JP2017224600A - Silicon oxide based negative electrode material - Google Patents

Silicon oxide based negative electrode material Download PDF

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JP2017224600A
JP2017224600A JP2017113290A JP2017113290A JP2017224600A JP 2017224600 A JP2017224600 A JP 2017224600A JP 2017113290 A JP2017113290 A JP 2017113290A JP 2017113290 A JP2017113290 A JP 2017113290A JP 2017224600 A JP2017224600 A JP 2017224600A
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悠介 柏谷
Yusuke Kashitani
悠介 柏谷
木崎　信吾
Shingo Kizaki
信吾 木崎
浩樹 竹下
Hiroki Takeshita
浩樹 竹下
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Osaka Titanium Technologies Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a silicon oxide based negative electrode material used for forming a negative electrode of a lithium ion secondary battery, containing Mg for irreversible capacity cancellation, and capable of avoiding as much as possible reduction in battery performance caused by nonuniformity of Mg concentration distribution.SOLUTION: The silicon oxide based negative electrode material is made of a ternary material of Si-Mg-O. It further contains a Si phase, contains as a Mg containing compounds any one of five of MgSiO, MgSiO, MgO, MgSiO3+MgSiOor MgSiO+MgO, and contains none of SiO, metal Mg, and MgSi alloy. The composition is represented by SiMgO, satisfying 3y>z>y and 2x+y>z.SELECTED DRAWING: Figure 1

Description

本発明は、Ｌｉイオン二次電池の負極形成に使用される酸化珪素系負極材及びその製造方法に関し、より詳しくは、不可逆容量キャンセルのためにＭｇをドープされた酸化珪素系負極材及びその製造方法に関する。   The present invention relates to a silicon oxide-based negative electrode material used for forming a negative electrode of a Li-ion secondary battery and a manufacturing method thereof, and more particularly, a silicon oxide-based negative electrode material doped with Mg for irreversible capacity cancellation and the manufacture thereof. Regarding the method.

酸化珪素（ＳｉＯX）は電気容量が大きく、寿命特性に優れたＬｉイオン二次電池用負極材であることが知られている。この酸化珪素系負極材は、酸化珪素粉末、導電助剤及びバインダーを混合してスラリー化したものを、銅箔等からなる集電体上に塗工して薄膜状の負極とされる。ここにおける酸化珪素粉末は、例えば二酸化珪素と珪素との混合物を加熱して生成した一酸化珪素ガスを冷却し、析出させた後、細かく破砕することにより得られる。このような析出法で製造される酸化珪素粉末は、アモルファスの部分を多く含み、充放電時の膨張収縮・微粉化を抑制し、サイクル特性を向上させることが知られている。 Silicon oxide (SiO x ) is known to be a negative electrode material for Li ion secondary batteries having a large electric capacity and excellent life characteristics. This silicon oxide-based negative electrode material is formed by mixing a silicon oxide powder, a conductive additive and a binder into a slurry and coating it on a current collector made of copper foil or the like to form a thin-film negative electrode. The silicon oxide powder here is obtained, for example, by cooling and precipitating silicon monoxide gas generated by heating a mixture of silicon dioxide and silicon, and then finely crushing. It is known that the silicon oxide powder produced by such a precipitation method includes many amorphous portions, suppresses expansion / contraction and pulverization during charge / discharge, and improves cycle characteristics.

このような酸化珪素系負極材に特徴的な問題点として初期効率の低さがある。これは充放電に寄与しない不可逆容量となるＬｉ化合物が初回充電時に生成されることにより、初回放電容量が顕著に減少する現象であり、これを解消する手法として、酸化珪素粉末に他種元素を添加する他元素ドープが知られている。   A characteristic characteristic of such a silicon oxide negative electrode material is low initial efficiency. This is a phenomenon in which the initial discharge capacity is remarkably reduced due to the generation of Li compounds that become irreversible capacity that does not contribute to charge and discharge during the first charge. Other element doping to be added is known.

例えば、特許文献１では、他元素としてのＡｌ、Ｃａ、Ｍｇ、Ｔｉを酸化珪素であるＳｉＯと、ボールミルにより機械的に混合し合金化して、Ｓｉ相、ＳｉＯ2 及び他元素化合物を含むナノ複合体を作製することにより、初期効率を高める固相法が提案されている。また、特許文献２では、ＳｉＯガスと他元素蒸気ガスとを別々に発生させた後、両ガスを混合し、冷却して回収する気相法が提案されている。 For example, in Patent Document 1, Al, Ca, Mg, and Ti as other elements are mechanically mixed with SiO, which is silicon oxide, and alloyed by a ball mill to form a nanocomposite containing Si phase, SiO 2 and other element compounds. Solid phase methods have been proposed that increase the initial efficiency by creating a body. Patent Document 2 proposes a gas phase method in which SiO gas and other element vapor gas are separately generated, and then both gases are mixed, cooled and recovered.

いずれの手法でも、充放電に寄与しない不可逆容量となる他元素化合物が事前に生成されることにより、初回充放電時に不可逆容量となるＬｉ化合物が生成されるのが抑制されて、初期効率の向上が図られる。これが不可逆容量キャンセル処理である。   In any method, by generating other elemental compounds with irreversible capacity that do not contribute to charging / discharging in advance, the generation of Li compounds that become irreversible capacity at the first charging / discharging is suppressed, and the initial efficiency is improved. Is planned. This is irreversible capacity cancellation processing.

他元素ドープにおけるドープ元素としては、Ｌｉが比較的多く採用されているが、Ｌｉ、Ｌｉ化合物は反応性、水溶性が高く、取り扱いが簡単でない上に、電極塗工のためのスラリー化の工程で不具合を生じ、電池性能を低下させる原因になる。これ対し、Ｍｇはこれらの問題がない上に、不可逆容量キャンセル効果についてはＬｉと大差ないとされている。   Li is used as a doping element in doping with other elements, but Li and Li compounds are highly reactive and water-soluble, are not easy to handle, and are a slurry process for electrode coating. This can cause problems and reduce battery performance. On the other hand, Mg does not have these problems, and the irreversible capacity canceling effect is not much different from Li.

しかしながら、他元素ドープによる不可逆容量キャンセル処理を受けた酸化珪素系負極材では、他元素が不均一にドープされることに起因して電池性能の低下を招くことが問題視されており、Ｍｇドープも例外ではない。   However, the silicon oxide negative electrode material that has been subjected to irreversible capacity cancellation treatment by doping with other elements has been regarded as a problem that it causes deterioration in battery performance due to non-uniform doping of other elements. Is no exception.

すなわち、Ｍｇドープにおいて、例えばＳｉＯとＭｇを１：１で反応させた場合、元素が均一に分布していれば、熱力学上はＳｉとＭｇＯのみが存在することになるが、元素濃度分布が不均一な場合は、ＳｉとＭｇＯのみならず、未反応のＳｉＯ、金属Ｍｇといった別の物質も存在することになる。そして、Ｌｉイオン電池の充放電では、化合物の種類によってＬｉの脱挿方法、電圧等が異なるので、一部だけ別の物質が混じっていると、そこが起点として粒子が割れたり、別の物質の反応性が高い場合は、バインダーや電解液がダメージを受けたりする。また、金属Ｍｇが存在する場合は、充放電時にＭｇが溶けだし、別の場所で析出することで電池内部の部材を破壊するなどの影響も考えられる。これらは何れも電池性能、特に初期効率を低下させる原因になる。   That is, in Mg doping, for example, when SiO and Mg are reacted at a ratio of 1: 1, if the elements are uniformly distributed, only Si and MgO exist in terms of thermodynamics, but the element concentration distribution is In the case of non-uniformity, not only Si and MgO but also other substances such as unreacted SiO and metal Mg are present. In Li-ion battery charging / discharging, the Li insertion and removal method, voltage, etc. differ depending on the type of compound. Therefore, if only a part of another substance is mixed, the particle may be cracked as a starting point. When the reactivity of is high, the binder and the electrolytic solution may be damaged. Further, when metal Mg is present, Mg starts to melt at the time of charging / discharging, and the effect of destroying members inside the battery due to precipitation at another place is also considered. Any of these causes a decrease in battery performance, particularly initial efficiency.

特許第５３５２１６９号公報Japanese Patent No. 5352169 特許第３８５２５７９号公報Japanese Patent No. 3852579

本発明の目的は、Ｍｇがドープされているにもかかわらず、Ｍｇ濃度分布の不均一に起因する電池性能の低下を可及的に回避できる酸化珪素系負極材及びその製造方法を提供することにある。   An object of the present invention is to provide a silicon oxide-based negative electrode material and a method for producing the same that can avoid as much as possible a decrease in battery performance due to non-uniform Mg concentration distribution despite being doped with Mg. It is in.

酸化珪素に対するＭｇドープを、前述したＳｉＯとＭｇとの反応を例にとって説明するならば、その反応はＭｇドープ量が増えるにつれて、化学式１中の（１）式、（２）式、（３）式の順に進行する。   If Mg doping with respect to silicon oxide is explained by taking the reaction of SiO and Mg as an example, the reaction is expressed by the following formulas (1), (2), and (3) as the Mg doping amount increases. Proceeds in the order of the formula.

（化学式１）
ＳｉＯ＋１／３Ｍｇ→２／３Ｓｉ＋１／３ＭｇＳｉＯ3 ・・・（１）
ＳｉＯ＋１／２Ｍｇ→３／４Ｓｉ＋１／４Ｍｇ2ＳｉＯ4 ・・・（２）
ＳｉＯ＋Ｍｇ→Ｓｉ＋ＭｇＯ・・・（３） (Chemical formula 1)
SiO + 1 / 3Mg → 2 / 3Si + 1 / 3MgSiO 3 (1)
SiO + 1 / 2Mg → 3 / 4Si + 1 / 4Mg 2 SiO 4 (2)
SiO + Mg → Si + MgO (3)

すなわち、ＳｉＯに対するＭｇ量が〜１／３であれば、（１）式の反応が起こり、１／３に至るまではＳｉ相とＭｇＳｉＯ3と未反応のＳｉＯが生じるが、１／３だとＳｉ相とＭｇＳｉＯ3が生じる。ＳｉＯに対するＭｇ量が１／３〜１／２であれば、（１）式の反応が終わった後に（２）式の反応が始まり、ＭｇＳｉＯ3の一部がＭｇ2ＳｉＯ4に変化するので、１／２に至るまではＳｉ相とＭｇＳｉＯ3とＭｇ2ＳｉＯ4が生じるが、１／２だとＳｉ相とＭｇ2ＳｉＯ4 が生じる。 That is, if the amount of Mg with respect to SiO is ˜1 / 3, the reaction of the formula (1) occurs, and until it reaches Ｓｉ, Si phase, MgSiO 3 and unreacted SiO are generated. Si phase and MgSiO 3 are generated. If the amount of Mg with respect to SiO is 1/3 to 1/2, the reaction of formula (2) starts after the reaction of formula (1) ends, and a part of MgSiO 3 changes to Mg 2 SiO 4 . up to 1/2 Si phase and MgSiO 3 and Mg 2 SiO 4 occurs, but 1/2 but the Si phase and the Mg 2 SiO 4 is generated.

同様に、ＳｉＯに対するＭｇ量が１／２〜１であれば、（２）式の反応が終わった後に（３）式の反応が始まり、Ｍｇ2ＳｉＯ4の一部がＭｇＯに変化するので、１に至るまではＳｉ相とＭｇ2ＳｉＯ4とＭｇＯが生じるが、１だとＳｉ相とＭｇＯが生じる。ＳｉＯに対するＭｇ量が１〜であれば、Ｓｉ相とＭｇＯと余剰Ｍｇとしての金属Ｍｇ、ＭｇＳｉ合金が生じる。 Similarly, if the amount of Mg with respect to SiO is 1/2 to 1, the reaction of formula (3) starts after the reaction of formula (2) ends, and a part of Mg 2 SiO 4 changes to MgO. Up to 1, Si phase, Mg 2 SiO 4 and MgO are generated, but when 1, Si phase and MgO are generated. If the amount of Mg with respect to SiO is 1 to, a metal phase Mg, MgSi alloy as Si phase, MgO, and excess Mg is generated.

