JP2008251369A - Negative electrode for lithium secondary battery, lithium secondary battery equipped with it, and manufacturing method of negative electrode for lithium secondary battery - Google Patents

Negative electrode for lithium secondary battery, lithium secondary battery equipped with it, and manufacturing method of negative electrode for lithium secondary battery Download PDF

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JP2008251369A
JP2008251369A JP2007091827A JP2007091827A JP2008251369A JP 2008251369 A JP2008251369 A JP 2008251369A JP 2007091827 A JP2007091827 A JP 2007091827A JP 2007091827 A JP2007091827 A JP 2007091827A JP 2008251369 A JP2008251369 A JP 2008251369A
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negative electrode
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JP5108355B2 (en
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Kazuya Iwamoto
和也 岩本
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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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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    • Y02E60/10—Energy storage using batteries

Abstract

<P>PROBLEM TO BE SOLVED: To improve a charge-discharge cycle characteristic by preventing separation of a negative electrode active material body from a surface of a collector, in a negative electrode for a lithium secondary battery with a plurality of negative electrode active material bodies containing silicon oxide formed on a collector. <P>SOLUTION: This negative electrode 100 for a lithium secondary battery is provided with the collector 1, and the plurality of negative electrode active material bodies 5 arranged on the collector 1 by being spaced apart from one another, and containing silicon oxide. In the negative electrode for a lithium secondary battery, a plurality of first projecting parts 2A supporting the plurality of negative electrode active material bodies 5 are arranged on a surface of the collector 1; each first projecting part 2A has a plurality of projecting parts 2B each having a height smaller than that of the first projecting part 2A; the average value of a molar ratio of the quantity of oxygen to that of silicon of each negative electrode active material body 5 is 0.1-1.2; and the difference between the maximum value and the minimum value of the molar ratio of the quantity of oxygen to that of silicon in the vicinity of an interfacial surface between each negative electrode active material body 5 and the collector 1 is not larger than 0.4. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、リチウム二次電池用負極およびそれを備えたリチウム二次電池、ならびにリチウム二次電池用負極の製造方法に関する。   The present invention relates to a negative electrode for a lithium secondary battery, a lithium secondary battery including the negative electrode, and a method for producing a negative electrode for a lithium secondary battery.

リチウムイオン二次電池が用いられるＰＣ（Ｐｅｒｓｏｎａｌ Ｃｏｍｐｕｔｅｒ）、携帯電話、ＰＤＡ（Ｐｅｒｓｏｎａｌ Ｄｉｇｉｔａｌ Ａｓｓｉｓｔａｎｔ）等の携帯情報端末や、ビデオレコーダー、メモリーオーディオプレーヤー等のオーディオビジュアル機器の小型化および高性能化が進んでいる。これに伴い、リチウムイオン二次電池の高容量化も望まれている。高容量化のための負極活物質としては、金属リチウムや、リチウムと合金化するケイ素、スズなどが検討されている。   Advances in miniaturization and high performance of portable information terminals such as PCs (Personal Computers), mobile phones, and PDAs (Personal Digital Assistants) that use lithium ion secondary batteries, as well as audio-visual devices such as video recorders and memory audio players. It is out. Accordingly, it is desired to increase the capacity of the lithium ion secondary battery. As a negative electrode active material for increasing the capacity, metallic lithium, silicon alloyed with lithium, tin, and the like have been studied.

しかし、これらの負極活物質はリチウムイオンと反応する際に大きな体積変化を伴うため、充放電を繰り返すことによって、負極活物質が集電体から剥離したり、負極に変形が生じるという問題がある。   However, since these negative electrode active materials are accompanied by a large volume change when reacting with lithium ions, there is a problem that the negative electrode active material is peeled off from the current collector or the negative electrode is deformed by repeated charge and discharge. .

このような問題を解決するための電極構造が特許文献１に開示されている。特許文献１に開示された構造では、リチウムと合金化しない材料からなる集電体上に、リチウムと合金化する活物質からなる複数の柱状体が形成されている。このような柱状体は、例えば、集電体上に活物質の膜を形成し、これをフォトリソグラフィーによりパターニングすることによって形成される。または、メッキ技術を用いて集電体上に選択的に活物質を堆積させることによって形成される。この電極構造によると、柱状体間の空隙を埋めるように柱状体が膨張するので、膨張応力による電極特性の低下を抑えることができる。   An electrode structure for solving such a problem is disclosed in Patent Document 1. In the structure disclosed in Patent Document 1, a plurality of columnar bodies made of an active material alloyed with lithium are formed on a current collector made of a material not alloyed with lithium. Such a columnar body is formed, for example, by forming a film of an active material on a current collector and patterning the film by photolithography. Alternatively, it is formed by selectively depositing an active material on a current collector using a plating technique. According to this electrode structure, since the columnar bodies expand so as to fill the gaps between the columnar bodies, it is possible to suppress a decrease in electrode characteristics due to expansion stress.

特許文献１の負極では、各柱状体は集電体の法線方向に沿って直立している。このような負極を用いてリチウム二次電池を構成すると、正極活物質層の大部分が、活物質からなる柱状体と対向せず、集電体表面のうち活物質で覆われていない部分（「集電体の露出部」とする）と対向してしまうという問題がある。そのため、充電時に正極活物質層から供給されるリチウムは、負極活物質に吸蔵されずに、負極集電体の露出部に析出しやすくなる。その結果、放電時に負極からリチウムを効率良く放出され難くなるので、充放電効率が低下する。   In the negative electrode of Patent Document 1, each columnar body stands upright along the normal direction of the current collector. When a lithium secondary battery is configured using such a negative electrode, most of the positive electrode active material layer does not face the columnar body made of the active material, and the portion of the current collector surface that is not covered with the active material ( There is a problem that it faces the “exposed portion of the current collector”. Therefore, lithium supplied from the positive electrode active material layer at the time of charging is not occluded by the negative electrode active material, but tends to be deposited on the exposed portion of the negative electrode current collector. As a result, it becomes difficult to efficiently release lithium from the negative electrode at the time of discharge, so that the charge / discharge efficiency is lowered.

また、放電時には、負極活物質に対向している正極活物質のみが反応しやすいため、実質的な放電容量が低下する。さらに充放電サイクルの繰り返しにより、このような不均一な反応が進むと、正極中での粒子ごとの放電深度、すなわち粒子ごとの電位分布が拡大される。そのため、高電位状態にある正極活物質と接触した部位での電解液の分解による皮膜形成やガス発生といった副反応の割合が増加して放電容量が低下し、電池の劣化が進行する。特に、大きな電流値でハイレートの充放電を行うと、サイクル特性が著しく低下してしまう。   Moreover, since only the positive electrode active material facing the negative electrode active material is likely to react during discharge, the substantial discharge capacity is reduced. Further, when such a non-uniform reaction proceeds by repeating the charge / discharge cycle, the discharge depth for each particle in the positive electrode, that is, the potential distribution for each particle is expanded. Therefore, the rate of side reactions such as film formation and gas generation due to decomposition of the electrolyte solution at the site in contact with the positive electrode active material in a high potential state increases, the discharge capacity decreases, and the battery progresses further. In particular, when high-rate charging / discharging is performed with a large current value, the cycle characteristics are significantly deteriorated.

これに対して、本出願人による特許文献２は、集電体上に、集電体表面の法線方向に対して傾斜した長軸を有する柱状の活物質粒子を配置することを提案している。この構成によれば、正極活物質層のうち集電体の露出部と対向する部分の割合を小さくできるので、正極活物質と負極活物質とを十分に活用でき、特許文献１よりも高い容量維持率を得ることができる。   On the other hand, Patent Document 2 by the present applicant proposes to dispose columnar active material particles having a long axis inclined with respect to the normal direction of the current collector surface on the current collector. Yes. According to this configuration, since the ratio of the portion of the positive electrode active material layer facing the exposed portion of the current collector can be reduced, the positive electrode active material and the negative electrode active material can be fully utilized, and the capacity higher than that of Patent Document 1 A maintenance rate can be obtained.

このような活物質粒子は、表面に微小な凸部を有する集電体の表面に、酸素を含む雰囲気下で、集電体の法線方向に対して傾斜した方向からケイ素粒子を蒸着させることによって得られる（斜め蒸着）。このとき、集電体表面のうち凸部や凸部上に成長したケイ素酸化物の影となる部分にはケイ素粒子が蒸着されないので（シャドウイング効果）、集電体表面に体積膨張を吸収する隙間を確保しつつ、ケイ素酸化物を成長させることができる。
特開２００４−１２７５６１号公報 国際公開第２００７／０１５４１９号パンフレット Such active material particles are obtained by depositing silicon particles on the surface of a current collector having minute protrusions on the surface from a direction inclined with respect to the normal direction of the current collector in an oxygen-containing atmosphere. (Oblique deposition). At this time, since the silicon particles are not deposited on the convex portion or the shadowed portion of the silicon oxide grown on the convex portion of the current collector surface (shadowing effect), the current collector surface absorbs the volume expansion. Silicon oxide can be grown while ensuring a gap.
JP 2004-127561 A International Publication No. 2007/015419 Pamphlet

特許文献２では、上述したように、集電体表面の凸部を利用して斜め蒸着により活物質粒子を形成している。しかしながら、本願発明者らが検討したところ、集電体表面の凸部の形態と蒸着粒子（ここではケイ素粒子）の飛来方向との関係によって、各活物質粒子における集電体との界面近傍の酸素濃度に大きな分布が生じる可能性があることを見出した。酸素濃度に分布が生じてしまうメカニズムについては、後で図面を参照しながら詳述する。   In Patent Document 2, as described above, the active material particles are formed by oblique vapor deposition using the convex portions on the surface of the current collector. However, when the inventors of the present application examined, the relationship between the shape of the convex portion on the surface of the current collector and the flying direction of the vapor deposition particles (here, silicon particles), the vicinity of the interface with the current collector in each active material particle It has been found that a large distribution of oxygen concentration may occur. The mechanism by which the oxygen concentration is distributed will be described in detail later with reference to the drawings.

ケイ素酸化物は、その酸素比率（ケイ素量に対する酸素量のモル比）が高いほど、リチウム吸蔵・放出に伴う膨張・収縮の割合が低いため、活物質粒子に上記のような酸素比率の分布が生じると、その活物質粒子と集電体との界面近傍では、活物質の膨張および収縮の割合が異なる領域が存在する。その結果、活物質粒子が集電体から剥離しやすくなり、充放電サイクルの低下を引き起こすおそれがある。   The higher the oxygen ratio (the molar ratio of the oxygen amount to the silicon amount) of silicon oxide, the lower the rate of expansion / contraction associated with lithium occlusion / release, so the active material particles have a distribution of oxygen ratio as described above. When this occurs, there are regions in which the ratio of expansion and contraction of the active material differs in the vicinity of the interface between the active material particles and the current collector. As a result, the active material particles easily peel from the current collector, which may cause a decrease in charge / discharge cycle.

本発明は、上記問題を解決するためになされたものであり、その目的は、集電体の上に複数のケイ素酸化物を含む負極活物質体が形成されたリチウム二次電池用負極において、各負極活物質体と集電体との界面近傍における酸素比率を略均一にすることにより、負極活物質体の集電体表面からの剥離を抑制して充放電サイクル特性を向上させることにある。   The present invention has been made in order to solve the above problems, and the object thereof is a negative electrode for a lithium secondary battery in which a negative electrode active material body containing a plurality of silicon oxides is formed on a current collector. By making the oxygen ratio in the vicinity of the interface between each negative electrode active material body and the current collector substantially uniform, the separation of the negative electrode active material body from the current collector surface is suppressed and the charge / discharge cycle characteristics are improved. .

前述した従来の課題を解決するために、本発明のリチウム二次電池用負極は、集電体と、集電体の上に互いに間隔を空けて配置され、ケイ素酸化物を含む複数の負極活物質体とを備える。集電体の表面には、複数の負極活物質体を支持する複数の第１の凸部が配列されており、各第１の凸部は、前記第１の凸部よりも高さの小さい複数の第２の凸部を有している。各負極活物質体のケイ素量に対する酸素量のモル比の平均値は０．１以上１．２以下であり、各負極活物質体と集電体との界面近傍における、ケイ素量に対する酸素量のモル比の最大値と最小値との差が０．４以下である。   In order to solve the above-described conventional problems, a negative electrode for a lithium secondary battery according to the present invention is arranged on a current collector and a current collector so as to be spaced apart from each other, and includes a plurality of negative electrode actives containing silicon oxide. A substance. A plurality of first protrusions that support the plurality of negative electrode active material bodies are arranged on the surface of the current collector, and each first protrusion is smaller in height than the first protrusions. A plurality of second convex portions are provided. The average value of the molar ratio of the oxygen amount to the silicon amount of each negative electrode active material body is 0.1 or more and 1.2 or less, and the oxygen amount relative to the silicon amount in the vicinity of the interface between each negative electrode active material body and the current collector is The difference between the maximum value and the minimum value of the molar ratio is 0.4 or less.

上記構成によると、集電体表面に配列された第１の凸部によって、負極活物質体の配置や隣接する負極活物質体の間隔を制御できるので、負極活物質体の膨張のための空間を確保できる。また、第１の凸部の表面に設けられた第２の凸部により、各負極活物質体と集電体との接触面積を増大させることができるので、負極活物質体と集電体との密着性を向上できる。   According to the above configuration, the arrangement of the negative electrode active material bodies and the interval between the adjacent negative electrode active material bodies can be controlled by the first protrusions arranged on the surface of the current collector. Can be secured. Further, since the contact area between each negative electrode active material body and the current collector can be increased by the second convex part provided on the surface of the first convex part, the negative electrode active material body and the current collector Can improve the adhesion.

また、各負極活物質体のケイ素量に対する酸素量のモル比の平均値は０．１以上１．２以下であり、これによって、高い容量を確保しつつ、リチウム吸蔵による体積膨張を抑えることができる。   Further, the average value of the molar ratio of the oxygen amount to the silicon amount of each negative electrode active material body is 0.1 or more and 1.2 or less, thereby suppressing the volume expansion due to lithium occlusion while ensuring a high capacity. it can.

