JP2009048824A - Powder for lithium ion battery negative electrode material - Google Patents

Powder for lithium ion battery negative electrode material Download PDF

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JP2009048824A
JP2009048824A JP2007212565A JP2007212565A JP2009048824A JP 2009048824 A JP2009048824 A JP 2009048824A JP 2007212565 A JP2007212565 A JP 2007212565A JP 2007212565 A JP2007212565 A JP 2007212565A JP 2009048824 A JP2009048824 A JP 2009048824A
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powder
negative electrode
lithium ion
ratio
ion battery
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JP5518285B2 (en
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Akihiko Yanagiya
彰彦 柳谷
Yoshikazu Aikawa
芳和 相川
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Sanyo Special Steel Co Ltd
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Sanyo Special Steel Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powder for lithium ion battery negative electrode material whose main constituent elements are Co, Sn and Fe. <P>SOLUTION: The powder for lithium ion battery negative electrode material comprises Co-Sn-Fe alloy and has an alloy composition where the mass% ratio of the sum of Fe and Co to Sn satisfies the formula: (Co+Fe):Sn=5:5 to 1:9, and the mass% ratio of Fe to Co satisfies the formula: Co:Fe=1:3 to 3:1. Moreover, the powder for lithium ion battery negative electrode material is characterized in that one or more of Ti, In, C, Si and Ag are added at 0.1 to 10%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、ＣｏとＳｎおよびＦｅを主構成元素とするリチウムイオン電池負極材用粉末に関するものである。   The present invention relates to a powder for a negative electrode material for lithium ion batteries containing Co, Sn and Fe as main constituent elements.

近年、カメラ一体型ＶＴＲ（ビデオテープレコーダー）、携帯電話、ノートパソコンなどのポータブル電子機器が多く登場し、その小型化および軽量化が図られている。それに伴い、それらの電子機器のポータブル電源として用いられている電池、特に二次電池についてエネルギー密度の向上が強く要請されている。このような要求に応える二次電池としては、従来より、リチウムイオンの二次電池が実用化されている。   In recent years, many portable electronic devices such as a camera-integrated VTR (video tape recorder), a mobile phone, and a laptop computer have appeared, and their size and weight have been reduced. Accordingly, there is a strong demand for an improvement in energy density of batteries used as portable power sources for such electronic devices, particularly secondary batteries. Conventionally, lithium ion secondary batteries have been put to practical use as secondary batteries that meet such requirements.

しかしながら、近年の携帯用機器の高性能化に伴い、二次電池の容量に対する要求はさらに強いものとなっている。このような要求に応える二次電池として、リチウム金属などの軽金属をそのまま負極活物質として用いることが提案されている。この電池では、充電過程において負極に軽金属がデンドライト状に析出しやすくなり、デンドライトの先端で電流密度が非常に高くなる。このため、非水電解液の分離などによりサイクル寿命が低下したり、また、過度にデンドライトが成長して電池の内部短絡が発生したりするという問題があった。   However, with the recent improvement in performance of portable devices, the demand for the capacity of the secondary battery has become stronger. As a secondary battery that meets such requirements, it has been proposed to use a light metal such as lithium metal as a negative electrode active material as it is. In this battery, light metal tends to precipitate in a dendrite state on the negative electrode during the charging process, and the current density becomes very high at the end of the dendrite. For this reason, there has been a problem that the cycle life is reduced due to separation of the non-aqueous electrolyte, or the dendrite grows excessively and an internal short circuit of the battery occurs.

これに対し、種々の合金材料などを負極活物質として用いることが提案されている。例えば、珪素合金、Ｓｎ−Ｎｉ合金、Ｌｉ−Ａｌ−Ｓｎ合金、Ｓｎ−Ｚｎ合金、Ｐ−Ｓｎ合金Ｓｎ−Ｃｕ合金等が提案されている。しかし、これらの合金材料を用いた場合においても、十分なサイクル特性は得られず、合金材料における高容量負極の特徴を十分に活かしきれていないのが実状である。   On the other hand, using various alloy materials etc. as a negative electrode active material is proposed. For example, silicon alloys, Sn—Ni alloys, Li—Al—Sn alloys, Sn—Zn alloys, P—Sn alloys, Sn—Cu alloys and the like have been proposed. However, even when these alloy materials are used, sufficient cycle characteristics cannot be obtained, and the fact is that the characteristics of the high-capacity negative electrode in the alloy materials are not fully utilized.