なお、ＳｉＯはＳｉとＳｉＯ2の混合物（１／２Ｓｉ＋１／２ＳｉＯ2）であるので、実際の反応ではＳｉＯ2を生じる。 Since SiO is a mixture of Si and SiO 2 (1 / 2Si + 1 / 2SiO 2 ), SiO 2 is generated in the actual reaction.

ここで、ＳｉＯ2はＬｉと反応した際に珪酸リチウムが生成する不可逆反応を生じ、初期効率を低下させる原因になる。また、金属Ｍｇ及びＭｇＳｉ合金は活性で反応性が高く、電池作製時に部材と反応するなど、取り扱いを困難にする。このため、Ｍｇドープ酸化珪素系負極材では、ＳｉＯ2や金属Ｍｇ、ＭｇＳｉ合金が生じないように組成を厳密に管理しているが、実際は元素濃度分布の不均一に起因してＳｉＯ2や金属Ｍｇ、ＭｇＳｉ合金が生じる危険性がある。 Here, SiO 2 causes an irreversible reaction in which lithium silicate is generated when it reacts with Li, which causes a decrease in initial efficiency. In addition, metallic Mg and MgSi alloy are active and highly reactive, making them difficult to handle, such as reacting with members during battery fabrication. For this reason, in the Mg-doped silicon oxide negative electrode material, the composition is strictly controlled so as not to generate SiO 2 , metal Mg, and MgSi alloy, but in reality, SiO 2 and metal are caused by non-uniform element concentration distribution. There is a risk that Mg and MgSi alloys are formed.

すなわち、ＳｉＯ2も金属Ｍｇ、ＭｇＳｉ合金も生じないように組成管理が行われていても、その組成管理が功を奏するのは元素濃度分布が均一な場合だけであり、局所的なＭｇ過少部が発生するとＳｉＯ2が生成し、局所的なＭｇ過多部が発生すると金属Ｍｇ、ＭｇＳｉ合金が生じるのである。 That is, even if the composition management is performed so that neither SiO 2 nor metallic Mg, MgSi alloy is generated, the composition management is effective only when the element concentration distribution is uniform, and the local Mg low portion When SiO 2 is generated, SiO 2 is generated, and when an excessive Mg portion is generated, metallic Mg and MgSi alloy are generated.

これから分かるように、Ｍｇドープを受けた酸化珪素系負極材では、Ｍｇドープでの生成物の違いが、元素濃度分布の均一、不均一の指標となり得る。本発明者らはこの点に着目し、生成物のなかの特にＭｇ含有化合物の種類と、元素濃度分布の均一、不均一との関係について、実験を交えて詳細に調査した。その結果、以下のことが判明した。   As can be seen from this, in a silicon oxide negative electrode material that has undergone Mg doping, the difference in the product of Mg doping can be an indicator of uniform and non-uniform element concentration distribution. The present inventors paid attention to this point, and investigated in detail the relationship between the kind of the Mg-containing compound in the product and the uniformity and nonuniformity of the element concentration distribution through experiments. As a result, the following was found.

ＳｉＯに対しＭｇを０．４添加すると、そのＭｇ量は１／３〜０．５の範囲内であるので、元素濃度分布が均一でＭｇ量どおりの反応が起これば、前述したとおり、Ｓｉ相が生成すると共に、Ｍｇ含有化合物としてＭｇＳｉＯ3及びＭｇ2ＳｉＯ4が生成する。 When 0.4 Mg is added to SiO, the amount of Mg is in the range of 1 to 3 to 0.5. Therefore, if the element concentration distribution is uniform and the reaction occurs according to the amount of Mg, as described above, A phase is formed, and MgSiO 3 and Mg 2 SiO 4 are formed as Mg-containing compounds.

しかし、Ｍｇ量が同じ０．４でも、Ｓｉに対しＭｇが０．２しか存在しない部分と、Ｓｉに対しＭｇが０．６存在する部分が混在し、全体としてＭｇ量が０．４となる場合は、Ｍｇ量が０．２の部分ではＳｉＯ2とＳｉ相とＭｇとＭｇ含有化合物としてのＭｇＳｉＯ3が生じ、Ｍｇ量が０．６の部分ではＳｉ相とＭｇ含有化合物としてのＭｇ2ＳｉＯ4及びＭｇＯが生じる。その結果、全体ではＳｉＯ2、Ｓｉ相、並びにＭｇ含有化合物としてのＭｇＳｉＯ3、Ｍｇ2ＳｉＯ4及びＭｇＯが生じる。この組合せは、前述したとおり、元素濃度分布が均一の場合は生じることがないので、生成するＭｇ含有化合物の種類が、元素濃度分布が均一、不均一であることの指標となる。 However, even if the Mg amount is the same 0.4, a portion where only 0.2 Mg exists with respect to Si and a portion where 0.6 Mg exists relative to Si are mixed, resulting in an overall Mg amount of 0.4. In the case where Mg content is 0.2, SiO 2 and Si phase and MgSiO 3 as Mg and Mg-containing compound are produced, and Mg content is 0.6 and Mg 2 SiO as Si phase and Mg-containing compound are produced. 4 and MgO are produced. As a result, SiO 2 , Si phase, and MgSiO 3 , Mg 2 SiO 4 and MgO as Mg-containing compounds are generated as a whole. As described above, this combination does not occur when the element concentration distribution is uniform. Therefore, the type of the Mg-containing compound to be generated is an indicator that the element concentration distribution is uniform or non-uniform.

同様に、Ｓｉに対しＭｇが１／３存在する部分と、Ｓｉに対しＭｇが１存在する部分が混在し、全体としてＭｇ量が２／３となる場合は、Ｍｇ量が１／３の部分ではＳｉ相とＭｇ含有化合物としてのＭｇＳｉＯ3が生じ、Ｍｇ量が１の部分ではＳｉ相とＭｇ含有化合物としてのびＭｇＯが生じ、その結果、全体ではＳｉ相、並びにＭｇ含有化合物としてのＭｇＳｉＯ3及びＭｇＯが生じるが、この組合せも又、元素濃度分布が均一の場合は生じることがない。ちなみに、元素濃度分布が均一の場合、Ｍｇ量が２／３だとＳｉ相、並びにＭｇ含有化合物としてのＭｇ2ＳｉＯ4及びＭｇＯが生じる。 Similarly, when a portion where 1/3 of Mg is present with respect to Si and a portion where 1 Mg is present with respect to Si are mixed and the amount of Mg is 2/3 as a whole, the portion where the amount of Mg is 1/3 Produces MgSiO 3 as the Si phase and Mg-containing compound, and produces MgO as the Si phase and Mg-containing compound in the portion where the amount of Mg is 1, resulting in the overall Si phase and MgSiO 3 as the Mg-containing compound and Although MgO is generated, this combination also does not occur when the element concentration distribution is uniform. Incidentally, when the element concentration distribution is uniform, if the amount of Mg is 2/3, the Si phase and Mg 2 SiO 4 and MgO as Mg-containing compounds are generated.

本発明の酸化珪素系負極材は、かかる知見を基礎として開発されたものであり、Ｌｉイオン二次電池の負極形成に使用される酸化珪素系負極材であって、Ｓｉ−Ｍｇ−Ｏの３元系材料からなり、Ｓｉ相を含むと共に、Ｍｇ含有化合物としてＭｇＳｉＯ3、Ｍｇ2ＳｉＯ4 、ＭｇＯ、ＭｇＳｉＯ3＋Ｍｇ2ＳｉＯ4又はＭｇ2ＳｉＯ4＋ＭｇＯの５種のうちの何れか１種を含む一方、ＳｉＯ2、金属Ｍｇ及びＭｇＳｉ合金の何れも含まないことを構成上の特徴点としている。 The silicon oxide negative electrode material of the present invention was developed on the basis of such knowledge, and is a silicon oxide negative electrode material used for forming a negative electrode of a Li ion secondary battery, which is made of Si—Mg—O 3. It is made of a base material and contains an Si phase and includes any one of five kinds of MgSiO 3 , Mg 2 SiO 4 , MgO, MgSiO 3 + Mg 2 SiO 4 or Mg 2 SiO 4 + MgO as an Mg-containing compound. On the other hand, the feature of the constitution is that none of SiO 2 , metal Mg and MgSi alloy is contained.

また、本発明の酸化珪素系負極材の製造方法は、ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させ、それらのガスを蒸着面上で冷却して回収するものである。   Moreover, the manufacturing method of the silicon oxide type negative electrode material of the present invention generates SiO gas and Mg gas at the same time in the same container and cools and recovers these gases on the vapor deposition surface.

本発明の酸化珪素系負極材において、Ｍｇ含有化合物の種類をＭｇＳｉＯ３、Ｍｇ2ＳｉＯ4、ＭｇＯ、ＭｇＳｉＯ3＋Ｍｇ2ＳｉＯ4又はＭｇ2ＳｉＯ4＋ＭｇＯの何れか一種に限定したのは、これが元素濃度分布が均一であることの証左であるからである。ここに規定していないＭｇＳｉＯ３及びＭｇＯの組合せ、並びにＭｇＳｉＯ3、Ｍｇ2ＳｉＯ4及びＭｇＯの組合せが、元素濃度分布の不均一を意味することと合わせ、（１）式〜（３）式により説明したとおりである。 In the silicon oxide negative electrode material of the present invention, the kind of Mg-containing compound is limited to any one of MgSiO 3 , Mg 2 SiO 4 , MgO, MgSiO 3 + Mg 2 SiO 4 or Mg 2 SiO 4 + MgO. This is because it is evidence that the concentration distribution is uniform. The combination of MgSiO 3 and MgO not specified here, and the combination of MgSiO 3 , Mg 2 SiO 4 and MgO mean that the element concentration distribution is non-uniform, and is explained by the formulas (1) to (3). Just as you did.

また、ＳｉＯ2、金属Ｍｇ及びＭｇＳｉ合金も、前述したとおり、局所的なＭｇ過少部及び局所的なＭｇ過多部において生じるので、これらを含まないことも又、元素濃度分布が均一であることの証左である。 Further, as described above, SiO 2 , metal Mg and MgSi alloy are also generated in the local Mg excess portion and the local Mg excess portion, so that these elements are not included or the element concentration distribution is uniform. This is evidence.

また、Ｓｉ相が必須であるのは、ＳｉがＬｉを充放電するので、Ｓｉ相が存在しないと電池容量が発現しないからである。Ｓｉ相は結晶質でもアモルファスでもよいが、充放電時の膨張収縮が小さく、電池性能が高くなることから、アモルファス若しくはこれに近い相が望ましく、ＣｕＫα線を用いたＸＲＤ測定を行った際に、２θ＝２８．４±０．３°付近に表れるＳｉに由来のピークの半値幅から算出するＳｉ結晶粒子径で表して４０ｎｍ以下であることが必要である。   In addition, the Si phase is essential because Si charges and discharges Li, so that the battery capacity does not develop unless the Si phase exists. The Si phase may be crystalline or amorphous. However, since the expansion and contraction during charging and discharging are small and the battery performance is high, the amorphous phase or a phase close to this is desirable. When XRD measurement using CuKα rays is performed, It must be 40 nm or less in terms of the Si crystal particle diameter calculated from the half width of the peak derived from Si appearing in the vicinity of 2θ = 28.4 ± 0.3 °.

本発明の酸化珪素系負極材は、組成管理が行われていることを前提とする。組成管理が行われていなければ、ＳｉＯ2や金属Ｍｇ、ＭｇＳｉ合金の生成が避けられない。組成管理が行われているにもかかわらず、元素濃度分布の不均一に起因して不可避的に生じる物質の生成を阻止することにより、その不均一を安定的に解消して電池性能の向上を図るのが、本発明の酸化珪素系負極材である。 The silicon oxide negative electrode material of the present invention is premised on the composition management being performed. If the composition management has not been performed, SiO 2 and metals Mg, generation of MgSi alloy inevitable. Despite the composition management, by preventing the generation of substances inevitably caused by the nonuniform element concentration distribution, the nonuniformity is stably eliminated and the battery performance is improved. The aim is the silicon oxide negative electrode material of the present invention.