さらに、各負極活物質体と集電体との界面近傍における、ケイ素量に対する酸素量のモル比の最大値と最小値との差が０．４以下に抑えられているため、各活物質粒子は、集電体との界面近傍で略均一な割合で膨張・収縮する。従って、上記界面近傍における膨張や収縮の割合の差による局所的な応力集中を防止できるので、そのような応力集中に起因する活物質粒子の集電体からの剥離を抑制でき、その結果、リチウム二次電池の充放電サイクル特性を向上できる。   Furthermore, since the difference between the maximum value and the minimum value of the molar ratio of the oxygen amount to the silicon amount in the vicinity of the interface between each negative electrode active material body and the current collector is suppressed to 0.4 or less, each active material particle Expands and contracts at a substantially uniform rate near the interface with the current collector. Therefore, local stress concentration due to the difference in the expansion and contraction ratios in the vicinity of the interface can be prevented, so that the separation of the active material particles from the current collector due to such stress concentration can be suppressed. The charge / discharge cycle characteristics of the secondary battery can be improved.

本発明によれば、リチウム二次電池用負極において、活物質粒子と集電体との界面近傍における活物質粒子の酸素濃度分布に起因する活物質粒子の剥離を抑制できる。従って、充放電サイクル特性に優れたリチウム二次電池を提供できる。   ADVANTAGE OF THE INVENTION According to this invention, in the negative electrode for lithium secondary batteries, peeling of the active material particle resulting from the oxygen concentration distribution of the active material particle in the vicinity of the interface of an active material particle and a collector can be suppressed. Therefore, a lithium secondary battery excellent in charge / discharge cycle characteristics can be provided.

以下、図面を参照しながら、本発明によるリチウム二次電池用負極の実施形態を説明する。   Hereinafter, embodiments of a negative electrode for a lithium secondary battery according to the present invention will be described with reference to the drawings.

まず、図１を参照する。図１は、本実施形態のリチウム二次電池用負極（以下、「負極」ともいう）の概略断面図である。   First, refer to FIG. FIG. 1 is a schematic cross-sectional view of a negative electrode for a lithium secondary battery (hereinafter also referred to as “negative electrode”) of the present embodiment.

負極１００は、集電体１と、集電体１の表面に互いに間隔を空けて配置された複数の負極活物質体５とを備えている。負極活物質体５は、ケイ素酸化物を含んでおり、そのケイ素量に対する酸素量のモル比（以下、単に「酸素比率」ともいう）の平均値は０．１以上１．２以下である。また、各負極活物質体５と集電体１との界面近傍では、各負極活物質体５における酸素比率の最大値Ｒｍａｘと最小値Ｒｍｉｎとの差ΔＲは０．４以下である
。 The negative electrode 100 includes a current collector 1 and a plurality of negative electrode active material bodies 5 that are arranged on the surface of the current collector 1 at intervals. The negative electrode active material body 5 contains silicon oxide, and the average value of the molar ratio of the oxygen amount to the silicon amount (hereinafter also simply referred to as “oxygen ratio”) is 0.1 or more and 1.2 or less. Further, in the vicinity of the interface between each negative electrode active material body 5 and current collector 1, the difference ΔR between the maximum value Rmax and the minimum value Rmin of the oxygen ratio in each negative electrode active material body 5 is 0.4 or less.

なお、負極活物質体５は、ケイ素酸化物以外に負極活物質体５に補填あるいは吸蔵されたリチウムや、Ｆｅ、Ａｌ、Ｃａ、Ｍｎ、Ｔｉなどの不純物などを含んでいてもよい。また、複数の負極活物質体５は、互いに間隔を空けて配置されているが、充電時にリチウムを吸蔵して膨張することにより、隣接する負極活物質体５が部分的に接触する場合もある。   In addition, the negative electrode active material body 5 may contain impurities such as lithium, Fe, Al, Ca, Mn, and Ti that are supplemented or occluded in the negative electrode active material body 5 in addition to silicon oxide. Moreover, although the some negative electrode active material body 5 is arrange | positioned at intervals, the adjacent negative electrode active material body 5 may partially contact by occluding and expanding lithium at the time of charge. .

集電体１の表面には、複数の第１の凸部２Ａが配列されており、各第１の凸部２Ａの表面は、第１の凸部２Ａよりも高さの小さい複数の第２の凸部を有している。集電体１のうち第１の凸部２Ａが形成されていない領域（「溝」ともいう）４は略平坦である。   A plurality of first convex portions 2A are arranged on the surface of the current collector 1, and the surface of each first convex portion 2A has a plurality of second projections that are smaller in height than the first convex portions 2A. It has a convex part. A region 4 (also referred to as “groove”) 4 of the current collector 1 where the first convex portion 2A is not formed is substantially flat.

第１の凸部２Ａは、負極活物質体５の配置を制御し、負極活物質体５の間に適当な空隙を確保できるようなサイズおよびピッチで配列されている。複数の第２の凸部２Ｂの少なくとも一部は、第１の凸部２Ａの表面のうち負極活物質体５が形成される部分に配置されていることが好ましく、これにより、負極活物質体５と集電体１との接触面積を大きくできるので、負極活物質体５と集電体１との密着性を向上させることができる。   The first protrusions 2 </ b> A are arranged with a size and a pitch that control the disposition of the negative electrode active material bodies 5 and can ensure appropriate gaps between the negative electrode active material bodies 5. It is preferable that at least a part of the plurality of second protrusions 2B is disposed on a portion of the surface of the first protrusion 2A where the negative electrode active material body 5 is formed, whereby the negative electrode active material body Since the contact area between 5 and the current collector 1 can be increased, the adhesion between the negative electrode active material body 5 and the current collector 1 can be improved.

第１の凸部２Ａの形状は、特に限定されないが、例えば半球状、角柱状、円柱状である。なお、第１の凸部２Ａは、集電体１の表面に垂直な断面において、各第１の凸部２Ａの表面のうち負極活物質体５と接触する部分に９０°以下の角（かど）を有していないことが好ましい。これにより、後で詳述するように、集電体１と負極活物質体５との界面近傍における酸素比率の分布幅（上記ΔＲ）を小さく抑えることが可能になる。   The shape of the first convex portion 2A is not particularly limited, but is, for example, hemispherical, prismatic, or cylindrical. Note that the first protrusion 2A has a 90 ° or less corner (corner) at a portion of the surface of each first protrusion 2A that contacts the negative electrode active material body 5 in a cross section perpendicular to the surface of the current collector 1. ) Is preferably not included. As a result, as will be described in detail later, it is possible to reduce the oxygen ratio distribution width (ΔR) in the vicinity of the interface between the current collector 1 and the negative electrode active material body 5.

なお、負極１００では、第１の凸部２Ａの上面のみに第２の凸部２Ｂが形成されているが、第２の凸部２Ｂは、第１の凸部２Ａの側面にも形成されていてもよい。また、集電体１の溝４は略平坦であるが、溝４の表面にも凹凸が形成されていてもよい。ただし、負極活物質体５の膨張空間を確実に確保するためには、溝４の表面凹凸の高さは、第２の凸部２Ｂの高さと同等か、またはそれよりも小さいことが好ましい。   In the negative electrode 100, the second convex portion 2B is formed only on the upper surface of the first convex portion 2A. However, the second convex portion 2B is also formed on the side surface of the first convex portion 2A. May be. Further, the groove 4 of the current collector 1 is substantially flat, but the surface of the groove 4 may be uneven. However, in order to ensure the expansion space of the negative electrode active material body 5, the height of the surface irregularities of the grooves 4 is preferably equal to or smaller than the height of the second convex portions 2 </ b> B.

負極活物質体５は、図１に示すように、集電体１の法線方向Ｎに対して傾斜した成長方向Ｇを有することが好ましい。このような構成により、リチウム二次電池において、正極活物質層のうち負極活物質体５と対向する部分の面積を増加させることができるので、充放電効率を高めることができる。このような負極活物質体５は、例えば、酸素ガスが導入されたチャンバー内で、集電体１の表面に、集電体１の法線方向Ｎに対して傾斜した方向からケイ素を入射することによって形成できる（斜め蒸着）。   As shown in FIG. 1, the negative electrode active material body 5 preferably has a growth direction G that is inclined with respect to the normal direction N of the current collector 1. With such a configuration, in the lithium secondary battery, the area of the portion of the positive electrode active material layer facing the negative electrode active material body 5 can be increased, so that the charge / discharge efficiency can be increased. In such a negative electrode active material body 5, for example, silicon is incident on the surface of the current collector 1 from a direction inclined with respect to the normal direction N of the current collector 1 in a chamber into which oxygen gas is introduced. Can be formed (oblique deposition).

負極活物質体５の成長方向Ｇと集電体１の法線方向Ｎとのなす角度は、１０°以上であることが好ましい。良好な密着性を得るためには、負極活物質体５と集電体１との接触面積が大きい方がよく、すなわち、上記角度が０°であればよいが、その場合には、シャドウイング効果が生じないので、隣接する負極活物質体５の間に隙間を形成することができない。しかしながら、上記角度が１０°以上であれば、負極活物質体５間に隙間を形成しつつ十分な接触面積を得ることができる。一方、上記角度は９０°未満であればよいが、９０°に近づくほど負極活物質体５を形成することが困難となるため、８０°未満であることが好ましい。なお、負極活物質体５は成長方向Ｇの異なる複数の部分を有していてもよく、その場合でも、負極活物質体５のうち集電体１との界面近傍に位置する部分の成長方向Ｇが、集電体１の法線方向Ｎに対して傾斜していることが好ましく、その傾斜角度の好適な範囲は１０°以上９０°未満である。   The angle formed by the growth direction G of the negative electrode active material body 5 and the normal direction N of the current collector 1 is preferably 10 ° or more. In order to obtain good adhesion, it is better that the contact area between the negative electrode active material body 5 and the current collector 1 is large, that is, the angle may be 0 °. Since no effect is produced, a gap cannot be formed between the adjacent negative electrode active material bodies 5. However, if the angle is 10 ° or more, a sufficient contact area can be obtained while forming a gap between the negative electrode active material bodies 5. On the other hand, the angle may be less than 90 °, but the closer to 90 °, the more difficult it is to form the negative electrode active material body 5, and therefore it is preferably less than 80 °. The negative electrode active material body 5 may have a plurality of portions having different growth directions G. Even in this case, the growth direction of the portion of the negative electrode active material body 5 located near the interface with the current collector 1 G is preferably inclined with respect to the normal direction N of the current collector 1, and a preferable range of the inclination angle is 10 ° or more and less than 90 °.

第１の突起の頂上からの負極活物質体５の厚さｔ５は、特に限定しないが、電池のエネルギー密度、生産性、信頼性などの観点から、０．５μｍ以上５０μｍ以下であることが好ましい。厚さｔ５が０．５μｍ以上、より好ましくは５μｍ以上であれば、より高い電池エネルギーを得ることができる。また、厚さｔ５が５０μｍ以下、より好ましくは３０μｍ以下であれば、負極活物質体５を形成する際に生じるクラックを低減できるので、負極１００の信頼性を高めることができる。   The thickness t5 of the negative electrode active material body 5 from the top of the first protrusion is not particularly limited, but is preferably 0.5 μm or more and 50 μm or less from the viewpoint of battery energy density, productivity, reliability, and the like. . If the thickness t5 is 0.5 μm or more, more preferably 5 μm or more, higher battery energy can be obtained. In addition, if the thickness t5 is 50 μm or less, more preferably 30 μm or less, cracks generated when the negative electrode active material body 5 is formed can be reduced, so that the reliability of the negative electrode 100 can be improved.

負極活物質体５に含まれるケイ素酸化物における酸素比率の平均値は、上述したように０．１以上１．２以下である。一般に、ケイ素を含む負極活物質では、その酸素比率が低いほど、高い充放電容量が得られるが、充電による体積膨脹率が大きくなる。一方、酸素比率が高くなるほど、体積膨脹率は抑えられるが、充放電容量が低下する。本実施形態における負極活物質体５では、上記酸素比率の平均値が０．１以上であり、充放電に伴う膨張および収縮が抑えられているので、負極活物質体５の集電体１からの剥離を抑制できる。また、上記酸素比率の平均値が１．２以下であるため、十分な充放電容量を確保でき、高率充放電特性を維持できる。なお、酸素比率の平均値が０．１以上０．６以下であれば、より確実に、適度な充放電サイクル特性と高率充放電特性とをバランス良く得ることができる。なお、負極活物質体５における酸素濃度プロファイルは、厚さ方向に略均一であることが好ましいが、厚さ方向に変化していてもよく、その場合でも、負極活物質体５における酸素比率のモル比の平均値が上記範囲内であればよい。   The average value of the oxygen ratio in the silicon oxide contained in the negative electrode active material body 5 is 0.1 or more and 1.2 or less as described above. In general, in a negative electrode active material containing silicon, the lower the oxygen ratio, the higher the charge / discharge capacity, but the larger the volume expansion rate due to charging. On the other hand, the higher the oxygen ratio, the smaller the volume expansion rate, but the lower the charge / discharge capacity. In the negative electrode active material body 5 in the present embodiment, the average value of the oxygen ratio is 0.1 or more, and expansion and contraction associated with charge / discharge are suppressed. Can be prevented. Moreover, since the average value of the said oxygen ratio is 1.2 or less, sufficient charge / discharge capacity can be ensured and a high rate charge / discharge characteristic can be maintained. In addition, if the average value of the oxygen ratio is 0.1 or more and 0.6 or less, it is possible to more surely obtain an appropriate charge / discharge cycle characteristic and a high rate charge / discharge characteristic with a good balance. The oxygen concentration profile in the negative electrode active material body 5 is preferably substantially uniform in the thickness direction, but may vary in the thickness direction. The average value of molar ratio should just be in the said range.

また、各負極活物質体５と集電体１との界面近傍では、各負極活物質体５における酸素比率の最大値Ｒｍａｘと最小値Ｒｍｉｎとの差ΔＲは０．４以下である。上記の界面近傍
の酸素比率は、リチウムイオン波長分散型Ｘ線マイクロアナライザを用いて測定することができる。 Further, in the vicinity of the interface between each negative electrode active material body 5 and current collector 1, the difference ΔR between the maximum value Rmax and the minimum value Rmin of the oxygen ratio in each negative electrode active material body 5 is 0.4 or less. The oxygen ratio in the vicinity of the interface can be measured using a lithium ion wavelength dispersion X-ray microanalyzer.

以下、図面を参照しながら、負極活物質体５と集電体との界面近傍におけるケイ素量に対する酸素量のモル比の差ΔＲの測定方法の一例を説明する。   Hereinafter, an example of a method for measuring the difference ΔR in the molar ratio of the oxygen amount to the silicon amount in the vicinity of the interface between the negative electrode active material body 5 and the current collector will be described with reference to the drawings.