これに対して、例えば特開２００６−１３４７８２号公報（特許文献１）に開示されているように、Ｓｎ−Ｃｏ−Ｃとを構成元素とし、Ｃの含有量が１６．８〜２４．８％、ＳｎとＣｏとの合計に対するＣｏの割合が３０〜４５％であるＣｏＳｎＣ含有材料を含有し、負極活物質層に対する正極活物質層の面密度比が２．７７〜３．９０の範囲にある電池が提案されている。
特開２００６−１３４７８２号公報 On the other hand, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-134782 (Patent Document 1), Sn—Co—C is used as a constituent element, and the C content is 16.8 to 24.8%. And a CoSnC-containing material in which the ratio of Co to the total of Sn and Co is 30 to 45%, and the surface density ratio of the positive electrode active material layer to the negative electrode active material layer is in the range of 2.77 to 3.90. Batteries have been proposed.
JP 2006-134782 A

上記、特許文献１による電池によれば、負極活物質層に、特にＣｏの割合３０〜４５％含有することが必須要件であり、このような高ＣｏであるＣｏＳｎＣ含有材料を用い、正極活物質層と負極活物質層との面密度比を所定の範囲内とするようにしたので、確かに高いエネルギー密度を得ることができると共に、優れたサイクル特性を得ることができる。しかしながら、Ｃｏは高価な原料であるため、生産性に課題がある。また、Ｃｏを少なくすると組織中に純Ｓｎの相が析出し、これが電池容量の低下を招き、電池の製品寿命を低減させるという問題がある。   According to the battery according to Patent Document 1, it is essential that the negative electrode active material layer contains 30 to 45% of Co in particular, and such a high Co CoSnC-containing material is used. Since the surface density ratio between the layer and the negative electrode active material layer is set within the predetermined range, it is possible to surely obtain a high energy density and to obtain excellent cycle characteristics. However, since Co is an expensive raw material, there is a problem in productivity. Further, when Co is decreased, a pure Sn phase is precipitated in the structure, which causes a problem that the battery capacity is lowered and the product life of the battery is reduced.

上述したような問題を解消するために、発明者らは鋭意開発を進めた結果、純Ｓｎの相を出さずに高い電池容量を達成し、かつ高価なＣｏを低減する方策として、Ｃｏより廉価で、同等の電池容量を有する元素として高価なＣｏ元素に変えて、従来考えられなかった安価なＦｅを見出したものである。ただ、Ｆｅ−Ｓｎ系は液相で２相分離反応を起こして純Ｓｎが析出し、電池容量に悪影響を及ぼすことから、Ｃｏ−Ｆｅ−Ｓｎ系であれば、２相分離が起こらない組成範囲であることを見出したもので、これにより廉価で、かつ同等の電池容量を有するＣｏとＳｎおよびＦｅを主構成元素とするリチウムイオン電池負極材用粉末を提供するものである。   In order to solve the above-described problems, the inventors have intensively developed, and as a measure to achieve high battery capacity without producing a pure Sn phase and reduce expensive Co, it is less expensive than Co. Thus, instead of an expensive Co element as an element having an equivalent battery capacity, an inexpensive Fe that has not been considered in the past has been found. However, since the Fe—Sn system undergoes a two-phase separation reaction in the liquid phase and pure Sn precipitates, adversely affecting the battery capacity, the Co—Fe—Sn system has a composition range in which two-phase separation does not occur. Accordingly, the present invention provides a powder for a negative electrode material for lithium ion batteries having Co, Sn and Fe as main constituent elements, which is inexpensive and has an equivalent battery capacity.

