lithium metal as a negative electrode active material and an oxide of a transition metal typified by Co, Mn, Ni as a positive electrode active material is typical. However, when lithium metal is used for the negative electrode, the lithium metal grows into dendritic dendrites during charging, causing an internal short circuit or high activity of the dendrites, and there is a risk of ignition. Therefore, a calcined carbonaceous material negative electrode capable of inserting and releasing lithium as an alternative active material has been put into practical use. However, the carbonaceous material has a drawback of low charge / discharge capacity per volume. Therefore, in order to develop a secondary battery having a higher voltage of 3 to 4 V and a higher capacity, a negative electrode active material having a larger capacity is required.
[0003]
Examples of the negative electrode active material that inserts and releases lithium include transition metal chalcogen compounds, transition metal oxides having a rutile structure, for example, spinel compounds such as WO 2 (US Pat. No. 4,1984,476) and Li x Fe (Fe 2 ) O 4 . (Japanese Patent Laid-Open No. 58-220362), electrochemically synthesized Fe 2 O 3 lithium compound (US Pat. No. 4,464,447), Fe 2 O 3 lithium compound (Japanese Patent Laid-Open No. 3-11070) Nb 2 O 5 (Japanese Patent Laid-Open Nos. 62-59412 and 2-82447), iron oxide and cobalt oxide (FeO, Fe 2 O 3 , Fe 3 O 4 , CoO, Co 2 O 3 , Co 3 O 4 ) (Japanese Patent Laid-Open No. 3-291862) is known. On the other hand, Sn, Cd (Proceedings of the Electrochemical Society, 87-1, 1987), Al (Solid State Ionics, 20, 1986), Si, Pb, Bi, Sb (known to form alloys with lithium) Proceedings of the Electrochemical Society, 87-1, 1987) and the use of these alloys with lithium as negative electrode active materials are also being studied (for example, JP-A-7-29602).
[0004]
[Problems to be solved by the invention]
However, the electrode potential of the transition metal chalcogen compound, the transition metal oxide of the rutile structure, the spinel compound, and the transition metal oxide is extremely large with respect to the electrode potential of metallic lithium, and these negative electrode active materials are used as the negative electrode. Even if the battery is configured in combination with the positive electrode, there is a problem that a high voltage of 3 to 4 V cannot be obtained. In addition, Sn, Cd, Al, Si, Pb, Bi, Sb and their alloys with lithium have a problem that the capacity is small at a high current density (for example, 1 mA / cm 2 ) and the cycle life of charge / discharge is short. There is. In addition, when Si is used as an active material, a high capacity can be expected, but the volume of the electrode changes greatly with repeated charging and discharging, so there is a problem that the capacity is reduced due to electrode cracking and internal short-circuiting easily occurs. .
[0005]
Accordingly, an object of the present invention is to provide a non-aqueous secondary battery having a high voltage, a high capacity, and good charge / discharge cycle characteristics even at a high current density.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the present invention has been completed by finding that the above-mentioned problems can be solved by constituting a battery using a negative electrode active material mainly composed of copper silicide. The non-aqueous secondary battery of the present invention includes a negative electrode including a negative electrode active material mainly composed of copper silicide, a positive electrode including a positive electrode active material including a metal oxide including a transition metal as a constituent element, and a lithium ion conductive material. It consists of a non-aqueous medium. By using copper silicide for the negative electrode active material, the volume change of the negative electrode during charging / discharging is suppressed as compared with the case of using silicon, and the charge / discharge cycle characteristics are improved. Here, copper silicide is a compound of silicon and copper and refers to a composition such as CuSi, Cu 2 Si, Cu 3 Si, Cu 5 Si, or the like. Further, it is not particularly limited whether it is crystalline or amorphous.
[0008]
Also, copper silicide, if example embodiment, it is possible to use those produced by a vacuum deposition method described later.
[0011]
Moreover, you may use the copper silicide thin film formed by heat-processing in the non-oxidizing atmosphere the silicon thin film formed by the vacuum film-forming method on the surface of a copper substrate as said negative electrode active material. By the heat treatment, a reaction between the silicon thin film and copper as the substrate proceeds, and a copper silicide thin film is formed. And by making a copper substrate into a collector, preparation of a negative electrode active material and preparation of a negative electrode can be performed simultaneously. Furthermore, the internal resistance of the battery can be reduced because the reaction with the copper substrate lowers the resistance at the interface between the copper substrate that is the current collector and the negative electrode active material.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
As a manufacturing method of the negative electrode used in the present invention, a vacuum film forming method such as a vapor deposition method, a sputtering method, an ion plating method, a CVD method and a heat treatment may be combined. As a desirable manufacturing method using the vacuum film forming method, for example, there is a method in which a silicon thin film is formed on a copper substrate by a sputtering method, and then the entire substrate is heat-treated in a non-oxidizing atmosphere. The heat treatment temperature is preferably 300 to 900 ° C.