図２（ａ）は、単一の負極活物質体５を示す模式的な拡大図であり、集電体１に垂直で、かつ、負極活物質体５の成長方向を含む断面を示している。ここでは、図示する断面において、負極活物質体５と集電体１との接触面から負極活物質体５の側に約２μｍ程度離れた領域７を測定領域とする。この測定領域７を、測定領域７の一端からの距離ｙに応じて少なくとも３つのサブ領域に分ける。例えば、測定領域７の一端をｙ＝０、反対側の端をｙ＝Ｙとすると、３つのサブ領域７ａ（ｙ／Ｙ：０〜１／３）、７ｂ（ｙ／Ｙ：１／３〜２／３）および７ｃ（ｙ／Ｙ：２／３〜１）に分ける。これらのサブ領域７ａ〜７ｃから１箇所ずつ測定位置を選択し、リチウムイオン波長分散型Ｘ線マイクロアナライザを用いて各測定位置の酸素比率を求める。続いて、図２（ｂ）に示すように、各サブ領域７ａ〜７ｃの酸素比率の測定値のうち最大値Ｒｍａｘと最小値Ｒｍｉｎとの差ΔＲを算出する
。なお、複数個の負極活物質体５のそれぞれについて最大値Ｒｍａｘと最小値Ｒｍｉｎとの差を算出し、それらの平均値をΔＲとしてもよい。 FIG. 2A is a schematic enlarged view showing a single negative electrode active material body 5, and shows a cross section perpendicular to the current collector 1 and including the growth direction of the negative electrode active material body 5. . Here, in the cross section shown in the figure, a region 7 that is about 2 μm away from the contact surface between the negative electrode active material body 5 and the current collector 1 toward the negative electrode active material body 5 is taken as a measurement region. The measurement region 7 is divided into at least three sub-regions according to the distance y from one end of the measurement region 7. For example, if one end of the measurement region 7 is y = 0 and the opposite end is y = Y, three sub-regions 7a (y / Y: 0 to 1/3), 7b (y / Y: 1/3) 2/3) and 7c (y / Y: 2/3 to 1). Measurement positions are selected one by one from these sub-regions 7a to 7c, and the oxygen ratio at each measurement position is determined using a lithium ion wavelength dispersion X-ray microanalyzer. Subsequently, as shown in FIG. 2B, the difference ΔR between the maximum value Rmax and the minimum value Rmin among the measured values of the oxygen ratio in each of the sub-regions 7a to 7c is calculated. Note that the difference between the maximum value Rmax and the minimum value Rmin may be calculated for each of the plurality of negative electrode active material bodies 5, and the average value thereof may be ΔR.

なお、上記の測定方法では、集電体１と負極活物質体５との「界面近傍」として、負極活物質体５のうち集電体１の表面との界面から２μｍの領域を測定領域としたが、測定領域は、負極活物質体５のうち集電体１の表面との界面から３μｍ以内の部分から任意に選択することができる。また、負極活物質体５と集電体１との間に他の層が設けられ、負極活物質体５が集電体１の表面に接していない場合でも、負極活物質体５のうち集電体１の側の負極活物質体５の端面から３μｍ以内の部分から測定領域を選択し、上記と同様の方法でΔＲを求めることができる。   In the above measurement method, as the “near the interface” between the current collector 1 and the negative electrode active material body 5, a region of 2 μm from the interface with the surface of the current collector 1 in the negative electrode active material body 5 is defined as the measurement region. However, the measurement region can be arbitrarily selected from a portion within 3 μm from the interface with the surface of the current collector 1 in the negative electrode active material body 5. Even if another layer is provided between the negative electrode active material body 5 and the current collector 1 and the negative electrode active material body 5 is not in contact with the surface of the current collector 1, A measurement region is selected from a portion within 3 μm from the end face of the negative electrode active material body 5 on the side of the electric conductor 1, and ΔR can be obtained by the same method as described above.

既に説明したように、ケイ素酸化物（ＳｉＯｘ、０≦ｘ≦２）は、その酸素含有量によってＬｉの吸蔵量が異なるために、Ｌｉの吸蔵による体積膨張の程度が異なる。例えば、酸素比率がゼロ（Ｓｉ）の場合、Ｓｉ原子１個についてＬｉは４．４個（Ｌｉ22Ｓｉ5）の組成まで、リチウムを吸蔵することができるが、その際の体積膨張は４．４倍になる。一方、酸素比率が２（ＳｉＯ2）になると、リチウムを吸蔵することができないため体積膨張はしない。つまり１倍である。このように、酸素比率（ｘ値）が大きくなるほど、ケイ素酸化物（ＳｉＯx）の体積膨張が小さくなる。 As already described, silicon oxide (SiOx, 0 ≦ x ≦ 2) has different amounts of Li storage depending on its oxygen content, and therefore the degree of volume expansion due to storage of Li varies. For example, when the oxygen ratio is zero (Si), lithium can be occluded up to a composition of Li (Li 22 Si 5 ) per Si atom, but the volume expansion at that time is 4. 4 times. On the other hand, when the oxygen ratio is 2 (SiO 2 ), lithium cannot be occluded, so that volume expansion does not occur. In other words, it is 1 time. Thus, as the oxygen ratio (x value) increases, the volume expansion of silicon oxide (SiO x ) decreases.

従って、集電体と各負極活物質体との界面におけるＳｉＯxの酸素比率の分布幅が大きく、例えば上記ΔＲが０．４よりも大きいと、この界面に体積膨張率が著しく異なる領域
が存在し、充放電に伴うリチウムの吸蔵・放出によって界面の一部に応力集中が生じるおそれがある。そのため、充放電を繰り返すと、負極活物質体５が集電体１から剥離しやすくなり、充放電サイクル特性の低下を引き起こす可能性がある。 Therefore, the distribution range of the oxygen ratio of SiO x at the interface between the current collector and each negative electrode active material body is large. For example, if ΔR is greater than 0.4, there is a region where the volume expansion coefficient is significantly different at this interface. However, stress concentration may occur in a part of the interface due to insertion and extraction of lithium accompanying charging and discharging. Therefore, when charging / discharging is repeated, the negative electrode active material body 5 is easily peeled off from the current collector 1, which may cause deterioration in charge / discharge cycle characteristics.

これに対し、本実施形態では、上記ΔＲが０．４以下に抑えられており、集電体１と負
極活物質体５との界面における酸素比率の分布幅が小さいので、界面における活物質の膨張・収縮の割合を略均一にできる。よって、リチウムの吸蔵・放出によって界面に生じる応力分布も略均一になり、局所的な応力集中が生じないため、負極活物質体５の剥離を抑制でき、良好な充放電サイクル特性が得られる。 On the other hand, in the present embodiment, the ΔR is suppressed to 0.4 or less, and the distribution width of the oxygen ratio at the interface between the current collector 1 and the negative electrode active material body 5 is small. The ratio of expansion / contraction can be made substantially uniform. Therefore, the stress distribution generated at the interface due to insertion and extraction of lithium becomes substantially uniform and local stress concentration does not occur. Therefore, peeling of the negative electrode active material body 5 can be suppressed, and good charge / discharge cycle characteristics can be obtained.

本実施形態のように斜め蒸着を利用して負極活物質体５を形成する場合、集電体１と各負極活物質体５との界面における酸素比率の分布幅を抑えるためには、集電体１に対する活物質（例えばＳｉ原子）の蒸着方向と、集電体１の表面に形成された第１の凸部２Ａおよび第２の凸部２Ｂの形状との関係を制御することが重要となる。   When the negative electrode active material body 5 is formed by using oblique deposition as in the present embodiment, in order to suppress the distribution width of the oxygen ratio at the interface between the current collector 1 and each negative electrode active material body 5, It is important to control the relationship between the vapor deposition direction of the active material (for example, Si atoms) with respect to the body 1 and the shapes of the first and second convex portions 2A and 2B formed on the surface of the current collector 1. Become.

例えば、集電体１の表面に垂直な断面において、集電体１の表面のうち負極活物質体５と接触する部分に９０°以下の「かど（とがって突出した部分、エッジ部）」が存在していないことが好ましい。蒸着方向から見て、集電体１の表面に９０°以下の「かど（以下、「角」とする）」が存在しないことが好ましい。なお、「９０°以下の角が存在しない」とは、第１の凸部２Ａの角が９０°以下であればよく、第１の凸部２Ａに形成された微小な凹凸（第２の凸部２Ｂ）に９０°以下の角があってもよい。ただし、蒸着方向から見て、第１の凸部２Ａのみでなく、第２の凸部２Ｂも９０°以下の角を有していなければかど、より効果的に酸素比率の分布幅を低減できる。また、各第１の凸部２Ａの角は丸みを帯びており、明確な頂点を有していないことが好ましい。   For example, in a cross section perpendicular to the surface of the current collector 1, a portion of the surface of the current collector 1 that is in contact with the negative electrode active material body 5 has a “corner (a protruding portion, an edge portion)” of 90 ° or less. Preferably it is not present. When viewed from the vapor deposition direction, it is preferable that there is no “corner (hereinafter referred to as“ corner ”)” of 90 ° or less on the surface of the current collector 1. Note that “the angle of 90 ° or less does not exist” means that the angle of the first protrusion 2A is 90 ° or less, and the minute unevenness (second protrusion) formed on the first protrusion 2A. The part 2B) may have an angle of 90 ° or less. However, as viewed from the vapor deposition direction, not only the first convex portion 2A but also the second convex portion 2B does not have an angle of 90 ° or less, so the distribution width of the oxygen ratio can be reduced more effectively. . Moreover, it is preferable that the corner | angular of each 1st convex part 2A is roundish, and does not have a clear vertex.

図３（ａ）は、第１の凸部２Ａの断面形状が９０°の角を有する場合、および、図３（ｂ）は第１の凸部２Ａの断面形状が９０°以下の角を有していない場合の蒸着工程を説明するための模式的な断面図である。   FIG. 3A shows a case where the cross-sectional shape of the first convex portion 2A has an angle of 90 °, and FIG. 3B shows that the cross-sectional shape of the first convex portion 2A has an angle of 90 ° or less. It is typical sectional drawing for demonstrating the vapor deposition process in the case of not doing.

図３（ａ）に示すように、集電体１の表面に垂直な断面において、各第１の凸部２Ａが負極活物質体５との接触面で９０°以下の角（図示する例では９０°）を有している場合、集電体１の法線方向Ｎに対して角度θの方向からケイ素原子を入射させる。このとき、ケイ素原子のフラックス（単位面積・単位時間あたりに飛来するケイ素原子の数）をｆとすると、第１の凸部２Ａの上面に位置する領域αに供給されるケイ素原子のフラックスはｆｃｏｓθ、第１の凸部２Ａの側面に位置する領域βに供給されるケイ素原子のフラックスはｆｃｏｓ（９０−θ）で表わされる。蒸着の際の成長レートはフラックスによって決まることから、領域αおよび領域βの上では成長レートが異なり、その結果、ケイ素原子の蒸着時に反応する酸素量も異なるので、酸素比率の異なるケイ素酸化物が堆積する。   As shown in FIG. 3A, in a cross section perpendicular to the surface of the current collector 1, each first protrusion 2 </ b> A has an angle of 90 ° or less on the contact surface with the negative electrode active material body 5 (in the example shown in the figure). 90 °), silicon atoms are incident from the direction of the angle θ with respect to the normal direction N of the current collector 1. At this time, if the flux of silicon atoms (the number of silicon atoms flying per unit area / unit time) is f, the flux of silicon atoms supplied to the region α located on the upper surface of the first convex portion 2A is fcosθ. The flux of silicon atoms supplied to the region β located on the side surface of the first convex portion 2A is represented by fcos (90−θ). Since the growth rate at the time of vapor deposition is determined by the flux, the growth rate is different on the region α and the region β. As a result, the amount of oxygen that reacts during the deposition of silicon atoms is also different. accumulate.

一方、図３（ｂ）に示すように、集電体１の表面に垂直な断面において、第１の凸部２Ａの角が丸みを帯びており、かつ、９０°よりも大きい角度を有している場合には、集電体１の法線方向Ｎに対して角度θの方向からケイ素原子を入射させても、そのような角を含む領域に対するケイ素原子のフラックスに分布が生じにくくなる。従って、第１の凸部２Ａの表面に略均一な速度でケイ素酸化物を成長させることができるので、酸素比率の略均一な負極活物質体５が得られる。なお、第１の凸部２Ａの表面のうち活物質が蒸着される面に９０°以下の角が存在していなければ、酸素比率の分布を抑える効果が得られるので、第１の凸部２Ａの表面のうち活物質が蒸着しない面に９０°以下の角があってもかまわない。例えば、第１の凸部２Ａの断面形状が９０°以下の頂角を有する三角形であっても、第１の凸部２Ａの側面にのみ活物質を入射させるような角度で斜め蒸着を行えば、負極活物質体５の酸素比率の分布を抑えることができる。   On the other hand, as shown in FIG. 3B, in the cross section perpendicular to the surface of the current collector 1, the corners of the first protrusions 2A are rounded and have an angle larger than 90 °. In this case, even if silicon atoms are incident from the direction of the angle θ with respect to the normal direction N of the current collector 1, the distribution of the silicon atom flux with respect to the region including such angles is unlikely to occur. Therefore, since the silicon oxide can be grown on the surface of the first convex portion 2A at a substantially uniform rate, the negative electrode active material body 5 having a substantially uniform oxygen ratio can be obtained. In addition, since the effect which suppresses distribution of an oxygen ratio will be acquired if the angle of 90 degrees or less does not exist in the surface where the active material is vapor-deposited among the surfaces of the 1st convex part 2A, since the effect which suppresses distribution of oxygen ratio is acquired, 1st convex part 2A There may be an angle of 90 ° or less on the surface where no active material is deposited. For example, even if the sectional shape of the first convex portion 2A is a triangle having an apex angle of 90 ° or less, oblique deposition is performed at an angle that allows the active material to enter only the side surface of the first convex portion 2A. The oxygen ratio distribution of the negative electrode active material body 5 can be suppressed.