その発明の要旨とするとこは、
（１）Ｃｏ−Ｓｎ−Ｆｅ系合金であって、ＦｅとＣｏの和とＳｎのｍａｓｓ％比が下記式（１）を満たし、ＦｅとＣｏのｍａｓｓ％比が式（２）を満たす合金組成であることを特徴とするリチウムイオン電池負極材用粉末。
（Ｃｏ＋Ｆｅ）：Ｓｎ＝５：５〜１：９ … （１）
Ｃｏ：Ｆｅ＝１：３〜３：１ … （２）
（２）前記（１）に記載のＣｏ−Ｓｎ−Ｆｅ系合金に、Ｔｉ，Ｉｎ，Ｃ，Ｓｉ，Ａｇの１種または２種以上を０．１〜１０％添加することを特徴とするリチウムイオン電池負極材用粉末にある。 The gist of the invention is that
(1) Co—Sn—Fe-based alloy in which the sum of Fe and Co and the mass% ratio of Sn satisfy the following formula (1), and the mass% ratio of Fe and Co satisfies the formula (2) The powder for lithium ion battery negative electrode materials characterized by these.
(Co + Fe): Sn = 5: 5 to 1: 9 (1)
Co: Fe = 1: 3 to 3: 1 (2)
(2) Lithium characterized by adding 0.1 to 10% of one or more of Ti, In, C, Si, and Ag to the Co—Sn—Fe based alloy described in (1). It is in the powder for ion battery negative electrode materials.

以上述べたように、本発明により廉価で、かつ同等の電池容量を有する生産性の高いリチウムイオン電池負極材用粉末の作製が可能となった。   As described above, according to the present invention, it is possible to produce a powder for a lithium ion battery negative electrode material that is inexpensive and has an equivalent battery capacity and high productivity.

以下、本発明について詳細に説明する。
上述したように、Ｆｅ−Ｓｎの２元系では、ＦｅとＳｎが分離して純Ｓｎが析出する。純Ｓｎが析出せずに従来よりも高い電池容量を達成し、且つ高価なＣｏを低減する方策としてＣｏ−Ｆｅ−Ｓｎ系で、さらに、最適なＦｅとＣｏの比率を見出した。すなわち、最適なＦｅとＣｏの比率として、（Ｃｏ＋Ｆｅ）：Ｓｎ＝５：５〜１：９、かつＣｏ：Ｆｅ＝１：３〜３：１とするものである。 Hereinafter, the present invention will be described in detail.
As described above, in the Fe—Sn binary system, Fe and Sn are separated and pure Sn is deposited. As a measure for achieving a battery capacity higher than that of the prior art without depositing pure Sn and reducing expensive Co, a Co—Fe—Sn system was further found, and an optimum Fe to Co ratio was found. That is, the optimum ratio of Fe and Co is (Co + Fe): Sn = 5: 5 to 1: 9 and Co: Fe = 1: 3 to 3: 1.

（Ｃｏ＋Ｆｅ）：Ｓｎ＝５：５〜１：９とした理由は、（Ｃｏ＋Ｆｅ）の比率がＳｎに比較して高い場合には電池容量が低下する。逆にＳｎの比率が高い場合も同様に純Ｓｎが析出し電池容量が低下する。かつ、Ｃｏ：Ｆｅ＝１：３〜３：１とした理由は、Ｃｏの比率が高い場合、電池容量が低下すると共に、高価なＣｏ量が増加するのでコストに課題が生じる。逆にＦｅの比率が高い場合はＦｅとＳｎが分離して純Ｓｎが析出し、電池容量が低下することから、それぞれの最適な比率範囲に特徴がある。   The reason why (Co + Fe): Sn = 5: 5 to 1: 9 is that when the ratio of (Co + Fe) is higher than Sn, the battery capacity decreases. Conversely, when the Sn ratio is high, pure Sn is similarly deposited and the battery capacity is reduced. The reason why Co: Fe = 1: 3 to 3: 1 is that when the ratio of Co is high, the battery capacity decreases and the amount of expensive Co increases, which causes a problem in cost. On the contrary, when the ratio of Fe is high, Fe and Sn are separated and pure Sn is deposited, and the battery capacity is lowered.