[0017]
As the positive electrode material used as the positive electrode active material of the present invention, any conventionally known material can be used. For example, Li x CoO 2 , Li x NiO 2 , MnO 2 , LiMnO 2 , Li x Mn 2 O 4 , Li x Mn 2-y O 4 , α-V 2 O 5 , TiS 2 and the like can be mentioned.
[0018]
As the lithium ion conductive non-aqueous medium used in the present invention, a non-aqueous electrolytic solution in which a lithium compound is dissolved in an organic solvent, or an organic solvent in which a lithium compound is dissolved in a polymer or a lithium compound is dissolved in a polymer. A retained polymer solid electrolyte can be used. The non-aqueous electrolyte is prepared by appropriately combining an organic solvent and an electrolyte, and any of these organic solvents and electrolytes can be used as long as they are used for this type of battery. Examples of the organic solvent include propylene carbonate, ethylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane methyl formate, butyrolactone, tetrahydrofuran, and 2-methyl. Tetrahydrofuran, 1,3-dioxofuran, 4-methyl-1,3-dioxofuran, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile, butyronitrile, valeronitrile, benzonitrile, 1,2-dichloroethane, 4-methyl- 2-pentanone, 1,4-dioxane, anisole, diglyme, dimethylformamide, dimethyl sulfoxide and the like. Two or more of these solvents can be used in combination.
[0019]
Examples of the electrolyte include LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiB (C 6 H 5 ) 4 , LiCl, LiBr, LiI, LiCH 3 SO 3 , LiCF 3 SO 3 , LiAlCl 4, and the like. Can be used alone or in combination of two or more.
[0020]
As another medium used in the present invention, a medium in which an electrolyte selected from the above electrolytes is dissolved in the following polymer can be used. For example, a polymer having a polyether chain such as polyethylene oxide or polypropylene oxide, a polymer having a polyester chain such as polyethylene succinate or polycaprolactam, a polymer having a polyamine chain such as polyethyleneimine, or a polyalkylene sulfide. Such a polymer having a polysulfide chain is exemplified.
[0021]
Further, other media used in the present invention include polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethyl methacrylate, and the like. In addition, it is possible to use a non-aqueous electrolytic solution held and plasticized from the above polymer.
[0022]
Hereinafter, the present invention will be described in more detail with reference to examples.
【Example】
<Example 1>
After silicon was deposited on the copper substrate using a sputter deposition apparatus, the substrate was heat treated at 800 ° C. for 1 hour in a nitrogen atmosphere. From the X-ray diffraction measurement after the heat treatment, it was confirmed that silicon formed copper silicide.
[0023]
The positive electrode was produced as follows. Lithium carbonate Li 2 CO 3 and cobalt carbonate CoCO 3 were weighed so that the molar ratio of Li / Co was 1: 1, wet-mixed with a ball mill using isopropyl alcohol, and the solvent was evaporated at 800 ° C. Calcination was performed for 1 hour. The calcined powder was pulverized again with a vibration mill and then calcined at 800 ° C. for 10 hours to obtain LiCoO 2 powder. 100 parts of LiCoO 2 powder, 6 parts of graphite powder as a conductive agent, 8 parts of polyvinylidene difluoride as a binder are dissolved in a solvent n-methyl-2-pyrrolidone, and a slurry obtained by stirring and mixing is applied onto an aluminum foil. And dried at 140 ° C. to remove the solvent. The dried coating film was subjected to pressure bonding with a roll press machine and then cut into a predetermined size to obtain a positive electrode.
[0024]
The electrolytic solution used was a solution of 1 mol / l of LiPF 6 in a 1: 1 mixed solvent of ethylene carbonate and dimethyl carbonate. A button-type battery was prepared and aged at room temperature for a whole day and night, and then a charge / discharge test was performed at a current density of 200 mA / g. The results are shown in Table 1.
[0025]
< Comparative example 1 >
Silicon powder and copper powder were weighed so as to have a molar ratio of 1: 2, were dry mixed by a vibration mill, and then fired at 900 ° C. for 10 hours in a nitrogen atmosphere. The fired powder is made into a slurry using a binder, polyvinylidene fluoride and n-methyl-2-pyrrolidone, applied to a copper foil, dried at 140 ° C., then cut into a predetermined size with a roll press machine. Crimped. This coating film was heated at 800 ° C. for 3 hours under a nitrogen atmosphere and used as a negative electrode. The positive electrode and the electrolytic solution were produced in the same manner as in Example 1. Hereinafter, a battery was produced under the same conditions as in Example 1, and a charge / discharge test was performed. The results are shown in Table 1.