上述した特許文献２では、集電体として、表面粗さＲｚが２μｍ〜１０μｍの市販の粗面化銅箔を用いている。この銅箔の表面には、多様な形状の凸部がランダムに配置されており、凸部の上に活物質粒子が支持されている。このような場合、一部の活物質粒子は、凸部の形状に依存して、不均一な酸素濃度分布を有すると考えられる。そのため、活物質粒子と集電体との界面における酸素比率の分布幅を、全体として０．４以下に抑えることが困難である。これに対し、本実施形態では、各負極活物質体５を支持するための第１の凸部２Ａの形状が制御されており、第１の凸部２Ａにおけるケイ素原子の入射面には、ケイ素原子の入射方向に対する角度を著しく変化させるような角が存在しないので、負極活物質体５の界面における酸素比率の分布幅を抑えることができる。   In Patent Document 2 described above, a commercially available roughened copper foil having a surface roughness Rz of 2 μm to 10 μm is used as a current collector. Various convex portions are randomly arranged on the surface of the copper foil, and active material particles are supported on the convex portions. In such a case, it is considered that some of the active material particles have a non-uniform oxygen concentration distribution depending on the shape of the convex portion. Therefore, it is difficult to suppress the distribution width of the oxygen ratio at the interface between the active material particles and the current collector to 0.4 or less as a whole. On the other hand, in the present embodiment, the shape of the first convex portion 2A for supporting each negative electrode active material body 5 is controlled, and the silicon atom incident surface in the first convex portion 2A has no silicon. Since there is no angle that significantly changes the angle with respect to the incident direction of the atoms, the distribution width of the oxygen ratio at the interface of the negative electrode active material body 5 can be suppressed.

本実施形態における第１の凸部２Ａは、規則的に配列されていることが好ましく、その配列ピッチＰは例えば１０μｍ以上５０μｍ以下である。配列ピッチＰが1０μｍ以上であれば、負極活物質体５の厚さを増大させることなく、高い容量を確保でき、ピッチＰが５０μｍ以下であれば、隣接する負極活物質体５の間に、負極活物質体５が膨張するための空間をより確実に確保できるからである。また、第１の凸部２Ａの高さｈAは５μｍ以上であることが好ましい。高さｈAが５μｍ以上であれば、負極活物質体５を斜め蒸着で形成する際に、シャドウイング効果を利用して、より確実に負極活物質体５の配置を制御することができる。一方、高さｈAが大きすぎると集電体１が厚くなってしまうため、１０μｍ以下であることが好ましい。 The first convex portions 2A in the present embodiment are preferably arranged regularly, and the arrangement pitch P is, for example, not less than 10 μm and not more than 50 μm. If the arrangement pitch P is 10 μm or more, a high capacity can be secured without increasing the thickness of the negative electrode active material body 5, and if the pitch P is 50 μm or less, between the adjacent negative electrode active material bodies 5, This is because the space for the negative electrode active material body 5 to expand can be more reliably secured. The height h A of the first convex portion 2A is preferably 5 μm or more. When the height h A is 5 μm or more, the placement of the negative electrode active material body 5 can be more reliably controlled using the shadowing effect when the negative electrode active material body 5 is formed by oblique deposition. On the other hand, if the height h A is too large, the current collector 1 becomes thick, and therefore it is preferably 10 μm or less.

第２の凸部２Ｂの高さｈBは、好ましくは１μｍ以上５μｍ以下である。高さｈBがこの範囲内であれば、集電体１と負極活物質体５との付着力を十分に確保できるので、負極活物質体５の剥離を防止できる。 The height h B of the second convex portion 2B is preferably 1 μm or more and 5 μm or less. If the height h B is within this range, the adhesive force between the current collector 1 and the negative electrode active material body 5 can be sufficiently secured, so that the negative electrode active material body 5 can be prevented from peeling off.

第２の凸部２Ｂの高さｈBに対する第１の凸部２Ａの高さｈAの比ｈA／ｈBは、１より大きければよいが、好ましくは２以上である。上記比が小さくなりすぎると、すなわち、第２の凸部２Ｂが高くなりすぎると、第２の凸部２Ｂによるシャドウイング効果が生じて負極活物質体５と集電体１との接触面積が確保できなくなるおそれがあるからである。一方、上記比ｈA／ｈBは２５以下であることが好ましい。これにより、第２の凸部２Ｂによって第１の凸部２Ａと負極活物質体５との密着性を十分に高めることができる。なお、上記比ｈA／ｈBは、より好ましくは２以上１０以下である。 The ratio h A / h B of the height h A of the first protrusion 2A to the height h B of the second protrusion 2B may be larger than 1, but is preferably 2 or more. If the ratio is too small, that is, if the second convex portion 2B is too high, a shadowing effect is generated by the second convex portion 2B, and the contact area between the negative electrode active material body 5 and the current collector 1 is increased. This is because there is a possibility that it cannot be secured. On the other hand, the ratio h A / h B is preferably 25 or less. Thereby, the adhesiveness of 2 A of 1st convex parts and the negative electrode active material body 5 can fully be improved with the 2nd convex part 2B. The ratio h A / h B is more preferably 2 or more and 10 or less.

また、図１に示す断面において、第１の凸部２Ａの幅は５μｍ以上３０μｍ以下であることが好ましい。第１の凸部２Ａの幅が５μｍ未満であれば、負極活物質体５と第１の凸部２Ａとの接触面積を確保できないおそれがある。また、３０μｍよりも大きいと、溝４によって負極活物質体５の膨張応力を効果的に緩和できないおそれがある。   In the cross section shown in FIG. 1, the width of the first convex portion 2A is preferably 5 μm or more and 30 μm or less. If the width of the first convex portion 2A is less than 5 μm, the contact area between the negative electrode active material body 5 and the first convex portion 2A may not be ensured. Moreover, when larger than 30 micrometers, there exists a possibility that the expansion stress of the negative electrode active material body 5 cannot be relieve | moderated effectively by the groove | channel 4.

第２の凸部２Ｂの幅に対する第１の凸部２Ａの幅の比は２以上であることが好ましい。これにより、１つの第１の凸部２Ａの表面により多くの第２の凸部２Ｂが容易に形成できるので、第２の凸部２Ｂによって第１の凸部２Ａと負極活物質体５との密着性を十分に高めることができる。また、上記比は２０以下であることが好ましい。上記比が大きすぎると、すなわち、第２の凸部２Ｂの幅が小さくなりすぎると、負極活物質体５と集電体１との接触面積を十分に確保することが困難となるからである。   The ratio of the width of the first protrusion 2A to the width of the second protrusion 2B is preferably 2 or more. Thereby, since many 2nd convex parts 2B can be easily formed in the surface of one 1st convex part 2A, the 2nd convex part 2B WHEREIN: Between 1st convex part 2A and the negative electrode active material body 5 Adhesion can be sufficiently enhanced. The ratio is preferably 20 or less. This is because if the ratio is too large, that is, if the width of the second protrusion 2B is too small, it is difficult to ensure a sufficient contact area between the negative electrode active material body 5 and the current collector 1. .

次に、図面を参照しながら、負極１００の製造方法の概略を説明する。   Next, an outline of a method for manufacturing the negative electrode 100 will be described with reference to the drawings.

まず、表面に複数の第１の凸部を有する集電体を作製する。集電体の構成材料としては、例えば銅、銅合金などを用いることができる。第１の凸部は、例えば直径または１辺が５μｍ以上３０μｍ以下であり、かつ高さが５μｍ以上１０μｍ以下の半球状、円柱状または角柱状である。また、各第１の凸部の表面には、複数の第２の凸部が配置されている。第２の凸部の高さは、第１の凸部の高さよりも低く、例えば１μｍ以上５μｍ以下である。   First, a current collector having a plurality of first protrusions on the surface is produced. As a constituent material of the current collector, for example, copper, copper alloy, or the like can be used. The first convex portion has, for example, a hemispherical shape, a cylindrical shape, or a prismatic shape having a diameter or one side of 5 μm to 30 μm and a height of 5 μm to 10 μm. A plurality of second convex portions are arranged on the surface of each first convex portion. The height of the second convex portion is lower than the height of the first convex portion, for example, not less than 1 μm and not more than 5 μm.

続いて、斜め蒸着により、上記集電体の表面に複数の負極活物質体を形成する。各負極活物質体は、対応する第１の凸部の上に配置される。   Subsequently, a plurality of negative electrode active material bodies are formed on the surface of the current collector by oblique vapor deposition. Each negative electrode active material body is disposed on the corresponding first convex portion.

図４は、負極活物質体の形成に用いられる蒸着装置の構成を例示する概略図である。この図では、蒸着装置の真空チャンバー内の構成のみを示しており、真空チャンバーの外部の構成は省略している。   FIG. 4 is a schematic view illustrating the configuration of a vapor deposition apparatus used for forming the negative electrode active material body. In this drawing, only the configuration inside the vacuum chamber of the vapor deposition apparatus is shown, and the configuration outside the vacuum chamber is omitted.

図示するように、真空チャンバーの内部には、集電体１を固定するための固定台１１と、チャンバー内に酸素ガスを導入する酸素ノズル１４と、集電体１の表面にケイ素を供給するための蒸発源が装填された坩堝１２とが設置されている。蒸発源として、例えばケイ素を用いることができる。また、図示しないが、蒸発源の材料を蒸発させるための電子ビーム加熱手段を備えている。酸素ノズル１４は、酸素ノズル１４から出射する酸素ガス５が集電体１の表面近傍に供給されるように位置付けられている。固定台１１と坩堝１２とは、坩堝１２からの蒸着粒子（ここではケイ素原子）１６が、集電体１の法線方向Ｎに対して角度（蒸着角度）θの方向から集電体１の表面に入射するように配置されている。この例では、固定台１１は回転軸を有しており、この回転軸のまわりに固定台１１を回転させることによって、水平面１８に対する固定台１１の角度が所定の蒸着角度θに等しくなるように調整される。ここで、「水平面」とは、坩堝１２に装填された蒸発源の材料が気化されて固定台１１に向う方向に対して垂直な面をいう。   As shown in the drawing, inside the vacuum chamber, a fixing base 11 for fixing the current collector 1, an oxygen nozzle 14 for introducing oxygen gas into the chamber, and silicon are supplied to the surface of the current collector 1. And a crucible 12 loaded with an evaporation source. For example, silicon can be used as the evaporation source. Further, although not shown, an electron beam heating means for evaporating the material of the evaporation source is provided. The oxygen nozzle 14 is positioned so that the oxygen gas 5 emitted from the oxygen nozzle 14 is supplied near the surface of the current collector 1. The fixed base 11 and the crucible 12 are arranged such that vapor deposition particles (silicon atoms in this case) 16 from the crucible 12 form the current collector 1 from the direction of an angle (deposition angle) θ with respect to the normal direction N of the current collector 1. It arrange | positions so that it may inject into the surface. In this example, the fixed base 11 has a rotation axis. By rotating the fixed base 11 around the rotation axis, the angle of the fixed base 11 with respect to the horizontal plane 18 becomes equal to a predetermined deposition angle θ. Adjusted. Here, the “horizontal plane” refers to a plane perpendicular to the direction in which the material of the evaporation source charged in the crucible 12 is vaporized and faces the fixed base 11.

負極活物質体５の形成は、集電体１の表面近傍に酸素ノズル１４から酸素ガス１５を吹き付けながら、坩堝１２に装填したケイ素を電子（ＥＢ）銃（図示せず）で電子線を照射して溶解し、集電体１の上に入射させることによって行う（ＥＢ蒸着）。集電体１の表面では、ケイ素原子１６と酸素ガス１５とが反応してケイ素酸化物が成長する。このとき、ケイ素原子１６は、集電体１の法線方向に対して傾斜した方向から集電体３の表面に入射するために、集電体３の表面における第１の凸部（図１に示す凸部２Ａ）の上に蒸着しやすく、凸部上でのみケイ素酸化物が柱状に成長する。一方、集電体３の表面のうち柱状に成長していくケイ素酸化物の影となる部分では、Ｓｉ原子が入射せず、ケイ素酸化物は蒸着しない（シャドウイング効果）。   The negative electrode active material body 5 is formed by irradiating an electron beam with silicon (electron (EB) gun (not shown)) loaded on the crucible 12 while blowing an oxygen gas 15 from the oxygen nozzle 14 near the surface of the current collector 1. Then, it is melted and incident on the current collector 1 (EB vapor deposition). On the surface of the current collector 1, silicon atoms 16 and oxygen gas 15 react to grow silicon oxide. At this time, since the silicon atoms 16 are incident on the surface of the current collector 3 from a direction inclined with respect to the normal direction of the current collector 1, the first protrusions on the surface of the current collector 3 (FIG. 1). It is easy to vapor-deposit on the convex part 2A), and silicon oxide grows in a column shape only on the convex part. On the other hand, in the shadowed portion of the silicon oxide that grows in a columnar shape on the surface of the current collector 3, Si atoms do not enter and silicon oxide is not deposited (shadowing effect).

このようにして、集電体１の各凸部上に複数の負極活物質体が形成され、負極１００が完成する。負極活物質体における酸素比率の平均値は、真空チャンバー内に導入する酸素ガス量（すなわち雰囲気の酸素濃度）を調整することにより制御できる。   In this way, a plurality of negative electrode active material bodies are formed on each convex portion of the current collector 1, and the negative electrode 100 is completed. The average value of the oxygen ratio in the negative electrode active material body can be controlled by adjusting the amount of oxygen gas introduced into the vacuum chamber (that is, the oxygen concentration in the atmosphere).

なお、上記方法において、蒸着角度θを一定にして負極活物質体の形成を行うと、図１に示すように特定の方向に沿って成長した負極活物質体が得られる。また、ＥＢ蒸着を行っている間に、固定台１１を回転軸に沿って回転させて集電体１の設置方向を変えることにより、蒸着角度θを変化させてもよい。この場合には、成長方向の異なる複数の部分を有する負極活物質体が得られる。   In the above method, when the negative electrode active material body is formed with the vapor deposition angle θ kept constant, a negative electrode active material body grown along a specific direction is obtained as shown in FIG. Further, during the EB vapor deposition, the vapor deposition angle θ may be changed by rotating the fixed base 11 along the rotation axis to change the installation direction of the current collector 1. In this case, a negative electrode active material body having a plurality of portions with different growth directions is obtained.

図５は、本実施形態の負極の他の構成を例示する模式的な断面図であり、各負極活物質体は、成長方向の異なる複数の部分を有している。   FIG. 5 is a schematic cross-sectional view illustrating another configuration of the negative electrode of the present embodiment, and each negative electrode active material body has a plurality of portions having different growth directions.