上記Ｃｏ−Ｆｅ−Ｓｎ系合金に、さらにＴｉ，Ｉｎ，Ｃ，Ｓｉ，Ａｇの１種または２種以上を０．１〜１０％添加することで電池容量の増大を図ることができる。しかし、０．１％未満では、その効果が十分に得られず、１０％を超えるとその効果は飽和することから、その添加範囲を０．１〜１０％とした。好ましくは１〜５％とする。   The battery capacity can be increased by adding 0.1 to 10% of one or more of Ti, In, C, Si, and Ag to the Co—Fe—Sn alloy. However, if the content is less than 0.1%, the effect cannot be sufficiently obtained, and if the content exceeds 10%, the effect is saturated. Therefore, the addition range is set to 0.1 to 10%. Preferably it is 1 to 5%.

［実施例１］
以下、本発明について実施例によって具体的に説明する。
先ず、Ｃｏ−Ｆｅ−Ｓｎ含有材料粉末を次のようにして作製した。原料としてＣｏとＳｎとＦｅとを用意し、これらを表１に示すような、各種割合に調整した原料粉をガスアトマイズ法により作製した。アトマイズ時の条件は、ガス種類：Ａｒ、ノズル径：６ｍｍ、ガス圧：５ＭＰａである。この合金粉を−１０６μｍのふるいにて分級し、得られたＣｏ−Ｆｅ−Ｓｎ含有材料についての組成の分析を行った。 [Example 1]
Hereinafter, the present invention will be specifically described with reference to examples.
First, a Co—Fe—Sn-containing material powder was produced as follows. Co, Sn, and Fe were prepared as raw materials, and raw material powders adjusted to various ratios as shown in Table 1 were prepared by a gas atomization method. The conditions during atomization are gas type: Ar, nozzle diameter: 6 mm, and gas pressure: 5 MPa. This alloy powder was classified with a −106 μm sieve, and the composition of the obtained Co—Fe—Sn-containing material was analyzed.

評価項目としての、純Ｓｎの析出については、Ｘ線回折を行った結果、Ｘ線回折パターンとして２０〜８０°の間を測定し、この範囲にＳｎ（１１１）のピークの有無により、純Ｓｎの析出の有無を判断した。また、作製した二次電池についての電池容量の評価として、初回放電電力量を測定した。それらの結果を表１に示す。その際の電力量は次のようにして測定した。まず、電流値０．９Ａ、上限電圧４．２Ｖの定電流定電圧にて充電を３時間行った後、０．５Ｖの電圧で、電池電圧が２．５Ｖに達するまで放電を行うという充放電を繰り返した。電力量は、初回放電時の電圧と電流および放電時間の積として求めた。その結果を表１に示す。   About precipitation of pure Sn as an evaluation item, as a result of performing X-ray diffraction, an X-ray diffraction pattern was measured between 20 ° and 80 °, and pure Sn was determined depending on the presence or absence of a Sn (111) peak in this range. The presence or absence of precipitation was judged. In addition, as an evaluation of the battery capacity of the produced secondary battery, the initial discharge electric energy was measured. The results are shown in Table 1. The amount of power at that time was measured as follows. First, after charging for 3 hours at a constant current / constant voltage with a current value of 0.9A and an upper limit voltage of 4.2V, the battery is discharged at a voltage of 0.5V until the battery voltage reaches 2.5V. Was repeated. The amount of electric power was determined as the product of the voltage, current, and discharge time at the first discharge. The results are shown in Table 1.

［実施例２］
実施例１と同様に、Ｃｏ−Ｆｅ−Ｓｎに加えて、Ｔｉ，Ｉｎ，Ｃ，Ｓｉ，Ａｇの１種または２種以上を含む材料粉末を次のようにして作製した。原料としてＣｏとＳｎとＦｅとを用意し、これらを表１に示すような、各種割合に調整した原料粉をガスアトマイズ法により作製した。アトマイズ時の条件は、ガス種類：Ａｒ、ノズル径：６ｍｍ、ガス圧：５ＭＰａである。この合金粉を−１０６μｍのふるいにて分級し、得られたＣｏ−Ｆｅ−Ｓｎに加えて、Ｔｉ，Ｉｎ，Ｃ，Ｓｉ，Ａｇの１種または２種以上を含む材料粉末材料についての組成の分析を行った。 [Example 2]
Similarly to Example 1, in addition to Co—Fe—Sn, a material powder containing one or more of Ti, In, C, Si, and Ag was produced as follows. Co, Sn, and Fe were prepared as raw materials, and raw material powders adjusted to various ratios as shown in Table 1 were prepared by a gas atomization method. The conditions during atomization are gas type: Ar, nozzle diameter: 6 mm, and gas pressure: 5 MPa. This alloy powder is classified by a -106 μm sieve, and in addition to the obtained Co—Fe—Sn, the composition of the material powder material containing one or more of Ti, In, C, Si, Ag is used. Analysis was carried out.