参考までにその組成管理について簡単に説明すれば、その組成をＳｉxＭｇyＯzで表して、３ｙ＞ｚ＞ｙ、且つ２ｘ＋ｙ＞ｚであることが必要である。その理由は以下のとおりである。 To briefly explain the composition management for reference, it is necessary that the composition is expressed by Si x Mg y O z and 3y>z> y and 2x + y> z. The reason is as follows.

本発明の酸化珪素系負極材においては、Ｓｉ相を珪酸Ｍｇ、若しくはＭｇ酸化物が取り囲むことにより、Ｓｉ相の膨張収縮を抑え、高い電池性能を得ることができる。ＳｉＯ2を含まないことにより、Ｓｉ挿入時の珪酸Ｌｉ生成が抑制され、初期効率が改善する。ＳｉＯ2を含む場合、Ｌｉと反応して際に珪酸Ｌｉを生じる不可逆反応が起こり、初期効率が低下する。３ｙ＜ｚの場合は、酸素に対してＭｇが不足し、ＳｉＯ2が含有される。ｚ＜ｙの場合は、酸素が不足することで活性な金属Ｍｇ、ＭｇＳｉ合金が生じ、電池作製時に取り扱いが困難となる。したがって、３ｙ＞ｚ＞ｙであることが必要となる。また、２ｘ＋ｙ＞ｚであるならば、反応が平衡どおりに進むことにより、酸素が全てＳｉ、Ｍｇの酸化物として存在するので、Ｓｉ相（酸化していないＳｉ）が含有される。 In the silicon oxide-based negative electrode material of the present invention, when the Si phase is surrounded by Mg silicate or Mg oxide, expansion and contraction of the Si phase can be suppressed, and high battery performance can be obtained. By not containing SiO 2 , the production of Li silicate at the time of Si insertion is suppressed, and the initial efficiency is improved. When SiO 2 is contained, an irreversible reaction occurs in which Li silicate reacts with Li, and the initial efficiency is lowered. In the case of 3y <z, Mg is insufficient with respect to oxygen and SiO 2 is contained. In the case of z <y, active metal Mg and MgSi alloy are generated due to lack of oxygen, and handling becomes difficult during battery production. Therefore, 3y>z> y is required. Further, if 2x + y> z, the reaction proceeds in accordance with the equilibrium, so that all the oxygen exists as oxides of Si and Mg, so that the Si phase (non-oxidized Si) is contained.

ＳｉＯ2を含有しないことは、ＣｕＫα線を用いたＸＲＤ測定において２２°付近のアモルファスＳｉＯ2ピーク、及び２６．６°付近の結晶ＳｉＯ2ピークの両方が存在しないことで確認できる。 Contains no SiO 2 can be confirmed by amorphous SiO 2 peak near 22 ° in the XRD measurement using a CuKα line, and both the crystalline SiO 2 peak near 26.6 ° absent.

すなわち、２２°付近のアモルファスＳｉＯ2ピークについては、１４°と３４°のＸＲＤ強度を直線で結んでその直線をベース強度とした際に、２２°での回折強度Ｐ１と、２２°でのベース強度Ｂ１との比が、Ｐ１／Ｂ１＜１．２５を満たす場合にアモルファスＳｉＯ2ピークがないと判断する。 That is, for the amorphous SiO 2 peak near 22 °, when the XRD intensities at 14 ° and 34 ° are connected by a straight line and the straight line is used as the base intensity, the diffraction intensity P1 at 22 ° and the base at 22 ° When the ratio to the intensity B1 satisfies P1 / B1 <1.25, it is determined that there is no amorphous SiO 2 peak.

２６．６°付近の結晶ＳｉＯ2ピークについては、２θ＝２６．１°における回折強度と、２θ＝２７．１°における回折強度とを直線で結んでその直線をベース強度とした際に、２θ＝２６．６±０．３°における最大強度Ｐ２と、最大強度角度におけるベース強度Ｂ２との比が、Ｐ２／Ｂ２＜１．１を満たす場合に結晶ＳｉＯ2ピークがないと判断する。 Regarding the crystalline SiO 2 peak near 26.6 °, when the diffraction intensity at 2θ = 26.1 ° and the diffraction intensity at 2θ = 27.1 ° are connected by a straight line and the line is used as the base intensity, 2θ When the ratio between the maximum intensity P2 at 26.6 ± 0.3 ° and the base intensity B2 at the maximum intensity angle satisfies P2 / B2 <1.1, it is determined that there is no crystalline SiO 2 peak.

金属Ｍｇ、ＭｇＳｉ合金を含有しないことも同様に確認できる。すなわち、金属Ｍｇ を含有しないことは、ＣｕＫα線を用いたＸＲＤ測定において３４．４°付近の金属Ｍｇピークが存在しないことで、ＭｇＳｉ合金を含有しないことは、ＣｕＫα線を用いたＸＲＤ測定において２４．２°付近のＭｇ2Ｓｉピークが存在しないことで、それぞれ確認できる。 It can be confirmed in the same manner that no metal Mg or MgSi alloy is contained. That is, the absence of metal Mg 2 means that there is no metal Mg peak around 34.4 ° in the XRD measurement using CuKα rays, and that no MgSi alloy is contained in the XRD measurement using CuKα rays. Each can be confirmed by the absence of the Mg 2 Si peak around 2 °.

３４．４°付近の金属Ｍｇピークについては、２θ＝３４．０°における回折強度と、２θ＝３４．８°における回折強度とを直線で結んでその直線をベース強度とした際に、２θ＝３４．４±０．１°における最大強度Ｐ３と、最大強度角度におけるベース強度Ｂ３との比が、Ｐ３／Ｂ３＜１．１を満たす場合に金属Ｍｇピークがないと判断する。   For the metal Mg peak near 34.4 °, when the diffraction intensity at 2θ = 34.0 ° and the diffraction intensity at 2θ = 34.8 ° are connected by a straight line and the line is used as the base intensity, 2θ = When the ratio of the maximum intensity P3 at 34.4 ± 0.1 ° and the base intensity B3 at the maximum intensity angle satisfies P3 / B3 <1.1, it is determined that there is no metal Mg peak.

２４．２°付近のＭｇ2Ｓｉピークについては、２θ＝２３．５°における回折強度と、２θ＝２４．９°における回折強度とを直線で結んでその直線をベース強度とした際に、２θ＝２４．２±０．１°における最大強度Ｐ４と、最大強度角度におけるベース強度Ｂ４との比が、Ｐ４／Ｂ４＜１．１を満たす場合にＭｇＳｉ合金ピークがないと判断する。 For the Mg 2 Si peak near 24.2 °, when the diffraction intensity at 2θ = 23.5 ° and the diffraction intensity at 2θ = 24.9 ° are connected by a straight line and the line is used as the base intensity, 2θ When the ratio of the maximum intensity P4 at = 24.2 ± 0.1 ° and the base intensity B4 at the maximum intensity angle satisfies P4 / B4 <1.1, it is determined that there is no MgSi alloy peak.

一方、Ｍｇ含有化合物としてＭｇＳｉＯ3、Ｍｇ2ＳｉＯ4、ＭｇＯ、ＭｇＳｉＯ3＋Ｍｇ2ＳｉＯ4又はＭｇ2ＳｉＯ4＋ＭｇＯの５種のうちの何れか１種を含むことも、同様にＭｇＯ、Ｍｇ2ＳｉＯ4、ＭｇＳｉＯ3の３種類についてのＸＲＤピークの有無から確認できる。 On the other hand, MgSiO 3, Mg 2 SiO 4 , MgO as Mg-containing compound, also comprise MgSiO 3 + Mg 2 SiO 4 or Mg 2 SiO 4 + any one of five MgO, similarly MgO, Mg 2 SiO 4 It can be confirmed from the presence or absence of XRD peaks for three types of MgSiO 3 .

すなわち、ＭｇＯについては、２θ＝４１．８°における回折強度と、２θ＝４３．８°における回折強度とを直線で結んでその直線をベース強度とした際に、２θ＝４２．８±０．３°における最大強度Ｐ５と、最大強度角度におけるベース強度Ｂ５との比が、Ｐ５／Ｂ５＞１．１を満たす場合にＭｇＯが存在すると判断する。   That is, for MgO, when the diffraction intensity at 2θ = 41.8 ° and the diffraction intensity at 2θ = 43.8 ° are connected by a straight line and the straight line is used as the base intensity, 2θ = 42.8 ± 0. It is determined that MgO is present when the ratio of the maximum intensity P5 at 3 ° and the base intensity B5 at the maximum intensity angle satisfies P5 / B5> 1.1.

Ｍｇ2ＳｉＯ4については、２θ＝３１．３°における回折強度と、２θ＝３３．３°における回折強度とを直線で結んでその直線をベース強度とした際に、２θ＝３２．３±０．３°における最大強度Ｐ６と、最大強度角度におけるベース強度Ｂ６との比が、Ｐ６／Ｂ６＞１．１を満たす場合にＭｇ2ＳｉＯ4が存在すると判断する。 For Mg 2 SiO 4 , 2θ = 32.3 ± 0 when the diffraction intensity at 2θ = 31.3 ° and the diffraction intensity at 2θ = 33.3 ° are connected by a straight line and the straight line is used as the base intensity. It is determined that Mg 2 SiO 4 is present when the ratio of the maximum intensity P6 at 3 ° and the base intensity B6 at the maximum intensity angle satisfies P6 / B6> 1.1.

ＭｇＳｉＯ3については、２θ＝３１．８°における回折強度と、２θ＝３３．８°における回折強度とを直線で結んでその直線をベース強度とした際に、２θ＝３２．８±０．２°における最大強度Ｐ７と、最大強度角度におけるベース強度Ｂ７との比が、Ｐ７／Ｂ７＞１．１を満たす場合にＭｇＳｉＯ3が存在すると判断する。 For MgSiO 3 , 2θ = 32.8 ± 0.2 when the diffraction intensity at 2θ = 31.8 ° and the diffraction intensity at 2θ = 33.8 ° are connected by a straight line and the straight line is used as the base intensity. It is determined that MgSiO 3 is present when the ratio between the maximum intensity P7 at ° and the base intensity B7 at the maximum intensity angle satisfies P7 / B7> 1.1.

また、Ｓｉ相が存在することは、結晶ＳｉについてはＸＲＤピークの有無から確認できる。すなわち、２θ＝４６．４°における回折強度と、２θ＝４８．４°における回折強度とを直線で結んでその直線をベース強度とした際に、２θ＝４７．４±０．３°における最大強度Ｐ８と、最大強度角度におけるベース強度Ｂ８との比が、Ｐ８／Ｂ８＞１．１を満たす場合に、結晶Ｓｉが存在すると判断する。また、アモルファスＳｉについては元素分析結果から確認できる。   The presence of the Si phase can be confirmed from the presence or absence of the XRD peak for crystalline Si. That is, when the diffraction intensity at 2θ = 46.4 ° and the diffraction intensity at 2θ = 48.4 ° are connected by a straight line and the straight line is used as the base intensity, the maximum at 2θ = 47.4 ± 0.3 ° When the ratio between the intensity P8 and the base intensity B8 at the maximum intensity angle satisfies P8 / B8> 1.1, it is determined that crystalline Si exists. Moreover, about amorphous Si, it can confirm from an elemental analysis result.

本発明の酸化珪素系負極材の製造方法においては、ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させることにより、ＳｉＯとＭｇが均一に反応し、その結果、元素濃度分布が均一な酸化珪素系負極材の製造が可能となる。   In the method for producing a silicon oxide-based negative electrode material of the present invention, SiO gas and Mg gas are simultaneously generated in the same container, so that SiO and Mg react uniformly, and as a result, the element concentration distribution is oxidized uniformly. A silicon-based negative electrode material can be manufactured.