図示する例では、各負極活物質体５は、成長方向Ｇによって７つの部分ｐ１〜ｐ７に分けられる。このような負極活物質体５は、蒸着方向を変化させて複数段階の蒸着を行うことによって得られる。各負極活物質体５における複数の部分ｐ１〜ｐ７の成長方向は、全て異なっていてもよい。また、複数の部分ｐ１〜ｐ７の成長方向は、負極活物質体５ごとに同じであってもよいし、異なっていてもよい。   In the illustrated example, each negative electrode active material body 5 is divided into seven portions p1 to p7 according to the growth direction G. Such a negative electrode active material body 5 is obtained by performing a plurality of stages of vapor deposition by changing the vapor deposition direction. The growth directions of the plurality of portions p1 to p7 in each negative electrode active material body 5 may all be different. Moreover, the growth directions of the plurality of portions p1 to p7 may be the same for each negative electrode active material body 5 or may be different.

次に、図面を参照しながら、本実施形態の負極を適用して得られたリチウム二次電池の構成を、円筒型リチウム二次電池（以下、単に「円筒型電池」ともいう）を例に説明する。   Next, referring to the drawings, the configuration of the lithium secondary battery obtained by applying the negative electrode of the present embodiment is taken as an example of a cylindrical lithium secondary battery (hereinafter also simply referred to as “cylindrical battery”). explain.

図６は、本実施例の負極を用いた円筒型電池の概略断面図である。図６において円筒型電池６０は、円筒型の電極群６４と、これを収容する電池缶６８とを有する。電極群６４は、帯状の正極板６１と帯状の負極板６２とを、それらの間に配置された幅広のセパレータ６３とともに捲回することによって得られる。電極群６４には、リチウムイオンを伝導する電解質（図示せず）が含浸されている。電池缶６８の開口は、正極端子６５を有する封口板６９で塞がれている。正極板６１には、アルミニウム製の正極リード６１ａの一方の端が接続されており、他方の端は封口板６９の裏面に接続されている。封口板６９の周縁には、ポリプロピレン製の絶縁パッキン６６が配置されている。負極板６２には、銅製の負極リード（図示せず）の一方の端が接続されており、他方の端は電池缶６８に接続されている。電極群６４の上下には、それぞれ上部絶縁リング（図示せず）および下部絶縁リング６７が配置されている。   FIG. 6 is a schematic cross-sectional view of a cylindrical battery using the negative electrode of this example. In FIG. 6, a cylindrical battery 60 includes a cylindrical electrode group 64 and a battery can 68 that accommodates the electrode group 64. The electrode group 64 is obtained by winding a belt-like positive electrode plate 61 and a belt-like negative electrode plate 62 together with a wide separator 63 disposed therebetween. The electrode group 64 is impregnated with an electrolyte (not shown) that conducts lithium ions. The opening of the battery can 68 is closed by a sealing plate 69 having a positive electrode terminal 65. One end of an aluminum positive electrode lead 61 a is connected to the positive electrode plate 61, and the other end is connected to the back surface of the sealing plate 69. An insulating packing 66 made of polypropylene is disposed on the periphery of the sealing plate 69. One end of a copper negative electrode lead (not shown) is connected to the negative electrode plate 62, and the other end is connected to the battery can 68. An upper insulating ring (not shown) and a lower insulating ring 67 are disposed above and below the electrode group 64, respectively.

なお、本実施形態の負極を備えたリチウム二次電池の構成は、図６に示す構成に限定されない。本実施形態の負極は、円筒型の他に、コイン型、扁平型、角形等の様々な形状のリチウム二次電池に適用可能である。また、リチウム二次電池の封止形態や電池を構成する各要素の材料も特に限定されない。リチウム二次電池以外の非水電解質二次電池にも適用できる。   In addition, the structure of the lithium secondary battery provided with the negative electrode of this embodiment is not limited to the structure shown in FIG. The negative electrode of the present embodiment is applicable to lithium secondary batteries having various shapes such as a coin shape, a flat shape, and a square shape in addition to a cylindrical shape. Further, the sealing form of the lithium secondary battery and the material of each element constituting the battery are not particularly limited. It can also be applied to non-aqueous electrolyte secondary batteries other than lithium secondary batteries.

また、本発明のリチウム二次電池の各構成要素は、本発明の負極を用いる以外は、特に限定されるものではなく、本発明の効果を損なわない範囲でリチウムイオン電池用の材料として一般的に使用される種々のものを選択することが可能である。   Further, each component of the lithium secondary battery of the present invention is not particularly limited except that the negative electrode of the present invention is used, and is generally used as a material for a lithium ion battery within a range not impairing the effects of the present invention. It is possible to select various types used in the above.

（実施例１）
以下、本発明による負極の実施例１を説明する。ここでは、実施例として、成長方向の異なる複数の部分を有する負極活物質体を備えた負極を作製し、酸素比率の測定および特性の評価を行ったので、その方法および結果を説明する。 Example 1
Example 1 of the negative electrode according to the present invention will be described below. Here, as an example, a negative electrode provided with a negative electrode active material body having a plurality of portions having different growth directions was prepared, and the oxygen ratio was measured and the characteristics were evaluated. The method and results will be described.

（ｉ）負極の作製方法
＜集電体の作製＞
図７（ａ）〜（ｃ）は、本実施例における集電体の作製方法を説明するための断面工程図である。まず、図７（ａ）に示すように、表面粗さＲｚが１．５〜７μｍの銅箔（厚さ：２７μｍ）２３を用意した。なお、表面粗さＲｚは日本工業規格（ＪＩＳＢ ０６０１―１９９４）に定められた十点平均粗さＲｚを指す。ここでは、プリント配線基板用に市販されている粗面化銅箔（古河サーキットフォイル株式会社製）を用いた。 (I) Production method of negative electrode <Production of current collector>
7A to 7C are cross-sectional process diagrams for explaining a method of manufacturing a current collector in this example. First, as shown in FIG. 7A, a copper foil (thickness: 27 μm) 23 having a surface roughness Rz of 1.5 to 7 μm was prepared. The surface roughness Rz refers to a ten-point average roughness Rz defined in Japanese Industrial Standard (JISB 0601-1994). Here, the roughened copper foil (made by Furukawa Circuit Foil Co., Ltd.) marketed for printed wiring boards was used.

次いで、図７（ｂ）に示すように、第１の凸部を規定する複数の凹部２１を有するステンレスローラー２０と、これに対向するように配置された他のローラー（図示せず）との間に、銅箔２３を線圧１．５ｔ／ｃｍで通過させた。このようにして、図７（ｃ）に示すような集電体１を得た。   Next, as shown in FIG. 7 (b), a stainless roller 20 having a plurality of recesses 21 that define the first protrusions, and another roller (not shown) arranged to face the stainless roller 20 In the meantime, the copper foil 23 was passed at a linear pressure of 1.5 t / cm. In this way, a current collector 1 as shown in FIG.

ステンレスローラー２０のパターンの平面図および断面図を図８（ａ）および（ｂ）に示す。図示するように、ステンレスローラー２０は、規則的に配列された複数の凹部２１を有し、各凹部２１は、ステンレスローラー２０の法線方向から見て菱形とした。菱形の対角線の長さａ、ｂは、それぞれ、１０μｍおよび２０μｍであった。隣接する凹部２１の対角線ａに沿った間隔ｅを２０μｍ、対角線ｂに沿った間隔ｄを１０μｍ、菱形の辺に平行な方向における間隔ｃを１０μｍとした。従って、菱形における短い方の対角線ａに平行な方向２５における凹部の配列ピッチＰは３０μｍ（Ｐ＝ａ＋ｅ）となった。また、各凹部２１の深さＨは１０μｍであった。   A plan view and a sectional view of the pattern of the stainless roller 20 are shown in FIGS. As shown in the figure, the stainless steel roller 20 has a plurality of concave portions 21 regularly arranged, and each concave portion 21 has a rhombus shape when viewed from the normal direction of the stainless steel roller 20. The diagonal lengths a and b of the rhombus were 10 μm and 20 μm, respectively. The distance e along the diagonal line a of the adjacent recesses 21 was 20 μm, the distance d along the diagonal line b was 10 μm, and the distance c in the direction parallel to the rhombus sides was 10 μm. Therefore, the arrangement pitch P of the recesses in the direction 25 parallel to the shorter diagonal line a in the rhombus was 30 μm (P = a + e). Moreover, the depth H of each recessed part 21 was 10 micrometers.

ローラー間を通過した銅箔２３のうち、ステンレスローラー２０の凹部２１以外の部分でプレスされた領域は、図示するように平坦化された。一方、銅箔２３のうち凹部２１に対応する領域は、平坦化されずに凹部２１に入り込み、第１の凸部２Ａが形成された。第１の凸部２Ａの高さは、ステンレスローラー２０の凹部２１の深さＨより小さく、約
６μｍであった。得られた第１の凸部２Ａの角は丸みを帯びた形状となった。また、第１の凸部２Ａの表面には、銅箔２３の表面凹凸に対応して第２の凸部２Ｂが形成されており、第２の凸部２Ｂの高さは約２μｍであった。第２の凸部２Ｂの形状は、銅箔２３に含まれていた各凸部よりも丸みを帯びていた。 Of the copper foil 23 that passed between the rollers, the area that was pressed at a portion other than the recess 21 of the stainless roller 20 was flattened as shown in the figure. On the other hand, the region of the copper foil 23 corresponding to the concave portion 21 entered the concave portion 21 without being flattened, and the first convex portion 2A was formed. The height of the first convex portion 2A was smaller than the depth H of the concave portion 21 of the stainless roller 20, and was about 6 μm. The corners of the obtained first convex portion 2A were rounded. In addition, a second protrusion 2B was formed on the surface of the first protrusion 2A corresponding to the surface unevenness of the copper foil 23, and the height of the second protrusion 2B was about 2 μm. . The shape of the 2nd convex part 2B was roundish rather than each convex part contained in the copper foil 23. FIG.

＜負極活物質体の形成＞
上記（ｉ）の方法で得られた集電体１を、図４に示す真空チャンバー内の固定台１１に設置し、酸素ガス５を３０ｓｃｃｍで集電体１の表面に供給しながら、ケイ素を蒸発源とするＥＢ蒸着を行った。蒸着にあたり、固定台１１を、水平面１８と６０°の角度をなすように（θ＝６０°）傾斜させ、この状態で１５分間の蒸着を行った（第１段目の蒸着工程）。このとき、ケイ素単体の蒸発源に照射する電子ビームの加速電圧を−９ｋＶとし、エミッションを４００ｍＡに設定した。ケイ素の蒸気は、真空チャンバーに導入された酸素ガス５とともに、固定台１１に設置された集電体１の表面に供給され、その結果、集電体１の上にケイ素と酸素とを含む化合物（ＳｉＯx）が堆積された。 <Formation of negative electrode active material>
The current collector 1 obtained by the above method (i) is placed on the fixed base 11 in the vacuum chamber shown in FIG. 4, while supplying oxygen gas 5 to the surface of the current collector 1 at 30 sccm, silicon is added. EB vapor deposition was performed as an evaporation source. In the vapor deposition, the fixing base 11 was inclined so as to form an angle of 60 ° with the horizontal plane 18 (θ = 60 °), and vapor deposition was performed in this state for 15 minutes (first vapor deposition step). At this time, the acceleration voltage of the electron beam applied to the evaporation source of silicon alone was set to −9 kV, and the emission was set to 400 mA. The silicon vapor is supplied to the surface of the current collector 1 installed on the fixed base 11 together with the oxygen gas 5 introduced into the vacuum chamber, and as a result, a compound containing silicon and oxygen on the current collector 1. (SiO x ) was deposited.

続いて、固定台１１を中心軸のまわりに時計回りに回転させ、水平面１８に対して、上記第１段目の蒸着工程における固定台１１の傾斜方向と反対の方向に６０°の角度をなすように（θ＝−６０°）傾斜させた。この状態で、上記第１段目の蒸着工程と同様の条件で１５分間の蒸着を行った（第２段目の蒸着工程）。   Subsequently, the fixing base 11 is rotated clockwise around the central axis, and an angle of 60 ° is formed with respect to the horizontal plane 18 in a direction opposite to the inclination direction of the fixing base 11 in the first stage vapor deposition step. (Θ = −60 °). In this state, the deposition was performed for 15 minutes under the same conditions as the first-stage deposition process (second-stage deposition process).

この後、固定台１１の傾斜角度を再び第１段目の蒸着工程と同じ角度（θ＝６０°）に戻し、同様の蒸着を行った（第３段目の蒸着工程）。このようにして、固定台１１の傾斜角度θを６０°および−６０°との間で交互に切り換えて、第７段目まで蒸着を行い、負極活物質体を得た。   After that, the inclination angle of the fixed base 11 was returned again to the same angle (θ = 60 °) as that in the first stage vapor deposition step, and the same vapor deposition was performed (third vapor deposition step). In this manner, the inclination angle θ of the fixing base 11 was alternately switched between 60 ° and −60 °, and vapor deposition was performed up to the seventh stage to obtain a negative electrode active material body.

（ｉｉ）分析
＜電子顕微鏡による観察＞
上記方法で得られた負極活物質体の断面を電子顕微鏡で観察した。図９（ａ）および図１０（ａ）は、集電体表面に垂直な断面における負極活物質体の形状を示す電子顕微鏡写真であり、図９（ａ）は、負極活物質体の蒸着方向を含む断面図であり、図１０（ａ）は、集電体表面において蒸着方向と垂直な方向に沿った断面図である。 (Ii) Analysis <Observation with an electron microscope>
The cross section of the negative electrode active material obtained by the above method was observed with an electron microscope. 9 (a) and 10 (a) are electron micrographs showing the shape of the negative electrode active material body in a cross section perpendicular to the current collector surface, and FIG. 9 (a) is the deposition direction of the negative electrode active material body. FIG. 10A is a cross-sectional view along the direction perpendicular to the vapor deposition direction on the current collector surface.

図９（ａ）から、負極活物質体５は、その蒸着方向に起因して、ジグザグ状の断面形状を有していることがわかった。また、図１０（ａ）からは、負極活物質体５が、蒸着方向の異なる複数の層が積み重なった構造を有することがわかった。さらに、集電体１の表面における凸部の断面形状は、明確な９０°以下の角度を有していないことが確認された。   FIG. 9A shows that the negative electrode active material body 5 has a zigzag cross-sectional shape due to the deposition direction. Moreover, from FIG. 10A, it was found that the negative electrode active material body 5 had a structure in which a plurality of layers having different vapor deposition directions were stacked. Furthermore, it was confirmed that the cross-sectional shape of the convex portion on the surface of the current collector 1 does not have a clear angle of 90 ° or less.