[0026]
<Comparative Example 2 >
90 parts of graphite and 10 parts of polyvinylidene difluoride are made into a slurry in n-methyl-2-pyrrolidone, and a coating film obtained by coating and drying on copper foil is cut out to a predetermined size, and a roll press is used. Crimped. A button type battery was produced in the same manner as in Example 1 except that this was used as the negative electrode, and a charge / discharge test was performed. The results are shown in Table 1.
[0027]
[Table 1]
【The invention's effect】
In the present invention, by using a negative electrode active material mainly made of copper silicide, the volume change of the negative electrode can be suppressed even during charging and discharging, so that the high-capacity and high operating voltage is improved with improved cycle characteristics of charging and discharging. An aqueous secondary battery can be provided.
Claims (13)
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| JP17306498A JP4191281B2 (en) | 1998-06-19 | 1998-06-19 | Negative electrode active material, negative electrode and method for producing the same, and non-aqueous secondary battery |
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| JP17306498A JP4191281B2 (en) | 1998-06-19 | 1998-06-19 | Negative electrode active material, negative electrode and method for producing the same, and non-aqueous secondary battery |
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| JP4191281B2 true JP4191281B2 (en) | 2008-12-03 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001031724A1 (en) | 1999-10-22 | 2001-05-03 | Sanyo Electric Co., Ltd. | Electrode for lithium cell and lithium secondary cell |
| US7241533B1 (en) | 1999-10-22 | 2007-07-10 | Sanyo Electric Co., Ltd. | Electrode for rechargeable lithium battery and rechargeable lithium battery |
| WO2001029912A1 (en) * | 1999-10-22 | 2001-04-26 | Sanyo Electric Co., Ltd. | Electrode for lithium cell and lithium secondary cell |
| JP3733070B2 (en) | 1999-10-22 | 2006-01-11 | 三洋電機株式会社 | Electrode for lithium secondary battery and lithium secondary battery |
| CA2388016C (en) * | 1999-10-22 | 2009-12-22 | Sanyo Electric Co., Ltd. | Method for fabricating electrode for rechargeable lithium battery |
| AU7951300A (en) * | 1999-10-22 | 2001-04-30 | Sanyo Electric Co., Ltd. | Method for producing material for electrode for lithium cell |
| KR100500344B1 (en) * | 1999-10-22 | 2005-07-12 | 산요덴키가부시키가이샤 | Electrode for lithium cell and lithium secondary cell |
| WO2001084654A1 (en) | 2000-04-26 | 2001-11-08 | Sanyo Electric Co., Ltd. | Lithium secondary battery-use electrode and lithium secondary battery |
| CA2420104C (en) * | 2000-09-01 | 2012-10-30 | Sanyo Electric Co., Ltd. | Negative electrode for lithium secondary cell and method for producing the same |
| JP3895932B2 (en) | 2001-01-17 | 2007-03-22 | 三洋電機株式会社 | Negative electrode for lithium secondary battery and method for producing the same |
| CN100365849C (en) * | 2002-11-29 | 2008-01-30 | 三井金属矿业株式会社 | Negative electrode for nonaqueous secondary battery, process of producing the negative electrode, and nonaqueous secondary battery |
| AU2003302519A1 (en) | 2002-11-29 | 2004-06-23 | Mitsui Mining And Smelting Co., Ltd. | Negative electrode for non-aqueous electrolyte secondary cell and method for manufacture thereof, and non-aqueous electrolyte secondary cell |
| CN100359748C (en) * | 2003-06-19 | 2008-01-02 | 三洋电机株式会社 | Lithium secondary battery and method for producing same |
| JP4610213B2 (en) * | 2003-06-19 | 2011-01-12 | 三洋電機株式会社 | Lithium secondary battery and manufacturing method thereof |
| JP2018178153A (en) * | 2017-04-04 | 2018-11-15 | 東京印刷機材トレーディング株式会社 | METHOD FOR MANUFACTURING Cu-Si ALLOY PARTICLE, Cu-Si ALLOY PARTICLE, MANUFACTURING METHOD OF Ni-Si ALLOY PARTICLE, Ni-Si ALLOY PARTICLE, METHOD FOR MANUFACTURING Ti-Si ALLOY PARTICLE, Ti-Si ALLOY PARTICLE, METHOD FOR MANUFACTURING Fe-Si ALLOY PARTICLE, AND Fe-Si ALLOY PARTICLE |
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1998
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