従来は気相法においてもＳｉＯガスとＭｇガスを別々の容器で発生させ、それらのガスを混合後に冷却、回収するため、ＳｉＯとＭｇが不均一に反応し、その結果、製造される酸化珪素系負極材の元素濃度分布が不均一になっていたが、本発明の酸化珪素系負極材の製造方法においては、ＳｉＯガスとＭｇガスを同一容器内で同時に発生させることにより、ＳｉＯとＭｇが均一に反応し、その結果、元素濃度分布が均一な酸化珪素系負極材の製造が可能となるのである。   Conventionally, even in the vapor phase method, SiO gas and Mg gas are generated in separate containers, and these gases are mixed and then cooled and recovered, so that SiO and Mg react non-uniformly, resulting in silicon oxide produced. The element concentration distribution of the negative electrode material was non-uniform. However, in the method for producing a silicon oxide negative electrode material of the present invention, SiO gas and Mg gas were simultaneously generated in the same container, so that SiO and Mg were It reacts uniformly, and as a result, it becomes possible to produce a silicon oxide negative electrode material having a uniform element concentration distribution.

ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させる方法としては、Ｓｉ、Ｍｇ及びＯを含有する原料を同一の容器内で減圧加熱する方法があり、Ｓｉ、Ｍｇ及びＯを含有する原料としては、Ｓｉ単体とＭｇ・Ｏ含有化合物とを含む原料が望ましく、Ｍｇ・Ｏ含有化合物としては、例えばＭｇＯ、Ｍｇ2ＳｉＯ4、ＭｇＳｉＯ３、Ｍｇ2ＣＯ3、Ｍｇ（ＯＨ）2等が望ましい。原料の酸素量調整のために、原料に更にＳｉ酸化物を含有させることも可能である。 As a method for simultaneously generating SiO gas and Mg gas in the same container, there is a method in which a raw material containing Si, Mg and O is heated under reduced pressure in the same container, and as a raw material containing Si, Mg and O, Is preferably a raw material containing a simple substance of Si and a Mg.O-containing compound. Examples of the Mg.O-containing compound include MgO, Mg 2 SiO 4 , MgSiO 3 , Mg 2 CO 3 , and Mg (OH) 2 . In order to adjust the amount of oxygen in the raw material, it is possible to further contain Si oxide in the raw material.

本発明の酸化珪素系負極材は、Ｓｉ−Ｍｇ−Ｏの３元系材料からなり、その上でＳｉ相を含むと共に、Ｍｇ含有化合物としてＭｇＳｉＯ3、Ｍｇ2ＳｉＯ4、ＭｇＯ、ＭｇＳｉＯ3＋Ｍｇ2ＳｉＯ4又はＭｇ2ＳｉＯ4＋ＭｇＯの５種のうちの何れか１種を含む一方、ＳｉＯ2、金属Ｍｇ及びＭｇＳｉ合金の何れも含まないことにより、Ｍｇを含む各元素の濃度分布が均一となり、その元素濃度分布の不均一に起因する電池性能の低下を可及的に回避することができる。 The silicon oxide-based negative electrode material of the present invention is made of a ternary material of Si—Mg—O, contains a Si phase thereon, and includes MgSiO 3 , Mg 2 SiO 4 , MgO, MgSiO 3 + Mg 2 as Mg-containing compounds. While containing any one of five types of SiO 4 or Mg 2 SiO 4 + MgO, and not containing any of SiO 2 , metal Mg and MgSi alloy, the concentration distribution of each element including Mg becomes uniform, It is possible to avoid as much as possible a decrease in battery performance due to the nonuniform element concentration distribution.

また、本発明の酸化珪素系負極材の製造方法は、ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させ、それらのガスを蒸着面上で冷却して回収することにより、ＳｉＯとＭｇを均一に反応させて、元素濃度分布が均一な酸化珪素系負極材の製造を可能とする。   Also, the method for producing a silicon oxide negative electrode material of the present invention generates SiO gas and Mg gas at the same time in the same container, and cools and collects these gases on the vapor deposition surface to recover SiO and Mg. By reacting uniformly, it is possible to produce a silicon oxide negative electrode material having a uniform element concentration distribution.

本発明の酸化珪素系負極材のＸＲＤチャートである。3 is an XRD chart of the silicon oxide negative electrode material of the present invention. 従来の酸化珪素系負極材のＸＲＤチャートである。It is an XRD chart of the conventional silicon oxide type negative electrode material.

以下に本発明の実施形態を説明する。本発明の酸化珪素系負極材は次のような方法により製造可能である。   Embodiments of the present invention will be described below. The silicon oxide negative electrode material of the present invention can be manufactured by the following method.

本発明の酸化珪素系負極材は、ＳｉＯガスとＭｇガスを均一に反応させることで製造することができる。そして、ＳｉＯガスとＭｇガスを均一に反応させるためには、両ガスを同時に発生させることが重要であり、具体的には、ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させ、それらのガスを同じ蒸着面上で冷却、回収する方法により製造可能である。   The silicon oxide negative electrode material of the present invention can be produced by uniformly reacting SiO gas and Mg gas. In order to uniformly react SiO gas and Mg gas, it is important to generate both gases at the same time. Specifically, SiO gas and Mg gas are simultaneously generated in the same container, It can be produced by a method of cooling and collecting the gas on the same vapor deposition surface.

ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させる方法としては、Ｓｉ、Ｍｇ及びＯを含有する原料を同一容器内で減圧加熱する方法がある。Ｓｉ、Ｍｇ及びＯを含有する原料としては、ＳｉＯガス発生原料とＭｇガス発生原料とを単純に混合したものが考えられるが、この原料だと、ＳｉＯガスとＭｇガスが同時に発生することはない。蒸気厚が高いＭｇガスのみが優先して発生する。このためにＳｉＯとＭｇが均一に混合した材料は得られない。別の原料として、ＭｇＯ、Ｍｇ2ＳｉＯ4などのＭｇ・Ｏ含有化合物、すなわち、Ｏを含有するＭｇ化合物が考えられるが、このような化合物は単体では減圧下での加熱によってもガスを発生しない。しかしながら、このようなＭｇ・Ｏ含有化合物であっても、Ｓｉ、特にＳｉ単体が共存すると、減圧下での加熱によりＳｉＯガスとＭｇガスとが同時に発生し、ＳｉＯとＭｇが均一に混合した材料が得られる。 As a method for simultaneously generating SiO gas and Mg gas in the same container, there is a method in which a raw material containing Si, Mg and O is heated under reduced pressure in the same container. As a raw material containing Si, Mg and O, a simple mixture of a SiO gas generating raw material and a Mg gas generating raw material can be considered, but with this raw material, SiO gas and Mg gas are not generated simultaneously. . Only Mg gas with a high vapor thickness is preferentially generated. For this reason, a material in which SiO and Mg are uniformly mixed cannot be obtained. As another raw material, Mg.O-containing compounds such as MgO and Mg 2 SiO 4 , that is, Mg compounds containing O, can be considered, but such compounds alone do not generate gas even when heated under reduced pressure. . However, even with such Mg · O-containing compounds, when Si, particularly Si alone, coexists, SiO gas and Mg gas are simultaneously generated by heating under reduced pressure, and SiO and Mg are uniformly mixed. Is obtained.

この観点から、Ｓｉ、Ｍｇ及びＯを含有する原料としては、Ｓｉ単体とＭｇ・Ｏ含有化合物とを含む原料が望ましい。この原料は取り扱いが簡単で価格も安い。例えば、Ｓｉ単体と、Ｍｇ・Ｏ含有化合物としてのＭｇＯとを混合するならば、化学式２の反応によりＳｉＯガスとＭｇガスを同時に発生させることができる。ここでは、ＳｉＯガスとＭｇガスを使用しているために、Ｏ／Ｓｉ比は１に近い値をとり、０．８＜Ｏ／Ｓｉ＜１．２程度となる。   From this viewpoint, the raw material containing Si, Mg and O is preferably a raw material containing Si alone and an Mg · O-containing compound. This material is easy to handle and cheap. For example, if Si is mixed with MgO as the Mg · O-containing compound, SiO gas and Mg gas can be generated simultaneously by the reaction of Chemical Formula 2. Here, since SiO gas and Mg gas are used, the O / Si ratio takes a value close to 1, which is about 0.8 <O / Si <1.2.

（化学式２）
Ｓｉ（ｓ）＋ＭｇＯ（ｓ）→ＳｉＯ（ｇ）＋Ｍｇ（ｇ） (Chemical formula 2)
Si (s) + MgO (s) → SiO (g) + Mg (g)

Ｍｇ単体を原料に使用することも考えられ、例えば固体ＳｉＯと単体Ｍｇを原料に用いることが可能であるが、この場合は化学式２の反応を介さずに単体Ｍｇから直接Ｍｇガスが発生する上、そのＭｇガスはＳｉＯガスと比べ低温で発生するために、反応初期にＭｇガス、反応後期にＳｉＯガスが生成し、作製された材料の組成が不均一になってしまう。このため、単体Ｍｇを用いることは現実的でない。ＳｉＯガスが発生するまでにＭｇガスを発生せず、気化しないＭｇ・Ｏ含有化合物をＳｉ単体で還元することで、ＳｉＯガスとＭｇガスを同時に発生させることができるのである。   It is also conceivable to use Mg alone as a raw material. For example, solid SiO and simple Mg can be used as a raw material, but in this case, Mg gas is directly generated from the single Mg without the reaction of Chemical Formula 2. Since the Mg gas is generated at a lower temperature than the SiO gas, the Mg gas is generated in the early stage of the reaction and the SiO gas is generated in the late stage of the reaction, so that the composition of the produced material becomes non-uniform. For this reason, it is not realistic to use simple Mg. By reducing the Mg.O-containing compound that does not generate Mg gas and does not vaporize until SiO gas is generated with Si alone, SiO gas and Mg gas can be generated simultaneously.

Ｍｇ・Ｏ含有化合物としては、不要な金属元素の混入を防ぐために、例えばＭｇＯ、Ｍｇ2ＳｉＯ4、ＭｇＳｉＯ3、ＭｇＣＯ３、Ｍｇ（ＯＨ）2等が望ましい。特に、ＭｇＯ、Ｍｇ2ＳｉＯ4、ＭｇＳｉＯ３を使用することで、Ｓｉ、Ｏ、Ｍｇ以外の元素の混入を防ぐことができる。ＭｇＣＯ3、Ｍｇ（ＯＨ）2等は加熱によりＣＯ2等のガスを発生させるが、ＳｉＯガス発生反応温度よりも低い温度でガスの発生反応を完了させることで、ＭｇＯ等と同様に使用することができる。これらの化合物を用いた場合の反応は化学式３のように表される。原料の酸素量調整のために、原料に更にＳｉ酸化物を含有させてもよい。 As the Mg · O-containing compound, for example, MgO, Mg 2 SiO 4 , MgSiO 3 , MgCO 3 , Mg (OH) 2 or the like is desirable in order to prevent mixing of unnecessary metal elements. In particular, by using MgO, Mg 2 SiO 4 , or MgSiO 3 , it is possible to prevent contamination of elements other than Si, O, and Mg. MgCO 3 , Mg (OH) 2, etc. generate gas such as CO 2 by heating, but can be used in the same way as MgO etc. by completing the gas generation reaction at a temperature lower than the SiO gas generation reaction temperature. Can do. The reaction when these compounds are used is represented by Chemical Formula 3. In order to adjust the amount of oxygen in the raw material, the raw material may further contain Si oxide.