＜負極活物質体における酸素比率の平均値の測定＞
負極活物質体の酸素比率（ケイ素量に対する酸素量のモル比）の平均値は、負極活物質体５が形成された集電体１の表面から蛍光Ｘ線測定を行うことによって測定した。この結果、酸素比率の平均値は０．５８であった。 <Measurement of average value of oxygen ratio in negative electrode active material>
The average value of the oxygen ratio of the negative electrode active material body (molar ratio of the oxygen amount to the silicon amount) was measured by performing fluorescent X-ray measurement from the surface of the current collector 1 on which the negative electrode active material body 5 was formed. As a result, the average value of the oxygen ratio was 0.58.

＜負極活物質体と集電体との界面近傍における酸素比率分布＞
集電体１と負極活物質体５との界面における酸素比率は、図２を参照しながら上述したように、波長分散型Ｘ線マイクロアナライザ（日本電子製 ＪＸＡ−８９００）を用いて行った。具体的には、まず、試料を樹脂で固めた後、これを研磨することによって図９（ａ）に対応する研磨断面を形成した。次いで、得られた研磨断面に対してカーボンコーティングを行った。この後、波長分散型Ｘ線マイクロアナライザにより、負極活物質体５の組成分析を行った。加速電圧は５ｋＶとした。本実施例では、図１０（ａ）に対応する負極活物質体の断面に対しても同様の組成分析を行った。 <Oxygen ratio distribution in the vicinity of the interface between the negative electrode active material body and the current collector>
As described above with reference to FIG. 2, the oxygen ratio at the interface between the current collector 1 and the negative electrode active material body 5 was measured using a wavelength dispersive X-ray microanalyzer (JXA-8900 manufactured by JEOL). Specifically, first, a sample was hardened with a resin and then polished to form a polished cross section corresponding to FIG. Next, carbon coating was performed on the obtained polished cross section. Then, the composition analysis of the negative electrode active material body 5 was performed with the wavelength dispersion type | mold X-ray microanalyzer. The acceleration voltage was 5 kV. In this example, the same composition analysis was performed on the cross section of the negative electrode active material body corresponding to FIG.

図９（ａ）、図１０（ａ）に示す研磨断面における酸素マップおよびケイ素マップを、それぞれ図９（ｂ）、（ｃ）および図１０（ｂ）、（ｃ）に示す。これらのマップのＸ線強度から集電体１と負極活物質体５との界面における酸素比率を算出した。   The oxygen map and the silicon map in the polished cross section shown in FIGS. 9A and 10A are shown in FIGS. 9B and 10C, and FIGS. 10B and 10C, respectively. From the X-ray intensity of these maps, the oxygen ratio at the interface between the current collector 1 and the negative electrode active material body 5 was calculated.

図示するマップは、測定で得られたカラー像を白黒コピーしたものであり、明度によって各元素の濃度分布が表わされている。図９（ｂ）および図１０（ｂ）から、負極活物質体５における酸素濃度分布は略均一であることがわかった。また、図９（ｃ）からわかるように、負極活物質体５の中央付近では、図９（ａ）に示す負極活物質体５の形状に対応して、ケイ素濃度の低い領域が縦に延びているが、負極活物質体５と集電体１との界面近傍におけるケイ素濃度の分布は略均一となっていた。図１０（ｃ）に示す断面では、負極活物質体５におけるケイ素濃度は略均一であった。   The map shown is a black and white copy of a color image obtained by measurement, and the concentration distribution of each element is represented by brightness. From FIG. 9B and FIG. 10B, it was found that the oxygen concentration distribution in the negative electrode active material body 5 was substantially uniform. Further, as can be seen from FIG. 9C, in the vicinity of the center of the negative electrode active material body 5, a region having a low silicon concentration extends vertically corresponding to the shape of the negative electrode active material body 5 shown in FIG. However, the distribution of the silicon concentration in the vicinity of the interface between the negative electrode active material body 5 and the current collector 1 was substantially uniform. In the cross section shown in FIG. 10C, the silicon concentration in the negative electrode active material body 5 was substantially uniform.

図９（ａ）に示すｍ１、ｍ２、ｍ３および図１０（ａ）に示すｍ４、ｍ５、ｍ６の６点を測定位置とし、それぞれの酸素比率を定量したところ、表１に示すような値が得られた。表１からわかるように、酸素比率の最大値Ｒｍａｘと最小値Ｒｍｉｎとの差ΔＲは０．
３８であった。 When the six oxygen oxygen ratios m1, m2, and m3 shown in FIG. 9 (a) and m4, m5, and m6 shown in FIG. 10 (a) were measured positions, and the respective oxygen ratios were quantified, the values shown in Table 1 were obtained. Obtained. As can be seen from Table 1, the difference ΔR between the maximum value Rmax and the minimum value Rmin of the oxygen ratio is 0.
38.

（ｉｉｉ）電池の作製および評価
＜電池の作製＞
本実施例では、図６を参照しながら前述した構成の円筒型の電池を、以下のようにして作製した。 (Iii) Production and evaluation of battery <Production of battery>
In this example, a cylindrical battery having the above-described configuration with reference to FIG. 6 was produced as follows.

まず、上記（ｉ）の方法で集電体１の上に負極活物質体５を形成することによって、円筒型電池用の負極板６２を作製した。また、ニッケル酸リチウムを主体とする活物質をＡｌ箔上に塗工することによって正極板６１を得た。次いで、負極板６２と正極板６１とをポリエチレン製セパレータ６３を介して対向させて捲回することにより、電極群６４を構成した。この電極群６４を電池缶６８に挿入し、電解液を注入した後、封口板６９を設置した。このようにして、１８６５０サイズの円筒型の電池を得た。   First, a negative electrode plate 62 for a cylindrical battery was produced by forming the negative electrode active material body 5 on the current collector 1 by the method (i). Moreover, the positive electrode plate 61 was obtained by coating the active material which has lithium nickelate as a main body on Al foil. Next, the negative electrode plate 62 and the positive electrode plate 61 were wound so as to face each other with a polyethylene separator 63 therebetween, whereby an electrode group 64 was configured. After this electrode group 64 was inserted into the battery can 68 and the electrolyte was injected, a sealing plate 69 was installed. In this way, a 18650 size cylindrical battery was obtained.

＜評価方法および結果＞
上記（ｉｉｉ）の方法で作製した電池に対して、１Ｃ相当の電流で繰り返し充放電試験を行った。図１１は、充放電試験の結果得られた充放電サイクル特性を示す図であり、縦軸は容量維持率（％）、横軸はサイクル数（回）を表している。図１１に示す結果から、本実施例の電池は、優れた充放電サイクル特性を有することを確認した。 <Evaluation method and results>
The battery produced by the method (iii) was repeatedly subjected to a charge / discharge test at a current equivalent to 1C. FIG. 11 is a diagram showing the charge / discharge cycle characteristics obtained as a result of the charge / discharge test. The vertical axis represents the capacity retention rate (%), and the horizontal axis represents the number of cycles (times). From the results shown in FIG. 11, it was confirmed that the battery of this example had excellent charge / discharge cycle characteristics.

また、充放電試験を行った後、電池を分解して負極板６２を観察したところ、負極活物質が集電体１から剥離したり脱落している様子は認められなかった。   Further, after the charge / discharge test was performed, the battery was disassembled and the negative electrode plate 62 was observed. As a result, it was not observed that the negative electrode active material was peeled off or removed from the current collector 1.

（比較例１）
以下、本発明による負極の比較例１を説明する。比較例１では、実施例１とは異なる方法で集電体を作製する点で、実施例１と異なっている。 (Comparative Example 1)
Hereinafter, Comparative Example 1 of the negative electrode according to the present invention will be described. Comparative Example 1 differs from Example 1 in that the current collector is produced by a method different from Example 1.

（ｉ）負極の作製方法
まず、圧延銅箔（厚さ：２７μｍ）の上にネガ型フォトレジストを塗布し、複数の菱形のパターンを有するネガ型マスクを用いて、ネガ型フォトレジストの露光・現像を行った。これによって、フォトレジストに複数の開口部が形成された。続いて、これらの開口部に電解法により銅粒子を析出させた後、フォトレジストを除去した。このようにして、銅箔の上に、菱形の上面を有する柱状の凸部を形成し、集電体を得た。 (I) Method for producing negative electrode First, a negative photoresist is applied onto a rolled copper foil (thickness: 27 μm), and the negative photoresist is exposed using a negative mask having a plurality of rhombus patterns. Developed. This formed a plurality of openings in the photoresist. Subsequently, after the copper particles were deposited by electrolytic method in these openings, the photoresist was removed. Thus, the columnar convex part which has a rhombus upper surface was formed on copper foil, and the electrical power collector was obtained.

得られた集電体では、集電体表面の各凸部の高さは１０μｍ、凸部の上面の表面粗さＲｚは０．９μｍであった。また、凸部の上面における菱形の対角線の長さは２８μｍおよび１２μｍ、隣接する凹部の短い方の対角線に沿った間隔を１８μｍ、長い方の対角線に沿った間隔を２０μｍ、菱形の辺に平行な間隔を１５μｍであった。さらに、集電体表面に垂直な断面において、各凸部の上面と側面とのなす角度は略９０°であった。   In the obtained current collector, the height of each convex portion on the surface of the current collector was 10 μm, and the surface roughness Rz of the upper surface of the convex portion was 0.9 μm. In addition, the lengths of the rhombus diagonals on the upper surface of the convex part are 28 μm and 12 μm, the distance along the shorter diagonal line of the adjacent concave part is 18 μm, the distance along the longer diagonal line is 20 μm, and is parallel to the side of the rhombus The interval was 15 μm. Further, in the cross section perpendicular to the current collector surface, the angle formed between the upper surface and the side surface of each convex portion was approximately 90 °.

上記のようにして得られた集電体の表面に、実施例１と同様の方法で、ケイ素の入射方向を７段階で変化させながら斜め蒸着を行い、負極活物質体を形成した。   Diagonal vapor deposition was performed on the surface of the current collector obtained as described above in the same manner as in Example 1 while changing the incident direction of silicon in seven steps to form a negative electrode active material body.

（ｉｉ）分析
得られた負極活物質体の酸素比率の平均値を、実施例１と同様の方法で測定したところ、０．６２であった。また、実施例１と同様の方法で、負極活物質体と集電体との界面近傍に位置する６点の酸素比率を測定し、その最大値および最小値の差ΔＲを算出したとこ
ろ、０．８２であった。 (Ii) Analysis When the average value of the oxygen ratio of the obtained negative electrode active material body was measured by the same method as in Example 1, it was 0.62. Further, the oxygen ratio at six points located in the vicinity of the interface between the negative electrode active material body and the current collector was measured in the same manner as in Example 1, and the difference ΔR between the maximum value and the minimum value was calculated. .82.

（ｉｉｉ）電池の作製および評価
比較例１の負極板を用いて、図６に示す構成を有する円筒型電池を作製し、その充放電サイクル試験を行った。電池の作製方法および試験方法は実施例１で説明した方法と同様とした。 (Iii) Production and Evaluation of Battery Using the negative electrode plate of Comparative Example 1, a cylindrical battery having the configuration shown in FIG. 6 was produced, and a charge / discharge cycle test was performed. The battery fabrication method and test method were the same as those described in Example 1.

図１２は、充放電サイクル試験の結果得られた充放電サイクル特性を示す図である。図１２に示す結果から、比較例１の電池では、初期から放電容量が著しく低下し、１５０サイクル後には最大容量の５０％程度になることがわかった。   FIG. 12 is a diagram showing charge / discharge cycle characteristics obtained as a result of the charge / discharge cycle test. From the results shown in FIG. 12, it was found that in the battery of Comparative Example 1, the discharge capacity was remarkably reduced from the initial stage and reached about 50% of the maximum capacity after 150 cycles.

充放電試験を行った後、電池を分解して負極板を観察したところ、負極活物質の一部が集電体から剥離していることを確認した。よって、比較例１では、充放電の繰り返すと、負極活物質体の界面における酸素比率分布に起因して負極活物質が集電体表面から剥離し、その結果、放電容量を低下させると考えられた。   After conducting the charge / discharge test, the battery was disassembled and the negative electrode plate was observed. As a result, it was confirmed that a part of the negative electrode active material was peeled from the current collector. Thus, in Comparative Example 1, it is considered that when charging / discharging is repeated, the negative electrode active material peels from the current collector surface due to the oxygen ratio distribution at the interface of the negative electrode active material body, and as a result, the discharge capacity is reduced. It was.

（実施例２）
以下、本発明による負極の実施例２を説明する。ここでは、実施例１と同様の方法で作製された集電体を用いて、斜め蒸着により一方向に成長させた負極活物質体を備えた負極を作製し、酸素比率の測定および特性の評価を行ったので、その方法および結果を説明する。 (Example 2)
Hereinafter, Example 2 of the negative electrode according to the present invention will be described. Here, a negative electrode provided with a negative electrode active material body grown in one direction by oblique vapor deposition was produced using a current collector produced in the same manner as in Example 1, and measurement of oxygen ratio and evaluation of characteristics were performed. The method and result will be described.

（ｉ）負極の作製方法
実施例１と同様の方法で作製した集電体１を、図４に示す真空チャンバー内の固定台１１に設置し、酸素ガス５を３０ｓｃｃｍで集電体１の表面に供給しながら、ケイ素を蒸発源とするＥＢ蒸着を行った。蒸着にあたり、固定台１１を、水平面１８と６０°の角度をなすように（θ＝６０°）傾斜させ、この状態で５０分間の蒸着を行った。このとき、ケイ素単体の蒸発源に照射する電子ビームの加速電圧を−９ｋＶとし、エミッションを４００ｍＡに設定した。ケイ素の蒸気は、真空チャンバーに導入された酸素ガス５とともに、固定台１１に設置された集電体１の表面に供給され、その結果、集電体１の上にケイ素と酸素とを含む化合物が成長した。このようにして、集電体１の表面に負極活物質体５を形成した。 (I) Method for Producing Negative Electrode The current collector 1 produced by the same method as in Example 1 was placed on the fixed base 11 in the vacuum chamber shown in FIG. 4, and the surface of the current collector 1 was charged with oxygen gas 5 at 30 sccm. EB deposition using silicon as an evaporation source was performed. In the vapor deposition, the fixing base 11 was inclined so as to form an angle of 60 ° with the horizontal plane 18 (θ = 60 °), and vapor deposition was performed in this state for 50 minutes. At this time, the acceleration voltage of the electron beam applied to the evaporation source of silicon alone was set to −9 kV, and the emission was set to 400 mA. The silicon vapor is supplied to the surface of the current collector 1 installed on the fixed base 11 together with the oxygen gas 5 introduced into the vacuum chamber, and as a result, a compound containing silicon and oxygen on the current collector 1. Has grown. Thus, the negative electrode active material body 5 was formed on the surface of the current collector 1.