［実施例３］
実施例１と同様に、Ｃｏ−Ｆｅ−Ｓｎ含有材料粉末を次のようにして作製した。原料としてＣｏとＳｎとＦｅとを用意し、これらを表１に示すような、割合に調整した原料粉を水アトマイズ法により作製した。この合金粉を−１０６μｍのふるいにて分級し、得られたＣｏ−Ｆｅ−Ｓｎ含有材料についての組成の分析を行った。 [Example 3]
Similarly to Example 1, a Co—Fe—Sn-containing material powder was produced as follows. Co, Sn, and Fe were prepared as raw materials, and raw material powders adjusted to the ratios shown in Table 1 were prepared by a water atomization method. This alloy powder was classified with a −106 μm sieve, and the composition of the obtained Co—Fe—Sn-containing material was analyzed.

［実施例４］
実施例２と同様に、Ｃｏ−Ｆｅ−Ｓｎに加えて、Ｔｉ，Ｉｎ，Ｃ，Ｓｉ，Ａｇの１種または２種以上を含む材料粉末を次のようにして作製した。原料としてＣｏとＳｎとＦｅとを用意し、これらを表１に示すような、割合に調整した原料粉を水アトマイズ法により作製した。この合金粉を−１０６μｍのふるいにて分級し、得られたＣｏ−Ｆｅ−Ｓｎに加えて、Ｔｉ，Ｉｎ，Ｃ，Ｓｉ，Ａｇの１種または２種以上を含む材料粉末材料についての組成の分析を行った。 [Example 4]
Similarly to Example 2, in addition to Co—Fe—Sn, a material powder containing one or more of Ti, In, C, Si, and Ag was produced as follows. Co, Sn, and Fe were prepared as raw materials, and raw material powders adjusted to the ratios shown in Table 1 were prepared by a water atomization method. This alloy powder is classified with a -106 μm sieve, and in addition to the obtained Co—Fe—Sn, the composition of the material powder material containing one or more of Ti, In, C, Si, Ag is used. Analysis was carried out.

［実施例５］
Ｃｏ−Ｆｅ−Ｓｎ含有材料粉末を次のようにして作製した。原料としてＣｏとＳｎとＦｅとを用意し、これらを表１に示すような、割合に調整した原料粉の合金溶湯を真空溶解し、鋳造したＣｏ−Ｆｅ−Ｓｎ合金インゴットを作製した。その後、このＣｏ−Ｆｅ−Ｓｎ合金インゴットを鋳造粉砕法にて粉砕する。この粉砕条件としては、メディア：ステンレス製ボールミル、回転速度：４００ｒｐｍ、粉砕時間：１０ｈｒにより作製した。この合金粉を−１０６μｍのふるいにて分級し、得られたＣｏ−Ｆｅ−Ｓｎ含有材料についての組成の分析を行った。 [Example 5]
A Co—Fe—Sn-containing material powder was produced as follows. Co, Sn, and Fe were prepared as raw materials, and the alloy powder of raw material powder adjusted to a ratio as shown in Table 1 was vacuum-melted to prepare a cast Co—Fe—Sn alloy ingot. Thereafter, the Co—Fe—Sn alloy ingot is pulverized by a casting pulverization method. The pulverization conditions were media: stainless steel ball mill, rotational speed: 400 rpm, and pulverization time: 10 hr. This alloy powder was classified with a −106 μm sieve, and the composition of the obtained Co—Fe—Sn-containing material was analyzed.