（化学式３）
３Ｓｉ(ｓ)＋Ｍｇ2ＳｉＯ4(ｓ)→４ＳｉＯ(ｇ)＋２Ｍｇ(ｇ)
２Ｓｉ(ｓ)＋ＭｇＳｉＯ３(ｓ）→３ＳｉＯ(ｇ)＋Ｍｇ(ｇ)
Ｓｉ(ｓ)＋ＭｇＣＯ３(ｓ)→ＳｉＯ(ｇ)＋Ｍｇ(ｇ)＋ＣＯ2(ｇ)
Ｓｉ(ｓ)＋Ｍｇ(ＯＨ)2(ｓ)→ＳｉＯ(ｇ)＋Ｍｇ(ｇ)＋Ｈ2Ｏ(ｇ) (Chemical formula 3)
3Si (s) + Mg 2 SiO 4 (s) → 4SiO (g) + 2Mg (g)
2Si (s) + MgSiO 3 (s) → 3SiO (g) + Mg (g)
Si (s) + MgCO 3 (s) → SiO (g) + Mg (g) + CO 2 (g)
Si (s) + Mg (OH) 2 (s) → SiO (g) + Mg (g) + H 2 O (g)

Ｓｉ、Ｍｇ及びＯの混合比は、１．０＜Ｓｉ／Ｏ＜１．５及び０．３３＜Ｍｇ／Ｏ＜１．０を満足することが望ましい。Ｓｉ量とＯ量が異なる場合、未反応で残留する原料が増えるために反応効率が低下する。特にＯが多い場合には、ＳｉＯガスが優先して生成し、Ｍｇ原料が残留してＭｇ量が低下するおそれがある。Ｍｇについては、少なすぎると生成物中にＳｉＯ２が含まれ、多すぎる場合には活性な金属Ｍｇの生成や原料残留のおそれが生じる。 The mixing ratio of Si, Mg and O desirably satisfies 1.0 <Si / O <1.5 and 0.33 <Mg / O <1.0. When the amount of Si and the amount of O are different, the raw material remaining unreacted increases, so the reaction efficiency decreases. In particular, when there is a large amount of O, SiO gas is preferentially generated, and there is a possibility that the Mg raw material remains and the amount of Mg decreases. As for Mg, if the amount is too small, SiO 2 is contained in the product, and if it is too much, active metal Mg may be generated or a raw material may remain.

蒸着面上での冷却、回収により作製された材料については、回収後、所定の粒度に粉砕、調整することで、電極用粉末材料とすることができる。粉砕方法は特定されないが、金属不純物が混入しないように粉末接触部にはセラミックス等の非金属材料を用いるのが望ましい。粉末粒子径はメディアン径Ｄ50で１〜２０μｍが望ましい。粉末粒子径がこの範囲内であると、粉末の分散性がよく、スラリー化の工程等で取り扱いが容易となり、結果的に電池性能が向上する。 About the material produced by cooling and collection | recovery on a vapor deposition surface, it can be set as the powder material for electrodes by grind | pulverizing and adjusting to a predetermined particle size after collection | recovery. Although the pulverization method is not specified, it is desirable to use a non-metallic material such as ceramics for the powder contact portion so that metal impurities are not mixed. The powder particle diameter is preferably 1 to 20 μm in median diameter D 50 . When the particle size of the powder is within this range, the dispersibility of the powder is good and the handling becomes easy in the slurrying process, resulting in improved battery performance.

ここにおける電極用粉末材料は、粉末粒子の表面もしくはその表面の一部に導電性材料が被覆されてもよい。導電性材料の被覆により、表面抵抗が下がり、電池性能が向上する。導電性材料としては、グラファイトが代表的であり、例えば炭化水素ガスを用いた熱ＣＶＤ反応により、粒子表面へグラファイトを被覆することができる。   In the electrode powder material here, the surface of the powder particles or a part of the surface may be coated with a conductive material. By covering the conductive material, the surface resistance is lowered and the battery performance is improved. A typical example of the conductive material is graphite. For example, graphite can be coated on the particle surface by a thermal CVD reaction using a hydrocarbon gas.

ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させ、それらのガスを同じ蒸着面上で冷却して回収する方法は、Ｍｇがドープされた酸化珪素系負極材の製造方法であるが、Ｍｇを他の金属元素に変えることにより、Ｍｇ以外の金属元素がドープされた酸化珪素系負極材の製造も可能である。   A method of simultaneously generating SiO gas and Mg gas in the same container and cooling and recovering these gases on the same vapor deposition surface is a method for producing a silicon oxide negative electrode material doped with Mg. It is also possible to manufacture a silicon oxide negative electrode material doped with a metal element other than Mg by changing to other metal elements.

すなわち、Ｓｉ単体と、酸素を含有する金属化合物とを含む原料を同一の容器内で同時に減圧加圧して、ＳｉＯガスと金属ガスとを同時に発生させ、それらのガスを同じ蒸着面上で冷却して回収することにより、Ｍｇ以外の金属元素がドープされた酸化珪素系負極材が製造される。   That is, a raw material containing a simple substance of Si and a metal compound containing oxygen is simultaneously decompressed and pressurized in the same container to simultaneously generate SiO gas and metal gas, and these gases are cooled on the same deposition surface. Thus, a silicon oxide negative electrode material doped with a metal element other than Mg is produced.

ここにおけるＭｇ以外の金属元素としては、ＳｉＯ以上の蒸気圧を有し、かつＳｉＯ2 を還元可能な元素が望ましく、例えばＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｃａ、Ｓｒ、Ｂａ、Ａｌなどを挙げることができる。原料に金属元素単体を用いると、生成する材料の組成が不均一となるおそれがあるため、金属元素の酸化物や水酸化物、炭酸塩、珪酸塩などの化合物を用いることが望ましい。化合物としては、ＳｉＯガス発生反応が進行するまで金属元素ガスを発生せず、気化しない材料が望ましい。ガス発生反応は化学式４のように表される。Ｓｉ、Ｏ比を調整するために原料に更にＳｉ酸化物を含有させてもよい。 The metal element other than Mg here is preferably an element having a vapor pressure higher than that of SiO and capable of reducing SiO 2 , such as Li, Na, K, Rb, Cs, Ca, Sr, Ba, Al, and the like. Can be mentioned. When a single metal element is used as a raw material, the composition of the material to be produced may be non-uniform, so it is desirable to use a compound such as an oxide, hydroxide, carbonate, or silicate of the metal element. As the compound, a material that does not generate metal element gas and does not vaporize until the SiO gas generation reaction proceeds is desirable. The gas generation reaction is expressed as in Chemical Formula 4. In order to adjust the Si and O ratio, the raw material may further contain Si oxide.

（化学式４）
ｘＳｉ(ｓ)＋ＭＯx(ｓ)→ｘＳｉＯ(ｇ)＋Ｍ(ｇ)
２ｘＳｉ(ｓ)＋Ｍ(ＳｉＯ3)x(ｓ)→３ｘＳｉＯ(ｇ)＋Ｍ(ｇ)
ｘＳｉ(ｓ)＋Ｍ(ＣＯ3)x(ｓ)→ｘＳｉＯ(ｇ)＋Ｍ(ｇ)＋ｘＣＯ2(ｇ)
ｘＳｉ(ｓ)＋Ｍ(ＯＨ)x(ｓ)→ｘＳｉＯ(ｇ)＋Ｍ(ｇ)＋ｘＨ2Ｏ(ｇ) (Chemical formula 4)
xSi (s) + MO x (s) → xSiO (g) + M (g)
2 × Si (s) + M (SiO 3 ) × (s) → 3 × SiO (g) + M (g)
xSi (s) + M (CO 3 ) x (s) → xSiO (g) + M (g) + xCO 2 (g)
xSi (s) + M (OH) x (s) → xSiO (g) + M (g) + xH 2 O (g)

（実施例１）
Ｓｉ粉末とＭｇＯ粉末とＭｇ2ＳｉＯ4粉末とを４：１：１のモル比で混合した（Ｓｉ：Ｍｇ：Ｏ＝１：０．６：１）。この混合粉末をＡｒ雰囲気、１Ｐａで１３５０℃に加熱し、発生したガスを上部に設置した蒸着板上で４００℃に冷却し析出させて回収した。回収した析出材料をアルミナボールミルで粉砕し、平均粒子径をメディアン径Ｄ５０で５μｍに調整した。 Example 1
Si powder, MgO powder, and Mg 2 SiO 4 powder were mixed at a molar ratio of 4: 1: 1 (Si: Mg: O = 1: 0.6: 1). The mixed powder was heated to 1350 ° C. in an Ar atmosphere and 1 Pa, and the generated gas was cooled to 400 ° C. on a vapor deposition plate installed on the upper side, and was collected. The collected precipitated material was pulverized with an alumina ball mill, and the average particle diameter was adjusted to 5 μm with a median diameter D50.

こうして得た粉末に対してＣｕＫα線を用いたＸＲＤ測定を行った。ＸＲＤデータを図１に示す。Ｓｉ、ＭｇＯ、Ｍｇ2ＳｉＯ4の各結晶ピークが確認できた一方で、ＭｇＳｉＯ3の結晶ピーク、ＳｉＯ2のアモルファスピーク及び結晶ピーク、並びに金属Ｍｇ及びＭｇＳｉ合金の結晶ピークは確認できなかった。 XRD measurement using CuKα rays was performed on the powder thus obtained. XRD data is shown in FIG. While each crystal peak of Si, MgO, and Mg 2 SiO 4 could be confirmed, the crystal peak of MgSiO 3 , the amorphous peak and crystal peak of SiO 2 , and the crystal peak of metal Mg and MgSi alloy could not be confirmed.

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．１８(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝０．９１（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝０．９９（＜１．１）、ＭｇＳｉ合金の結晶ピークはＰ４／Ｂ４＝１．０４（＜１．１）であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝１．３７（＞１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝１．６７（＞１．１）であり、他方、ＭｇＳｉＯ３の結晶ピーク強度はＰ７／Ｂ７＝１．０５（＜１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.18 (<1.25), and the crystal peak intensity was P2 / B2 = 0.91 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 0.99 (<1.1), and the crystal peak of MgSi alloy was P4 / B4 = 1.04 (<1.1). On the other hand, the crystal peak intensity of MgO is P5 / B5 = 1.37 (> 1.1), and the crystal peak intensity of Mg 2 SiO 4 is P6 / B6 = 1.67 (> 1.1), while MgSiO 3 The crystal peak intensity was P7 / B7 = 1.05 (<1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝２．３１であり、結晶粒子径は１２．２μｍであった。   Further, the crystal peak intensity of Si was P8 / B8 = 2.31, and the crystal particle diameter was 12.2 μm.

（実施例２）
Ｓｉ粉末とＭｇＯ粉末とＳｉＯ2粉末とを１９：１８：１のモル比で混合した（Ｓｉ：Ｍｇ：Ｏ＝１：０．９：１）。この混合粉末を実施例１と同じ条件で加熱、析出させ、粉末化した。得られた粉末に対して実施例１と同じＸＲＤ測定を行ったところ、Ｓｉ、ＭｇＯ、Ｍｇ2ＳｉＯ4の各結晶ピークが確認できた一方で、ＭｇＳｉＯ３の結晶ピーク、ＳｉＯ2のアモルファスピーク及び結晶ピーク、並びに金属Ｍｇ及びＭｇＳｉ合金の結晶ピークは確認できなかった。 (Example 2)
Si powder, MgO powder and SiO 2 powder were mixed at a molar ratio of 19: 18: 1 (Si: Mg: O = 1: 0.9: 1). This mixed powder was heated and precipitated under the same conditions as in Example 1 to form a powder. When the same XRD measurement as in Example 1 was performed on the obtained powder, Si, MgO, Mg 2 SiO 4 crystal peaks were confirmed, while MgSiO 3 crystal peak, SiO 2 amorphous peak, and A crystal peak and a crystal peak of metallic Mg and MgSi alloy could not be confirmed.

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．１９(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝１．０２（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝１．０２（＜１．１）、ＭｇＳｉ合金の結晶ピークはＰ４／Ｂ４＝１．０３（＜１．１）であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝２２（＞１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝１．７２（＞１．１）であり、他方、ＭｇＳｉＯ３の結晶ピーク強度はＰ７／Ｂ７＝１．０２（＜１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.19 (<1.25), and the crystal peak intensity was P2 / B2 = 1.02 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 1.02 (<1.1), and the crystal peak of MgSi alloy was P4 / B4 = 1.03 (<1.1). On the other hand, the crystal peak intensity of MgO is P5 / B5 = 22 (> 1.1 ), the crystalline peak intensity of Mg 2 SiO 4 is P6 / B6 = 1.72 (> 1.1 ), while the MgSiO 3 The crystal peak intensity was P7 / B7 = 1.02 (<1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝１４．８であり、結晶粒子径は３２．８μｍであった。   Further, the crystal peak intensity of Si was P8 / B8 = 14.8, and the crystal particle diameter was 32.8 μm.