（ｉｉ）分析
＜電子顕微鏡による観察＞
図１３（ａ）は、実施例２における単一の負極活物質体の電子顕微鏡写真であり、集電体表面に垂直で、かつ、蒸着方向を含む断面を示す。この図から、各負極活物質体５は、特定の方向に傾斜した断面形状を有していることを確認した。また、集電体１の表面における凸部の断面形状は、明確な９０°以下の角度を有していないことがわかった。 (Ii) Analysis <Observation with an electron microscope>
FIG. 13A is an electron micrograph of a single negative electrode active material body in Example 2, showing a cross section perpendicular to the current collector surface and including the vapor deposition direction. From this figure, it was confirmed that each negative electrode active material body 5 had a cross-sectional shape inclined in a specific direction. Moreover, it turned out that the cross-sectional shape of the convex part in the surface of the electrical power collector 1 does not have a clear angle of 90 degrees or less.

＜負極活物質体における酸素比率の平均値の測定＞
負極活物質体の酸素比率（ケイ素量に対する酸素量のモル比）の平均値を、実施例１と同様に蛍光Ｘ線測定で求めたところ、０．５６であった。 <Measurement of average value of oxygen ratio in negative electrode active material>
When the average value of the oxygen ratio (molar ratio of the oxygen amount to the silicon amount) of the negative electrode active material body was determined by fluorescent X-ray measurement in the same manner as in Example 1, it was 0.56.

＜負極活物質体と集電体との界面近傍における酸素比率分布＞
集電体１と負極活物質体５との界面近傍における酸素比率を、波長分散型Ｘ線マイクロアナライザを用いて測定した。測定は、実施例１と同様の方法で行った。ただし、実施例１では、互いに直交する２方向の断面に対して組成分析を行ったが、本実施例では、図１３（ａ）に示す断面に対する組成分析のみを行った。 <Oxygen ratio distribution in the vicinity of the interface between the negative electrode active material body and the current collector>
The oxygen ratio in the vicinity of the interface between the current collector 1 and the negative electrode active material body 5 was measured using a wavelength dispersive X-ray microanalyzer. The measurement was performed in the same manner as in Example 1. However, in Example 1, composition analysis was performed on cross sections in two directions orthogonal to each other. However, in this example, only composition analysis was performed on the cross section illustrated in FIG.

図１３（ａ）に示す断面の酸素マップおよびケイ素マップを図１３（ｂ）および（ｃ）に示す。図示するマップは、測定で得られたカラー像を白黒コピーしたものであり、明度によって各元素の濃度分布が表わされている。図１３（ｂ）および（ｃ）から、負極活物質体５における右側の側面近傍に、酸素濃度が若干低く、かつ、ケイ素濃度が若干高い領域が存在するものの、全体として大幅な濃度分布が生じていないことがわかった。   The oxygen map and silicon map of the cross section shown in FIG. 13 (a) are shown in FIG. 13 (b) and (c). The map shown is a black and white copy of a color image obtained by measurement, and the concentration distribution of each element is represented by brightness. From FIGS. 13B and 13C, although there is a region where the oxygen concentration is slightly low and the silicon concentration is slightly high in the vicinity of the right side surface of the negative electrode active material body 5, a large concentration distribution occurs as a whole. I found out.

また、図１３（ａ）に示すように、集電体１と負極活物質体５との界面におけるｍ７、ｍ８、ｍ９の３点を測定位置とし、Ｘ線強度からそれぞれの酸素比率を定量したところ、表２に示すような値が得られた。   Further, as shown in FIG. 13 (a), the oxygen ratios were quantified from the X-ray intensity by using three points m7, m8, and m9 at the interface between the current collector 1 and the negative electrode active material body 5 as measurement positions. However, values as shown in Table 2 were obtained.

実施例２では、表２からわかるように、酸素比率の最大値Ｒｍａｘは０．４２、最小値Ｒｍｉｎは０．２９であり、その差ΔＲは０．１３であった。   In Example 2, as can be seen from Table 2, the maximum value Rmax of the oxygen ratio was 0.42, the minimum value Rmin was 0.29, and the difference ΔR was 0.13.

（ｉｉｉ）電池の作製および評価
実施例２の負極板を用いて、図６に示す構成を有する円筒型電池を作製し、その充放電サイクル試験を行った。電池の作製方法および試験方法は実施例１で説明した方法と同様とした。 (Iii) Production and Evaluation of Battery Using the negative electrode plate of Example 2, a cylindrical battery having the configuration shown in FIG. 6 was produced, and a charge / discharge cycle test was performed. The battery fabrication method and test method were the same as those described in Example 1.

図１４は、充放電サイクル試験の結果得られた充放電サイクル特性を示す図である。図１４に示す結果から、実施例２の電池は、優れた充放電サイクル特性を有することを確認した。また、充放電試験を行った後、電池を分解して負極板を観察したところ、負極活物質が集電体１から剥離したり脱落している様子は認められなかった。   FIG. 14 is a diagram showing charge / discharge cycle characteristics obtained as a result of the charge / discharge cycle test. From the results shown in FIG. 14, it was confirmed that the battery of Example 2 had excellent charge / discharge cycle characteristics. Further, after the charge / discharge test was performed, the battery was disassembled and the negative electrode plate was observed. As a result, it was not observed that the negative electrode active material was peeled off or removed from the current collector 1.

（比較例２）
以下、本発明による負極の比較例２を説明する。比較例２では、比較例１と同様の方法で作製された集電体を用いる点で、実施例２の負極と異なっている。 (Comparative Example 2)
Hereinafter, Comparative Example 2 of the negative electrode according to the present invention will be described. Comparative Example 2 differs from the negative electrode of Example 2 in that a current collector produced by the same method as Comparative Example 1 is used.

（ｉ）負極の作製
比較例１と同様の方法で作製した集電体の表面に、特定の方向に傾斜した負極活物質体を形成した。負極活物質体は、実施例２と同様の方法および条件で斜め蒸着を行うことにより形成した。蒸着工程では、ケイ素の入射方向（集電体表面の法線方向に対して６０°傾斜した方向）に対して、集電体表面に配列された各凸部の上面および側面で構成される９０°の角が向き合うため、各凸部の上面および側面の両方にケイ素酸化物が堆積し、負極活物質体が形成された。 (I) Production of Negative Electrode A negative electrode active material body inclined in a specific direction was formed on the surface of a current collector produced by the same method as in Comparative Example 1. The negative electrode active material body was formed by performing oblique deposition under the same method and conditions as in Example 2. In the vapor deposition step, the upper surface and the side surface of each of the convex portions arranged on the current collector surface with respect to the incident direction of silicon (direction inclined by 60 ° with respect to the normal direction of the current collector surface) are 90. Since the corners at 0 ° face each other, silicon oxide was deposited on both the upper surface and the side surface of each convex portion, and a negative electrode active material body was formed.

（ｉｉ）分析
＜電子顕微鏡による観察＞
図１５（ａ）は、比較例２における単一の負極活物質体の電子顕微鏡写真であり、集電体表面に垂直で、かつ、蒸着方向を含む断面を示す。この図から、各負極活物質体５は、特定の方向に傾斜した断面形状を有していることを確認した。また、集電体１の表面における凸部の断面形状は、略９０°の角を有する矩形であることがわかった。 (Ii) Analysis <Observation with an electron microscope>
FIG. 15A is an electron micrograph of a single negative electrode active material body in Comparative Example 2, and shows a cross section perpendicular to the current collector surface and including the vapor deposition direction. From this figure, it was confirmed that each negative electrode active material body 5 had a cross-sectional shape inclined in a specific direction. Moreover, it turned out that the cross-sectional shape of the convex part in the surface of the electrical power collector 1 is a rectangle which has an angle of about 90 degrees.

＜負極活物質体における酸素比率の平均値の測定＞
負極活物質体の酸素比率（ケイ素量に対する酸素量のモル比）の平均値を、実施例１と同様に蛍光Ｘ線測定で求めたところ、０．６１であった。 <Measurement of average value of oxygen ratio in negative electrode active material>
When the average value of the oxygen ratio (molar ratio of the oxygen amount to the silicon amount) of the negative electrode active material body was determined by fluorescent X-ray measurement in the same manner as in Example 1, it was 0.61.

＜負極活物質体と集電体との界面近傍における酸素比率分布＞
集電体１と負極活物質体５との界面における酸素比率を、波長分散型Ｘ線マイクロアナライザを用いて測定した。測定は、実施例２と同様の方法で行った。 <Oxygen ratio distribution in the vicinity of the interface between the negative electrode active material body and the current collector>
The oxygen ratio at the interface between the current collector 1 and the negative electrode active material body 5 was measured using a wavelength dispersive X-ray microanalyzer. The measurement was performed in the same manner as in Example 2.

図１５（ａ）に示す断面の酸素マップおよびケイ素マップを、それぞれ、図１５（ｂ）および（ｃ）に示す。図示するマップは、測定で得られたカラー像を白黒コピーしたものであり、明度によって各元素の濃度分布が表わされている。図１５（ｂ）および（ｃ）からわかるように、負極活物質体５における左側の側面近傍、すなわち、集電体１の凸部の側面上に成長した領域では、他の領域に比べて酸素濃度が大幅に低くなり、かつ、ケイ素濃度が大幅に高くなっていた。   The oxygen map and silicon map of the cross section shown in FIG. 15A are shown in FIGS. 15B and 15C, respectively. The map shown is a black and white copy of a color image obtained by measurement, and the concentration distribution of each element is represented by brightness. As can be seen from FIGS. 15B and 15C, in the vicinity of the left side surface of the negative electrode active material body 5, that is, in the region grown on the side surface of the convex portion of the current collector 1, oxygen is larger than other regions. The concentration was significantly reduced and the silicon concentration was significantly increased.

図１５（ａ）に示すように、集電体１と負極活物質体５との界面におけるｍ１０、ｍ１１、ｍ１２の３点を測定位置とし、Ｘ線強度からそれぞれの酸素比率を定量したところ、表３に示すような値が得られた。   As shown in FIG. 15 (a), when three points m10, m11, and m12 at the interface between the current collector 1 and the negative electrode active material body 5 were measured positions, and the respective oxygen ratios were quantified from the X-ray intensity, Values as shown in Table 3 were obtained.

比較例２では、表３からわかるように、酸素比率の最大値Ｒｍａｘは１．１２、最小値Ｒｍｉｎは０．１９であり、その差ΔＲは０．９３であった。   In Comparative Example 2, as can be seen from Table 3, the maximum value Rmax of the oxygen ratio was 1.12, the minimum value Rmin was 0.19, and the difference ΔR was 0.93.

（ｉｉｉ）電池の作製および評価
比較例２の負極板を用いて、図６に示す構成を有する円筒型電池を作製し、その充放電サイクル試験を行った。電池の作製方法および試験方法は実施例１で説明した方法と同様とした。 (Iii) Production and Evaluation of Battery Using the negative electrode plate of Comparative Example 2, a cylindrical battery having the configuration shown in FIG. 6 was produced, and a charge / discharge cycle test was performed. The battery fabrication method and test method were the same as those described in Example 1.

図１６は、充放電サイクル試験の結果得られた充放電サイクル特性を示す図である。図１６に示す結果から、比較例２の電池では、初期から放電容量が著しく低下し、１００サイクル後には最大容量の８０％程度になることがわかった。   FIG. 16 is a diagram showing charge / discharge cycle characteristics obtained as a result of the charge / discharge cycle test. From the results shown in FIG. 16, it was found that the discharge capacity of the battery of Comparative Example 2 was significantly reduced from the beginning, and reached about 80% of the maximum capacity after 100 cycles.

次に、充放電サイクル試験を行った後の電池を分解して、負極板を電子顕微鏡で観察し、充放電サイクル試験の初期の負極板と比較した。   Next, the battery after the charge / discharge cycle test was disassembled, the negative electrode plate was observed with an electron microscope, and compared with the initial negative electrode plate of the charge / discharge cycle test.

図１７（ａ）および（ｂ）は、それぞれ、充放電サイクル試験初期の負極板および充放電サイクル試験後の負極板の電子顕微鏡写真である。これらの図からわかるように、図１７（ｂ）では、特に集電体１に形成された凸部の上面において、負極活物質が集電体から剥がれかけている部位が認められた。よって、比較例２では、充放電の繰り返しによって負極活物質が集電体表面から剥離し、その結果、放電容量が低下すると考えられる。   FIGS. 17A and 17B are electron micrographs of the negative electrode plate at the initial stage of the charge / discharge cycle test and the negative electrode plate after the charge / discharge cycle test, respectively. As can be seen from these drawings, in FIG. 17B, a part where the negative electrode active material was peeled off from the current collector was observed particularly on the upper surface of the convex portion formed on the current collector 1. Therefore, in Comparative Example 2, it is considered that the negative electrode active material peels from the current collector surface due to repeated charge and discharge, and as a result, the discharge capacity decreases.

なお、本発明の集電体の作製方法や構造は、上述した実施例１および２に限定されない。本発明の集電体は、負極活物質体を支持し、その配置を制御し得る第１の凸部と、第１の凸部の表面に設けられた第２の凸部とを有し、これらの凸部は、負極活物質体を形成するための蒸着方向との関係により、各負極活物質体と集電体との界面における酸素濃度分布を低減できるような形状を有していればよい。同様に、本発明の負極活物質体の構成や形成方法、形成条件なども、上述した実施例１および２に限定されない。例えば、集電体の法線方向に対するケイ素原子の入射方向（角度θ）は適宜選択される。また、実施例１および２では、集電体を真空チャンバー内の固定台に設置した状態で負極活物質層の形成を行ったが、代わりに、真空チャンバー内で、シート状の集電体をローラーを用いて走行させ、走行している集電体に対して負極活物質体を形成することもできる。   In addition, the manufacturing method and structure of the current collector of the present invention are not limited to the first and second embodiments described above. The current collector of the present invention has a first convex portion that supports the negative electrode active material body and can control the arrangement thereof, and a second convex portion provided on the surface of the first convex portion, If these protrusions have a shape that can reduce the oxygen concentration distribution at the interface between each negative electrode active material body and the current collector due to the relationship with the vapor deposition direction for forming the negative electrode active material body, Good. Similarly, the configuration, formation method, formation conditions, and the like of the negative electrode active material body of the present invention are not limited to those in Examples 1 and 2 described above. For example, the incident direction (angle θ) of silicon atoms with respect to the normal direction of the current collector is appropriately selected. In Examples 1 and 2, the negative electrode active material layer was formed in a state where the current collector was placed on a fixed base in the vacuum chamber. Instead, in the vacuum chamber, a sheet-like current collector was formed. The negative electrode active material body can also be formed on the traveling current collector by running using a roller.