Figure 2009048824
表１に示すように、Ｎｏ．１〜１６は本発明例であり、Ｎｏ．１７〜２３は比較例である。比較例Ｎｏ．１７はＣｏ：Ｆｅの比が１：４とＦｅの比率が高いためにＦｅとＳｎが分離して純Ｓｎが析出し、電池容量が低い。比較例Ｎｏ．１８はＣｏ：Ｆｅの比が４：１とＣｏの比率が高いために電池容量が低い。しかも、Ｃｏが多いためにコスト的に高価となる。
Figure 2009048824
 As shown in Table 1, no. 1 to 16 are examples of the present invention. 17-23 are comparative examples. Comparative Example No. In No. 17, since the ratio of Co: Fe is 1: 4 and the ratio of Fe is high, Fe and Sn are separated and pure Sn is precipitated, and the battery capacity is low. Comparative Example No. No. 18 has a low Co battery capacity because the Co: Fe ratio is 4: 1 and the Co ratio is high. Moreover, since there is much Co, it becomes expensive in terms of cost.

比較例Ｎｏ．１９は（Ｃｏ＋Ｆｅ）：Ｓｎの比率が６：４と（Ｃｏ＋Ｆｅ）の比率がＳｎに比較して高いために電池容量が低い。比較例Ｎｏ．２０は（Ｃｏ＋Ｆｅ）：Ｓｎの比率が０．５：９．５とＮｏ．１９とは逆にＳｎの比率が高いために純Ｓｎが析出し電池容量が低い。比較例Ｎｏ．２１〜Ｎｏ．２３はいずれもＦｅを含有しない場合であり、いずれも電池容量が低い。   Comparative Example No. No. 19 has a low battery capacity because the ratio of (Co + Fe): Sn is 6: 4 and the ratio of (Co + Fe) is higher than that of Sn. Comparative Example No. No. 20 has a ratio of (Co + Fe): Sn of 0.5: 9.5 and no. Contrary to 19, since the Sn ratio is high, pure Sn is deposited and the battery capacity is low. Comparative Example No. 21-No. No. 23 is a case where no Fe is contained, and any battery capacity is low.

これに対して、本発明例Ｎｏ．１〜１６はいずれも本発明の条件を満たしていることから、電池容量が高く、良好な値が得られる。しかも、Ｃｏの使用量を少なくすることで安価で生産性の高いリチウム電池負極用粉末を製造可能としたことは工業的に極めて優れた効果を奏するものである。


特許出願人 山陽特殊製鋼株式会社
代理人 弁理士 椎 名 彊 On the other hand, the present invention example No. Since 1-16 satisfy | fill the conditions of this invention, battery capacity is high and a favorable value is obtained. In addition, the fact that it is possible to produce an inexpensive and highly productive powder for a lithium battery negative electrode by reducing the amount of Co used has an extremely excellent industrial effect.


Patent Applicant Sanyo Special Steel Co., Ltd.
Attorney: Attorney Shiina

Claims (2)

Ｃｏ−Ｓｎ−Ｆｅ系合金であって、ＦｅとＣｏの和とＳｎのｍａｓｓ％比が下記式（１）を満たし、ＦｅとＣｏのｍａｓｓ％比が式（２）を満たす合金組成であることを特徴とするリチウムイオン電池負極材用粉末。
（Ｃｏ＋Ｆｅ）：Ｓｎ＝５：５〜１：９ … （１）
Ｃｏ：Ｆｅ＝１：３〜３：１ … （２） It is a Co—Sn—Fe-based alloy having an alloy composition in which the mass% ratio of the sum of Fe and Co and Sn satisfies the following formula (1), and the mass% ratio of Fe and Co satisfies the formula (2) A powder for a negative electrode material for a lithium ion battery.
(Co + Fe): Sn = 5: 5 to 1: 9 (1)
Co: Fe = 1: 3 to 3: 1 (2) 請求項１に記載のＣｏ−Ｓｎ−Ｆｅ系合金に、Ｔｉ，Ｉｎ，Ｃ，Ｓｉ，Ａｇの１種または２種以上を０．１〜１０％添加することを特徴とするリチウムイオン電池負極材用粉末。 A lithium ion battery negative electrode material, wherein 0.1 to 10% of one or more of Ti, In, C, Si, and Ag is added to the Co-Sn-Fe alloy according to claim 1 Powder.
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