（実施例３）
Ｓｉ粉末とＭｇＯ粉末とＳｉＯ2粉末とを７：４：３のモル比で混合した（Ｓｉ：Ｍｇ：Ｏ＝１：０．４：１）。この混合粉末を実施例１と同じ条件で加熱、析出させ、粉末化した。得られた粉末に対して実施例１と同じＸＲＤ測定を行ったところ、Ｓｉ、ＭｇＳｉＯ3、Ｍｇ2ＳｉＯ4の各結晶ピークが確認できた一方で、ＭｇＯの結晶ピーク、ＳｉＯ2のアモルファスピーク及び結晶ピーク、並びに金属Ｍｇ及びＭｇＳｉ合金の結晶ピークは確認できなかった。 (Example 3)
Si powder, MgO powder and SiO 2 powder were mixed at a molar ratio of 7: 4: 3 (Si: Mg: O = 1: 0.4: 1). This mixed powder was heated and precipitated under the same conditions as in Example 1 to form a powder. When the same XRD measurement as that of Example 1 was performed on the obtained powder, Si, MgSiO 3 , Mg 2 SiO 4 crystal peaks were confirmed, while MgO crystal peak, SiO 2 amorphous peak, and A crystal peak and a crystal peak of metallic Mg and MgSi alloy could not be confirmed.

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．１６(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝０．９４（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝０．９８（＜１．１）、ＭｇＳｉ合金の結晶ピークはＰ４／Ｂ４＝１．０１（＜１．１）であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝１．０４（＜１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝１．７０（＞１．１）であり、他方、ＭｇＳｉＯ3の結晶ピーク強度はＰ７／Ｂ７＝１．５３（＞１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.16 (<1.25), and the crystal peak intensity was P2 / B2 = 0.94 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 0.98 (<1.1), and the crystal peak of MgSi alloy was P4 / B4 = 1.01 (<1.1). On the other hand, the crystal peak intensity of MgO is P5 / B5 = 1.04 (<1.1), and the crystal peak intensity of Mg 2 SiO 4 is P6 / B6 = 1.70 (> 1.1), while MgSiO The crystal peak intensity of 3 was P7 / B7 = 1.53 (> 1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝１．９４であり、結晶粒子径は１０．３μｍであった。   The crystal peak intensity of Si was P8 / B8 = 1.94, and the crystal particle diameter was 10.3 μm.

（実施例４）
Ｓｉ粉末とＭｇＯ粉末とＳｉＯ2粉末とを２：１：１のモル比で混合した（Ｓｉ：Ｍｇ：Ｏ＝１：０．３３：１）。この混合粉末を実施例１と同じ条件で加熱、析出させ、粉末化した。得られた粉末に対して実施例１と同じＸＲＤ測定を行ったところ、Ｓｉ、ＭｇＳｉＯ3の各結晶ピークが確認できた一方で、ＭｇＯ、Ｍｇ2ＳｉＯ4の結晶ピーク、ＳｉＯ2のアモルファスピーク及び結晶ピーク、並びに金属Ｍｇ及びＭｇＳｉ合金の結晶ピークは確認できなかった。 Example 4
Si powder, MgO powder and SiO 2 powder were mixed at a molar ratio of 2: 1: 1 (Si: Mg: O = 1: 0.33: 1). This mixed powder was heated and precipitated under the same conditions as in Example 1 to form powder. When the same XRD measurement as in Example 1 was performed on the obtained powder, each crystal peak of Si and MgSiO 3 could be confirmed, while the crystal peak of MgO, Mg 2 SiO 4 , the amorphous peak of SiO 2 and A crystal peak and a crystal peak of metallic Mg and MgSi alloy could not be confirmed.

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．１５(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝０．９２（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝０．９９（＜１．１）、ＭｇＳｉ合金の結晶ピークはＰ／Ｂ＝１．０４（＜１．１）であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝１．０３（＜１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝１．００（＜１．１）であり、他方、ＭｇＳｉＯ3の結晶ピーク強度はＰ７／Ｂ７＝１．８５（＞１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.15 (<1.25), and the crystal peak intensity was P2 / B2 = 0.92 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 0.99 (<1.1), and the crystal peak of MgSi alloy was P / B = 1.04 (<1.1). On the other hand, the crystal peak intensity of MgO is P5 / B5 = 1.03 (<1.1), and the crystal peak intensity of Mg 2 SiO 4 is P6 / B6 = 1.00 (<1.1), while MgSiO The crystal peak intensity of No. 3 was P7 / B7 = 1.85 (> 1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝１．６９であり、結晶粒子径は８．５０μｍであった。   Further, the crystal peak intensity of Si was P8 / B8 = 1.69, and the crystal particle diameter was 8.50 μm.

（実施例５）
Ｓｉ粉末とＭｇＯ粉末とＳｉＯ2粉末とを３：２：１のモル比で混合した（Ｓｉ：Ｍｇ：Ｏ＝１：０．５：１）。この混合粉末を実施例１と同じ条件で加熱、析出させ、粉末化した。得られた粉末に対して実施例１と同じＸＲＤ測定を行ったところ、Ｓｉ、Ｍｇ2ＳｉＯ4の各結晶ピークが確認できた一方で、ＭｇＳｉＯ3、ＭｇＯの結晶ピーク、ＳｉＯ2のアモルファスピーク及び結晶ピーク、並びに金属Ｍｇ及びＭｇＳｉ合金の結晶ピークは確認できなかった (Example 5)
Si powder, MgO powder and SiO 2 powder were mixed at a molar ratio of 3: 2: 1 (Si: Mg: O = 1: 0.5: 1). This mixed powder was heated and precipitated under the same conditions as in Example 1 to form a powder. When the same XRD measurement as in Example 1 was performed on the obtained powder, each crystal peak of Si and Mg 2 SiO 4 could be confirmed, while the crystal peak of MgSiO 3 and MgO, the amorphous peak of SiO 2 and Crystal peak and metal Mg and MgSi alloy crystal peak could not be confirmed

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．１９(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝１．０１（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝０．９９（＜１．１）、ＭｇＳｉ合金の結晶ピークはＰ４／Ｂ４＝１．０２（＜１．１）であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝１．０５（＜１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝２．１４（＞１．１）であり、他方、ＭｇＳｉＯ3の結晶ピーク強度はＰ７／Ｂ７＝１．０３（＜１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.19 (<1.25), and the crystal peak intensity was P2 / B2 = 1.01 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 0.99 (<1.1), and the crystal peak of MgSi alloy was P4 / B4 = 1.02 (<1.1). On the other hand, the crystal peak intensity of MgO is P5 / B5 = 1.05 (<1.1), and the crystal peak intensity of Mg 2 SiO 4 is P6 / B6 = 2.14 (> 1.1), while MgSiO The crystal peak intensity of 3 was P7 / B7 = 1.03 (<1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝２．１２であり、結晶粒子径は１１．１μｍであった。   Further, the crystal peak intensity of Si was P8 / B8 = 2.12, and the crystal particle diameter was 11.1 μm.

（実施例６）
Ｓｉ粉末とＭｇＯ粉末とを１：１のモル比で混合した（Ｓｉ：Ｍｇ：Ｏ＝１：１：１）。この混合粉末を実施例１と同じ条件で加熱、析出させ、粉末化した。得られた粉末に対して実施例１と同じＸＲＤ測定を行ったところ、Ｓｉ、ＭｇＯの各結晶ピークが確認できた一方で、Ｍｇ2ＳｉＯ4、ＭｇＳｉＯ3の結晶ピーク、ＳｉＯ2のアモルファスピーク及び結晶ピーク、並びに金属Ｍｇ及びＭｇＳｉ合金の結晶ピークは確認できなかった。 (Example 6)
Si powder and MgO powder were mixed at a molar ratio of 1: 1 (Si: Mg: O = 1: 1: 1). This mixed powder was heated and precipitated under the same conditions as in Example 1 to form a powder. When the same XRD measurement as in Example 1 was performed on the obtained powder, each of Si and MgO crystal peaks could be confirmed, while Mg 2 SiO 4 , MgSiO 3 crystal peaks, SiO 2 amorphous peaks and A crystal peak and a crystal peak of metallic Mg and MgSi alloy could not be confirmed.

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．１５(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝１．０５（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝１．０１（＜１．１）、ＭｇＳｉ合金の結晶ピークはＰ４／Ｂ４＝１．０１（＜１．１）であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝２８．６（＞１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝１．０７（＜１．１）であり、他方、ＭｇＳｉＯ3の結晶ピーク強度はＰ７／Ｂ７＝１．０１（＜１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.15 (<1.25), and the crystal peak intensity was P2 / B2 = 1.05 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 1.01 (<1.1), and the crystal peak of MgSi alloy was P4 / B4 = 1.01 (<1.1). On the other hand, the crystal peak intensity of MgO is P5 / B5 = 28.6 (> 1.1), and the crystal peak intensity of Mg 2 SiO 4 is P6 / B6 = 1.07 (<1.1), while MgSiO The crystal peak intensity of 3 was P7 / B7 = 1.01 (<1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝１７．５であり、結晶粒子径は３８．１μｍであった。   Further, the crystal peak intensity of Si was P8 / B8 = 17.5, and the crystal particle diameter was 38.1 μm.

（実施例７）
Ｓｉ粉末とＭｇＳｉＯ３粉末とを２：１のモル比で混合した（Ｓｉ：Ｍｇ：Ｏ＝１：０．３３：１）。この混合粉末を実施例１と同じ条件で加熱、析出させ、粉末化した。得られた粉末に対して実施例１と同じＸＲＤ測定を行ったところ、Ｓｉ、ＭｇＳｉＯ3の各結晶ピークが確認できた一方で、ＭｇＯ、Ｍｇ2ＳｉＯ4の結晶ピーク、ＳｉＯ2のアモルファスピーク及び結晶ピーク、並びに金属Ｍｇ及びＭｇＳｉ合金の結晶ピークは確認できなかった。 (Example 7)
Si powder and MgSiO 3 powder were mixed at a molar ratio of 2: 1 (Si: Mg: O = 1: 0.33: 1). This mixed powder was heated and precipitated under the same conditions as in Example 1 to form a powder. When the same XRD measurement as in Example 1 was performed on the obtained powder, each crystal peak of Si and MgSiO 3 could be confirmed, while the crystal peak of MgO, Mg 2 SiO 4 , the amorphous peak of SiO 2 and A crystal peak and a crystal peak of metallic Mg and MgSi alloy could not be confirmed.

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．１４(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝０．９５（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝１．０１（＜１．１）、ＭｇＳｉ合金の結晶ピークはＰ／Ｂ＝１．０２（＜１．１）であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝０．９９（＜１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝１．０４（＜１．１）であり、他方、ＭｇＳｉＯ3の結晶ピーク強度はＰ７／Ｂ７＝１．９３（＞１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.14 (<1.25), and the crystal peak intensity was P2 / B2 = 0.95 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 1.01 (<1.1), and the crystal peak of MgSi alloy was P / B = 1.02 (<1.1). On the other hand, the crystal peak intensity of MgO is P5 / B5 = 0.99 (<1.1), and the crystal peak intensity of Mg 2 SiO 4 is P6 / B6 = 1.04 (<1.1), while MgSiO The crystal peak intensity of No. 3 was P7 / B7 = 1.93 (> 1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝１．４７であり、結晶粒子径は７．９３μｍであった。   The crystal peak intensity of Si was P8 / B8 = 1.47, and the crystal particle diameter was 7.93 μm.

（比較例１）
Ｓｉ粉末とＳｉＯ2粉末を１：１のモル比で混合した(Ｓｉ：Ｍｇ：Ｏ＝１：０：１)。この混合粉末を実施例１と同じ条件で加熱、析出させ、粉末化した。得られた粉末に対して実施例１と同じＸＲＤ測定を行ったところ、Ｓｉの結晶ピークは確認できなかった。しかし、ＳｉＯ2のアモルファスピークは確認され、Ｐ１／Ｂ１＝１．２８（＞１．２５）であった上、２ｘ＋ｙ＞ｚが満足されているので、得られた酸化珪素粉末はＳｉとＳｉＯ2の混合物でアモルファス状態と見ることができる。 (Comparative Example 1)
Si powder and SiO 2 powder were mixed at a molar ratio of 1: 1 (Si: Mg: O = 1: 0: 1). This mixed powder was heated and precipitated under the same conditions as in Example 1 to form a powder. When the same XRD measurement as Example 1 was performed with respect to the obtained powder, the crystal peak of Si was not able to be confirmed. However, an amorphous peak of SiO 2 was confirmed, P1 / B1 = 1.28 (> 1.25), and 2x + y> z was satisfied, so that the obtained silicon oxide powder was composed of Si and SiO 2. It can be seen as an amorphous state with a mixture of

（比較例２）
Ｓｉ粉末とＭｇ粉末を１：０．６のモル比で混合した（Ｓｉ：Ｍｇ：Ｏ＝１：０．６：１）。この混合粉末を実施例１と同じ条件で加熱、析出させ、粉末化した。得られた粉末に対して実施例１と同じＸＲＤ測定を行った。ＸＲＤデータを図２に示す。Ｓｉ、ＭｇＯ、Ｍｇ2ＳｉＯ4の各結晶ピーク、及びＳｉＯ2のアモルファスピークが確認できた。その一方で、金属Ｍｇ及びＭｇＳｉ合金の結晶ピーク、並びにＭｇＳｉＯ3の結晶ピークは確認できなかった。 (Comparative Example 2)
Si powder and Mg powder were mixed at a molar ratio of 1: 0.6 (Si: Mg: O = 1: 0.6: 1). This mixed powder was heated and precipitated under the same conditions as in Example 1 to form a powder. The same XRD measurement as in Example 1 was performed on the obtained powder. XRD data is shown in FIG. Each crystal peak of Si, MgO, Mg 2 SiO 4 and an amorphous peak of SiO 2 were confirmed. On the other hand, the crystal peak of metallic Mg and MgSi alloy and the crystal peak of MgSiO 3 could not be confirmed.

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．２８(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝０．９８（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝１．００、ＭｇＳｉ合金の結晶ピークはＰ４／Ｂ４＝１．０８であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝６．４２（＞１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝２．８２（＞１．１）であり、他方、ＭｇＳｉＯ３の結晶ピーク強度はＰ７／Ｂ７＝１．０７（＜１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.28 (<1.25), and the crystal peak intensity was P2 / B2 = 0.98 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 1.00, and the crystal peak of MgSi alloy was P4 / B4 = 1.08. On the other hand, the crystal peak intensity of MgO is P5 / B5 = 6.42 (> 1.1), and the crystal peak intensity of Mg 2 SiO 4 is P6 / B6 = 2.82 (> 1.1), while MgSiO The crystal peak intensity of No. 3 was P7 / B7 = 1.07 (<1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝９．０９であり、結晶粒子径は４１．６μｍであった。   Further, the crystal peak intensity of Si was P8 / B8 = 9.09, and the crystal particle diameter was 41.6 μm.

（比較例３）
容器を２つ用意し、一方の容器にＳｉ粉末とＳｉＯ2粉末を１：１のモル比で混合して仕込み（Ｓｉ：Ｍｇ：Ｏ＝１：０：１）、もう一方の容器に金属Ｍｇを上記Ｓｉに対して０．６の割合で仕込んだ。Ａｒ雰囲気、１Ｐａの条件下で、一方の容器は１３５０℃に加熱し、もう一方の容器は４５０℃に加熱し、２容器からガスを発生させた。これらのガスを上部に設置した蒸着板上で冷却した。他の条件は実施例１と同じとした。 (Comparative Example 3)
Two containers are prepared, and Si powder and SiO 2 powder are mixed and charged in a molar ratio of 1: 1 in one container (Si: Mg: O = 1: 0: 1), and metal Mg is charged in the other container. Was charged at a ratio of 0.6 to Si. Under conditions of Ar atmosphere and 1 Pa, one container was heated to 1350 ° C., the other container was heated to 450 ° C., and gas was generated from the two containers. These gases were cooled on the vapor deposition plate installed in the upper part. Other conditions were the same as in Example 1.

得られた粉末に対して実施例１と同じＸＲＤ測定を行ったところ、Ｓｉ、ＭｇＯ、Ｍｇ2ＳｉＯ4、ＭｇＳｉＯ3の各結晶ピーク、及びＳｉＯ2のアモルファスピークが確認できた。一方、金属Ｍｇ及びＭｇＳｉ合金の結晶ピークは確認できなかった。 When the obtained powder was subjected to the same XRD measurement as in Example 1, Si, MgO, Mg 2 SiO 4, the crystal peak of MgSiO 3, and amorphous peak of SiO 2 was confirmed. On the other hand, the crystal peak of metal Mg and MgSi alloy was not able to be confirmed.

すなわち、ＳｉＯ2のアモルファスピーク強度はＰ１／Ｂ１＝１．３１(＜１．２５)、結晶ピーク強度はＰ２／Ｂ２＝０．９９（＜１．１）であった。また、金属Ｍｇの結晶ピーク強度はＰ３／Ｂ３＝０．９６（＜１．１）、ＭｇＳｉ合金の結晶ピークはＰ４／Ｂ４＝１．０３（＜１．１）であった。一方、ＭｇＯの結晶ピーク強度はＰ５／Ｂ５＝２．６２（＞１．１）、Ｍｇ2ＳｉＯ4の結晶ピーク強度はＰ６／Ｂ６＝１．６６（＞１．１）、ＭｇＳｉＯ３の結晶ピーク強度はＰ７／Ｂ７＝１．２１（＜１．１）であった。 That is, the amorphous peak intensity of SiO 2 was P1 / B1 = 1.31 (<1.25), and the crystal peak intensity was P2 / B2 = 0.99 (<1.1). The crystal peak intensity of metal Mg was P3 / B3 = 0.96 (<1.1), and the crystal peak of MgSi alloy was P4 / B4 = 1.03 (<1.1). On the other hand, the crystal peak intensity of MgO is P5 / B5 = 2.62 (> 1.1), the crystal peak intensity of Mg 2 SiO 4 is P6 / B6 = 1.66 (> 1.1), and the crystal peak intensity of MgSiO 3 Was P7 / B7 = 1.21 (<1.1).

また、Ｓｉの結晶ピーク強度はＰ８／Ｂ８＝３．６７であり、結晶粒子径は１３．５μｍであった。   Further, the crystal peak intensity of Si was P8 / B8 = 3.67, and the crystal particle diameter was 13.5 μm.

（電池評価）
実施例１〜６及び比較例１〜３において製造された粉末試料に対して次の手順で電池評価を実施した。 (Battery evaluation)
Battery evaluation was performed on the powder samples produced in Examples 1 to 6 and Comparative Examples 1 to 3 by the following procedure.

粉末試料と非水系（有機系）バインダーであるＰＩバインダーと、導電助材であるＫＢとを８０：１５：５の重量比で混合し、有機系のＮＭＰを溶媒として混練してスラリーとした。作製したスラリーを銅箔上に塗工し、３５０℃で３０ｍｉｎ真空熱処理することで負極とした。この負極と対極（Ｌｉ箔）と電解液（ＥＣ：ＤＥＣ＝１：１）と電解質（ＬｉＰＦ６ １ｍｏｌ／Ｌ）とセパレータ（ポリエチレン製多孔質フィルム３０μｍ厚）とを組み合わせてコインセル電池を作製した。   A powder sample, a PI binder as a non-aqueous (organic) binder, and KB as a conductive aid were mixed at a weight ratio of 80: 15: 5, and kneaded into a slurry using organic NMP as a solvent. The prepared slurry was coated on a copper foil and vacuum heat-treated at 350 ° C. for 30 minutes to obtain a negative electrode. This negative electrode, counter electrode (Li foil), electrolyte (EC: DEC = 1: 1), electrolyte (LiPF6 1 mol / L) and separator (polyethylene porous film 30 μm thick) were combined to produce a coin cell battery.

作製されたコインセル電池に充放電試験を実施した。充電は、電池の両極間の電圧が０．０５Ｖに達するまでは０．５Ｃの定電流で行い、電圧が０．０５Ｖに達した後は電流が０．０１Ｃになるまで定電位充電で行った。放電は、電池の両極間の電圧が１．５Ｖに達するまでは０．１Ｃの定電流で行った。   A charge / discharge test was performed on the manufactured coin cell battery. Charging was performed at a constant current of 0.5C until the voltage between the two electrodes of the battery reached 0.05V, and was charged at a constant potential until the current reached 0.01C after the voltage reached 0.05V. . Discharging was performed at a constant current of 0.1 C until the voltage between both electrodes of the battery reached 1.5V.

この充放電試験により、初期充電容量、及び初期放電容量を測定して、初期効率を求めた。結果を粉末試料の主要な仕様（Ｍｇ／Ｓｉ比、含有物質、Ｓｉ結晶粒子径）と共に表１に示す。   By this charge / discharge test, the initial charge capacity and the initial discharge capacity were measured to determine the initial efficiency. The results are shown in Table 1 together with the main specifications of the powder sample (Mg / Si ratio, contained substances, Si crystal particle diameter).

Figure 2017224600
Figure 2017224600

実施例１〜実施例７では、Ｍｇがドープされているが、結晶Ｓｉ及び適切な種類のＭｇ含有化合物が含有され、その一方でＳｉＯ2や金属Ｍｇ、ＭｇＳｉ合金が存在せず、Ｓｉ結晶粒子径も４０ｎｍ以下に抑制されているため、比較例１で得られたＳｉとＳｉＯ2の混合物と比べて、Ｍｇドープによる初期効率の改善効果が顕著である。 In Examples 1 to 7, Mg is doped, but contains crystalline Si and an appropriate type of Mg-containing compound, while no SiO 2 , metal Mg, or MgSi alloy exists, and Si crystal particles Since the diameter is also suppressed to 40 nm or less, compared with the mixture of Si and SiO 2 obtained in Comparative Example 1, the effect of improving the initial efficiency by Mg doping is remarkable.

比較例２では、固相法ではあるが、機械的な合金化法ではなく、焼成法のため、反応の不均一は比較的軽いが、それでもＳｉＯ2が生じており、何よりも高熱処理のためにＳｉ結晶粒子径が増大した。これらによる影響のため初期効率の改善効果が小さい上に、充放電容量が大きく低下した。 In Comparative Example 2, although it is a solid-phase method, it is not a mechanical alloying method but a firing method, so the reaction non-uniformity is relatively light, but still SiO 2 is formed, and above all, for high heat treatment In addition, the Si crystal particle diameter increased. Because of these effects, the effect of improving the initial efficiency is small and the charge / discharge capacity is greatly reduced.

比較例３では、実施例と同じ気相法のため、Ｓｉ結晶粒子径は小さいものの、不均一なドープ反応により、不適切な組合せである３種類のＭｇ含有化合物が生じると共に、ＳｉＯ２ が生じ、比較例１よりも更に初期効率が低下する結果になった。   In Comparative Example 3, because of the same vapor phase method as in the example, the Si crystal particle size is small, but the heterogeneous doping reaction generates three kinds of Mg-containing compounds that are inappropriate combinations, and SiO2 is generated, As a result, the initial efficiency was lower than that of Comparative Example 1.

Claims (7)

Ｌｉイオン二次電池の負極形成に使用される酸化珪素系負極材であって、Ｓｉ−Ｍｇ−Ｏの３元系材料からなり、Ｓｉ相を含むと共に、Ｍｇ含有化合物としてＭｇＳｉＯ３、Ｍｇ2ＳｉＯ4、ＭｇＯ、ＭｇＳｉＯ３＋Ｍｇ2ＳｉＯ4又はＭｇ2ＳｉＯ4＋ＭｇＯの５種のうちの何れか１種を含む一方、ＳｉＯ2、金属Ｍｇ及びＭｇＳｉ合金の何れも含まない酸化珪素系負極材。 A silicon oxide negative electrode material used for forming a negative electrode of a Li ion secondary battery, which is made of a ternary material of Si-Mg-O, contains a Si phase, and includes MgSiO 3 and Mg 2 SiO as Mg-containing compounds. 4. A silicon oxide-based negative electrode material that contains any one of MgO, MgSiO 3 + Mg 2 SiO 4 or Mg 2 SiO 4 + MgO, but does not contain any of SiO 2 , metal Mg, and MgSi alloy. 請求項１に記載の酸化珪素系粉末負極材において、組成がＳｉxＭｇyＯzで表して、３ｙ＞ｚ＞ｙ、且つ２ｘ＋ｙ＞ｚを満足する酸化珪素系負極材。 In silicon oxide powder negative electrode material according to claim 1, the composition is expressed by Si x Mg y O z, 3y >z> y, and 2x + y> silicon oxide negative electrode material that satisfies z. 請求項１又は２に記載の酸化珪素系粉末負極材において、ＣｕＫα線を用いたＸＲＤ測定を行った際に、２θ＝２８．４±０．３°付近に表れるＳｉに由来のピークの半値幅から算出するＳｉ結晶粒子径が４０ｎｍ以下である酸化珪素系粉末負極材。   The half width of the peak derived from Si appearing in the vicinity of 2θ = 28.4 ± 0.3 ° when XRD measurement using a CuKα ray is performed in the silicon oxide powder negative electrode material according to claim 1 or 2. A silicon oxide-based powder negative electrode material having a Si crystal particle diameter of 40 nm or less calculated from Ｌｉイオン二次電池の負極形成に使用される酸化珪素系負極材の製造方法であって、ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させ、それらのガスを蒸着面上で冷却して回収する酸化珪素系負極材の製造方法。   A method for producing a silicon oxide negative electrode material used for forming a negative electrode of a Li ion secondary battery, wherein SiO gas and Mg gas are simultaneously generated in the same container, and these gases are cooled on a deposition surface. A method for producing a silicon oxide negative electrode material to be recovered. 請求項４に記載の酸化珪素系負極材の製造方法において、Ｓｉ、Ｍｇ及びＯを含有する原料を同一の容器内で減圧加熱することにより、ＳｉＯガスとＭｇガスを同一の容器内で同時に発生させる酸化珪素系負極材の製造方法。   5. The method for producing a silicon oxide negative electrode material according to claim 4, wherein SiO gas and Mg gas are simultaneously generated in the same container by heating the raw material containing Si, Mg and O under reduced pressure in the same container. A method for producing a silicon oxide negative electrode material. 請求項５に記載の酸化珪素系負極材の製造方法において、Ｓｉ、Ｍｇ及びＯを含有する原料はＳｉ単体とＭｇ・Ｏ含有化合物とを含み、Ｍｇ・Ｏ含有化合物はＭｇＯ、Ｍｇ2ＳｉＯ4、ＭｇＳｉＯ３、Ｍｇ2ＣＯ３、Ｍｇ（ＯＨ）2のうちの１種又は２種以上である酸化珪素系負極材の製造方法。 6. The method for producing a silicon oxide negative electrode material according to claim 5, wherein the raw material containing Si, Mg, and O contains Si alone and a Mg.O-containing compound, and the Mg.O-containing compound is MgO, Mg 2 SiO 4. , MgSiO 3 , Mg 2 CO 3 , Mg (OH) 2 , or a method for producing a silicon oxide negative electrode material that is one or more of them. Ｌｉイオン二次電池の負極形成に使用される酸化珪素系負極材の製造方法であって、Ｓｉ単体と、酸素を含有する金属化合物とを含む原料を同一の容器内で同時に減圧加圧して、ＳｉＯガスと金属ガスとを同時に発生させ、それらのガスを同じ蒸着面上で冷却して回収する酸化珪素系負極材の製造方法。   A method for producing a silicon oxide-based negative electrode material used for forming a negative electrode of a Li ion secondary battery, wherein a raw material containing a simple substance of Si and a metal compound containing oxygen is simultaneously decompressed and pressurized in the same container, A method for producing a silicon oxide-based negative electrode material, in which SiO gas and metal gas are simultaneously generated, and these gases are cooled and recovered on the same vapor deposition surface.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108987689A (en) * 2018-06-22 2018-12-11 杨庆 A kind of preparation method of silicon-carbon cathode material
CN109546122A (en) * 2018-11-23 2019-03-29 浙江众泰汽车制造有限公司 A kind of Si-C composite material of surface modification and its preparation method and application
CN110311120A (en) * 2019-07-10 2019-10-08 洛阳联创锂能科技有限公司 A kind of lithium ion battery negative electrode material of SiClx containing magnesia and preparation method thereof
WO2020122602A1 (en) * 2018-12-11 2020-06-18 주식회사 엘지화학 Anode for lithium secondary battery and lithium secondary battery comprising same
CN111466046A (en) * 2018-01-31 2020-07-28 株式会社Lg化学 Negative electrode active material, negative electrode comprising the same, and lithium secondary battery comprising the same
KR20200144855A (en) * 2019-06-19 2020-12-30 대주전자재료 주식회사 Carbon-silicon complex oxide compoite for anode material of secondary battery and method for preparing the same
CN112259708A (en) * 2020-10-28 2021-01-22 成都新柯力化工科技有限公司 Preparation method of multilayer core-shell structure silicon monoxide lithium battery cathode
CN112349900A (en) * 2019-08-07 2021-02-09 珠海冠宇电池股份有限公司 Negative pole piece and lithium ion battery containing same
EP3902035A4 (en) * 2019-01-18 2022-03-16 Lg Energy Solution, Ltd. Anode active material for lithium secondary battery, and lithium secondary battery comprising same
CN114447310A (en) * 2020-10-30 2022-05-06 特拉技术有限公司 Cathode material for secondary battery
CN115663151A (en) * 2022-11-10 2023-01-31 广东凯金新能源科技股份有限公司 Pre-magnesium-silicon-oxygen composite material, silicon-based negative electrode material, preparation method and secondary battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006066370A (en) * 2004-07-28 2006-03-09 Mitsubishi Chemicals Corp Negative electrode for nonaqueous electrolyte secondary battery, its manufacturing method and nonaqueous electrolyte secondary battery
JP2010170943A (en) * 2009-01-26 2010-08-05 Asahi Glass Co Ltd Negative electrode material for secondary battery, and its manufacturing method
WO2011077654A1 (en) * 2009-12-21 2011-06-30 株式会社豊田自動織機 Negative electrode active substance for nonaqueous secondary cell and method for producing the same
JP2014187007A (en) * 2013-02-21 2014-10-02 Ｃｏｎｎｅｘｘ Ｓｙｓｔｅｍｓ株式会社 Composite active material for lithium secondary battery and method for producing the same
US20140377653A1 (en) * 2013-06-21 2014-12-25 Unist Academy-Industry Research Corporation Porous silicon based negative electrode active material, method for manufacturing the same, and rechargeable lithium battery including the same
KR101586816B1 (en) * 2015-06-15 2016-01-20 대주전자재료 주식회사 Negative active material for non-aqueous electrolyte rechargeable battery, the preparation method thereof, and rechargeable battery including the same
WO2016085953A1 (en) * 2014-11-25 2016-06-02 Corning Incorporated Method and material for lithium ion battery anodes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006066370A (en) * 2004-07-28 2006-03-09 Mitsubishi Chemicals Corp Negative electrode for nonaqueous electrolyte secondary battery, its manufacturing method and nonaqueous electrolyte secondary battery
JP2010170943A (en) * 2009-01-26 2010-08-05 Asahi Glass Co Ltd Negative electrode material for secondary battery, and its manufacturing method
WO2011077654A1 (en) * 2009-12-21 2011-06-30 株式会社豊田自動織機 Negative electrode active substance for nonaqueous secondary cell and method for producing the same
JP2014187007A (en) * 2013-02-21 2014-10-02 Ｃｏｎｎｅｘｘ Ｓｙｓｔｅｍｓ株式会社 Composite active material for lithium secondary battery and method for producing the same
US20140377653A1 (en) * 2013-06-21 2014-12-25 Unist Academy-Industry Research Corporation Porous silicon based negative electrode active material, method for manufacturing the same, and rechargeable lithium battery including the same
WO2016085953A1 (en) * 2014-11-25 2016-06-02 Corning Incorporated Method and material for lithium ion battery anodes
KR101586816B1 (en) * 2015-06-15 2016-01-20 대주전자재료 주식회사 Negative active material for non-aqueous electrolyte rechargeable battery, the preparation method thereof, and rechargeable battery including the same

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111466046A (en) * 2018-01-31 2020-07-28 株式会社Lg化学 Negative electrode active material, negative electrode comprising the same, and lithium secondary battery comprising the same
JP2020529709A (en) * 2018-01-31 2020-10-08 エルジー・ケム・リミテッド Negative electrode active material, negative electrode containing it and lithium secondary battery
US11824184B2 (en) 2018-01-31 2023-11-21 Lg Energy Solution, Ltd. Negative electrode active material, negative electrode including the same and lithium secondary battery including the same
JP7337202B2 (en) 2018-01-31 2023-09-01 エルジー エナジー ソリューション リミテッド Negative electrode active material, negative electrode containing the same, and lithium secondary battery
CN111466046B (en) * 2018-01-31 2022-05-24 株式会社Lg新能源 Negative electrode active material, negative electrode comprising the same, and lithium secondary battery comprising the same
JP2022076482A (en) * 2018-01-31 2022-05-19 エルジー エナジー ソリューション リミテッド Negative electrode active material, negative electrode containing the same, and lithium secondary battery
JP7063981B2 (en) 2018-01-31 2022-05-09 エルジー エナジー ソリューション リミテッド Negative electrode active material, negative electrode containing it and lithium secondary battery
CN108987689A (en) * 2018-06-22 2018-12-11 杨庆 A kind of preparation method of silicon-carbon cathode material
CN109546122A (en) * 2018-11-23 2019-03-29 浙江众泰汽车制造有限公司 A kind of Si-C composite material of surface modification and its preparation method and application
WO2020122602A1 (en) * 2018-12-11 2020-06-18 주식회사 엘지화학 Anode for lithium secondary battery and lithium secondary battery comprising same
EP3902035A4 (en) * 2019-01-18 2022-03-16 Lg Energy Solution, Ltd. Anode active material for lithium secondary battery, and lithium secondary battery comprising same
US11942640B2 (en) 2019-01-18 2024-03-26 Lg Energy Solution, Ltd. Negative electrode active material for lithium secondary battery and lithium secondary battery comprising the same
KR20200144855A (en) * 2019-06-19 2020-12-30 대주전자재료 주식회사 Carbon-silicon complex oxide compoite for anode material of secondary battery and method for preparing the same
KR102374350B1 (en) 2019-06-19 2022-03-16 대주전자재료 주식회사 Carbon-silicon complex oxide compoite for anode material of secondary battery and method for preparing the same
KR20210146874A (en) * 2019-06-19 2021-12-06 대주전자재료 주식회사 Carbon-silicon complex oxide compoite for anode material of secondary battery and method for preparing the same
KR102452874B1 (en) 2019-06-19 2022-10-12 대주전자재료 주식회사 Carbon-silicon complex oxide compoite for anode material of secondary battery and method for preparing the same
CN110311120B (en) * 2019-07-10 2022-02-08 洛阳联创锂能科技有限公司 Magnesium-containing silicon oxide negative electrode material for lithium ion battery and preparation method thereof
CN110311120A (en) * 2019-07-10 2019-10-08 洛阳联创锂能科技有限公司 A kind of lithium ion battery negative electrode material of SiClx containing magnesia and preparation method thereof
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