本発明のリチウム二次電池用負極は、コイン型、円筒型、扁平型、角型などの様々なリチウム二次電池に適用できる。これらのリチウム二次電池は、高い充放電容量を確保しつつ、従来よりも優れた充放電サイクル特性を有するので、ＰＣ、携帯電話、ＰＤＡ等の携帯情報端末や、ビデオレコーダー、メモリーオーディオプレーヤー等のオーディオビジュアル機器などに広く使用され得る。   The negative electrode for a lithium secondary battery of the present invention can be applied to various lithium secondary batteries such as a coin type, a cylindrical type, a flat type, and a square type. These lithium secondary batteries have a charge / discharge cycle characteristic that is superior to conventional ones while ensuring a high charge / discharge capacity. Therefore, portable information terminals such as PCs, mobile phones, PDAs, video recorders, memory audio players, etc. It can be widely used for audio-visual equipment.

本発明による実施形態の負極を示す模式的な断面図である。It is typical sectional drawing which shows the negative electrode of embodiment by this invention. （ａ）は、負極活物質体と集電体との界面近傍における酸素比率を測定する方法を説明するための模式的な断面図であり、（ｂ）は、（ａ）の測定結果から酸素比率の最大値と最小値との差を求める方法を説明するための図である。(A) is typical sectional drawing for demonstrating the method to measure the oxygen ratio in the interface vicinity of a negative electrode active material body and a collector, (b) is oxygen from the measurement result of (a). It is a figure for demonstrating the method of calculating | requiring the difference of the maximum value and minimum value of a ratio. （ａ）および（ｂ）は、それぞれ、第１の凸部の断面形状が９０°以下の角を有する場合およびそのような角を有していない場合の蒸着工程を説明するための模式的な断面図である。(A) And (b) is typical for demonstrating the vapor deposition process when the cross-sectional shape of a 1st convex part has an angle | corner of 90 degrees or less, and a case where it does not have such an angle, respectively. It is sectional drawing. 本発明による実施形態の負極の製造装置の一例を示す模式的な断面図である。It is typical sectional drawing which shows an example of the manufacturing apparatus of the negative electrode of embodiment by this invention. 本発明による実施形態の負極の他の構成を示す模式的な断面図である。It is typical sectional drawing which shows the other structure of the negative electrode of embodiment by this invention. 本発明の負極を用いた円筒型電池を例示する概略図である。It is the schematic which illustrates the cylindrical battery using the negative electrode of this invention. （ａ）〜（ｃ）は、実施例１における集電体の作製方法を説明するための工程断面図である。(A)-(c) is process sectional drawing for demonstrating the preparation method of the electrical power collector in Example 1. FIG. （ａ）および（ｂ）は、それぞれ、実施例１における集電体の作製に使用するローラーのパターンを例示する平面図および断面図である。(A) And (b) is the top view and sectional drawing which illustrate the pattern of the roller used for preparation of the electrical power collector in Example 1, respectively. 実施例１における負極活物質体の分析結果を示す図であり、（ａ）は、負極活物質体の断面を示す電子顕微鏡写真であり、（ｂ）および（ｃ）は、それぞれ、酸素マップおよびケイ素マップである。It is a figure which shows the analysis result of the negative electrode active material body in Example 1, (a) is an electron micrograph which shows the cross section of a negative electrode active material body, (b) and (c) are respectively an oxygen map and It is a silicon map. 実施例１における負極活物質体の分析結果を示す図であり、（ａ）は、負極活物質体の断面を示す電子顕微鏡写真であり、（ｂ）および（ｃ）は、それぞれ、酸素マップおよびケイ素マップである。It is a figure which shows the analysis result of the negative electrode active material body in Example 1, (a) is an electron micrograph which shows the cross section of a negative electrode active material body, (b) and (c) are respectively an oxygen map and It is a silicon map. 実施例１の円筒型電池の充放電サイクル特性を示す図である。FIG. 3 is a diagram showing charge / discharge cycle characteristics of the cylindrical battery of Example 1. 比較例１の円筒型電池の充放電サイクル特性を示す図である。It is a figure which shows the charging / discharging cycle characteristic of the cylindrical battery of the comparative example 1. 実施例２における負極活物質体の分析結果を示す図であり、（ａ）は、負極活物質体の断面を示す電子顕微鏡写真であり、（ｂ）および（ｃ）は、それぞれ、酸素マップおよびケイ素マップである。It is a figure which shows the analysis result of the negative electrode active material body in Example 2, (a) is an electron micrograph which shows the cross section of a negative electrode active material body, (b) and (c) are respectively an oxygen map and It is a silicon map. 実施例２の円筒型電池の充放電サイクル特性を示す図である。It is a figure which shows the charging / discharging cycle characteristic of the cylindrical battery of Example 2. 比較例２における負極活物質体の分析結果を示す図であり、（ａ）は、負極活物質体の断面を示す電子顕微鏡写真であり、（ｂ）および（ｃ）は、それぞれ、酸素マップおよびケイ素マップである。It is a figure which shows the analysis result of the negative electrode active material body in the comparative example 2, (a) is an electron micrograph which shows the cross section of a negative electrode active material body, (b) and (c) are respectively an oxygen map and It is a silicon map. 比較例２の円筒型電池の充放電サイクル特性を示す図である。It is a figure which shows the charging / discharging cycle characteristic of the cylindrical battery of the comparative example 2. 比較例２の円筒型電池における負極板の電子顕微鏡写真であり、（ａ）および（ｂ）は、それぞれ、充放電サイクル試験初期および充放電サイクル試験後の負極板を示す図である。It is an electron micrograph of the negative electrode plate in the cylindrical battery of Comparative Example 2, and (a) and (b) are views showing the negative electrode plate at the initial stage of the charge / discharge cycle test and after the charge / discharge cycle test, respectively.

符号の説明Explanation of symbols

１ 集電体
２Ａ 第１の凸部
２Ｂ 第２の凸部
５ 負極活物質体
１００ 負極
７ 測定領域
１１ 固定台
１２ 坩堝
１４ 酸素ノズル
１５ 酸素ガス
１６ ケイ素原子
１８ 水平面
２０ ローラー
２１ 凹部
２３ 銅箔
６０ 電池
６１ 正極
６１ａ 正極リード
６２ 負極
６３ セパレータ
６４ 電極群
６５ 正極端子
６６ 絶縁パッキン
６７ 下部絶縁リング
６８ 電池缶
６９ 封口板 DESCRIPTION OF SYMBOLS 1 Current collector 2A 1st convex part 2B 2nd convex part 5 Negative electrode active material body 100 Negative electrode 7 Measurement area 11 Fixing base 12 Crucible 14 Oxygen nozzle 15 Oxygen gas 16 Silicon atom 18 Horizontal surface 20 Roller 21 Recessed part 23 Copper foil 60 Battery 61 Positive electrode 61a Positive electrode lead 62 Negative electrode 63 Separator 64 Electrode group 65 Positive electrode terminal 66 Insulating packing 67 Lower insulating ring 68 Battery can 69 Sealing plate

Claims (10)

集電体と、
前記集電体の上に互いに間隔を空けて配置され、ケイ素酸化物を含む複数の負極活物質体と
を備え、
前記集電体の表面には、前記複数の負極活物質体を支持する複数の第１の凸部が配列されており、
前記各第１の凸部は、前記第１の凸部よりも高さの小さい複数の第２の凸部を有し、
各負極活物質体のケイ素量に対する酸素量のモル比の平均値は０．１以上１．２以下であり、
前記各負極活物質体と前記集電体との界面近傍における、ケイ素量に対する酸素量のモル比の最大値と最小値との差が０．４以下であるリチウム二次電池用負極。 A current collector,
A plurality of negative electrode active material bodies that are disposed on the current collector and spaced apart from each other and that contain silicon oxide;
A plurality of first protrusions supporting the plurality of negative electrode active material bodies are arranged on the surface of the current collector,
Each of the first protrusions has a plurality of second protrusions having a height lower than that of the first protrusion.
The average value of the molar ratio of the oxygen amount to the silicon amount of each negative electrode active material body is 0.1 or more and 1.2 or less,
A negative electrode for a lithium secondary battery, wherein a difference between a maximum value and a minimum value of a molar ratio of an oxygen amount to a silicon amount in the vicinity of an interface between each of the negative electrode active material bodies and the current collector is 0.4 or less. 前記各第１の凸部と前記負極活物質体との接触面は、前記集電体の表面に垂直な断面において、９０°以下の角を有していない請求項１に記載のリチウム二次電池用負極。   2. The lithium secondary according to claim 1, wherein a contact surface between each of the first protrusions and the negative electrode active material body does not have an angle of 90 ° or less in a cross section perpendicular to the surface of the current collector. Battery negative electrode. 前記複数の第１の凸部は、１０μｍ以上のピッチで配列されている請求項１に記載のリチウム二次電池用負極。   2. The negative electrode for a lithium secondary battery according to claim 1, wherein the plurality of first protrusions are arranged at a pitch of 10 μm or more. 前記複数の第１の凸部の高さは５μｍ以上１０μｍ以下である請求項１に記載のリチウム二次電池用負極。   2. The negative electrode for a lithium secondary battery according to claim 1, wherein a height of the plurality of first protrusions is not less than 5 μm and not more than 10 μm. 前記複数の第２の凸部の高さは１μｍ以上５μｍ以下である請求項４に記載のリチウム二次電池用負極。   The negative electrode for a lithium secondary battery according to claim 4, wherein a height of the plurality of second convex portions is 1 μm or more and 5 μm or less. 前記各負極活物質体の成長方向は、前記集電体の法線方向に対して傾斜している請求項１に記載のリチウム二次電池用負極。   2. The negative electrode for a lithium secondary battery according to claim 1, wherein a growth direction of each of the negative electrode active material bodies is inclined with respect to a normal direction of the current collector. 前記各負極活物質体は、成長方向の異なる複数の部分を有している請求項１に記載のリチウム二次電池用負極。   The negative electrode for a lithium secondary battery according to claim 1, wherein each of the negative electrode active material bodies has a plurality of portions having different growth directions. 前記各負極活物質体と前記集電体との界面近傍において、前記各負極活物質体の成長方向と、前記集電体の法線方向とのなす角度は１０°以上８０°以下である請求項６または７に記載のリチウム二次電池用負極。   In the vicinity of the interface between each negative electrode active material body and the current collector, an angle formed by the growth direction of each negative electrode active material body and the normal direction of the current collector is 10 ° or more and 80 ° or less. Item 8. The negative electrode for a lithium secondary battery according to Item 6 or 7. リチウムイオンを吸蔵・放出可能な正極と、
請求項１から７のいずれかに記載のリチウム二次電池用負極と、
前記正極と前記リチウム二次電池用負極との間に配置されたセパレータと、
リチウムイオン伝導性を有する電解質と
を含むリチウム二次電池。 A positive electrode capable of inserting and extracting lithium ions;
A negative electrode for a lithium secondary battery according to any one of claims 1 to 7,
A separator disposed between the positive electrode and the negative electrode for a lithium secondary battery;
A lithium secondary battery comprising an electrolyte having lithium ion conductivity. 表面に第１の凸部が配列された集電体を用意する工程であって、各第１の凸部は、前記第１の凸部よりも高さの小さい複数の第２の凸部を有している工程と、
前記集電体の表面における前記各第１の凸部の上に、ケイ素酸化物を含む負極活物質体を形成する工程と
を含み、
各負極活物質体のケイ素量に対する酸素量のモル比の平均値は０．１以上１．２以下であり、
前記各負極活物質体と前記集電体との界面近傍における、ケイ素量に対する酸素量のモル比の最大値と最小値との差が０．４以下であるリチウム二次電池用負極の製造方法。 A step of preparing a current collector in which first protrusions are arranged on the surface, wherein each first protrusion includes a plurality of second protrusions having a height lower than that of the first protrusion; And having the process
Forming a negative electrode active material body containing silicon oxide on each of the first protrusions on the surface of the current collector,
The average value of the molar ratio of the oxygen amount to the silicon amount of each negative electrode active material body is 0.1 or more and 1.2 or less,
A method for producing a negative electrode for a lithium secondary battery, wherein the difference between the maximum value and the minimum value of the molar ratio of the oxygen amount to the silicon amount in the vicinity of the interface between each negative electrode active material body and the current collector is 0.4 or less .
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KR20160104560A (en) 2015-02-26 2016-09-05 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery, and producing method of negative electrode material for non-aqueous electrolyte secondary battery
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KR20180071297A (en) 2015-11-17 2018-06-27 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, a nonaqueous electrolyte secondary battery negative electrode, a lithium ion secondary battery, a manufacturing method of a negative electrode active material, and a manufacturing method of a lithium ion secondary battery
KR20180071296A (en) 2015-11-17 2018-06-27 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, a nonaqueous electrolyte secondary battery, a lithium ion secondary battery, and a manufacturing method of a negative electrode active material
KR20180093014A (en) 2016-01-07 2018-08-20 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, a nonaqueous electrolyte secondary battery negative electrode, a lithium ion secondary battery, a manufacturing method of a negative electrode active material, and a manufacturing method of a lithium ion secondary battery
KR20180093005A (en) 2016-01-04 2018-08-20 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and method for manufacturing negative active material for nonaqueous electrolyte secondary battery
WO2018168411A1 (en) 2017-03-13 2018-09-20 信越化学工業株式会社 Negative electrode material, method for producing said negative electrode material, and mixed negative electrode material
WO2018168196A1 (en) 2017-03-13 2018-09-20 信越化学工業株式会社 Negative-electrode active substance, mixed negative-electrode active substance material, and method for manufacturing negative-electrode active substance
US10096820B2 (en) 2012-08-06 2018-10-09 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, method preparing the same and rechargeable lithium battery including the same
WO2018221268A1 (en) 2017-06-01 2018-12-06 信越化学工業株式会社 Negative-electrode active substance, mixed negative-electrode active substance material, and method for manufacturing negative-electrode active substance particles
KR20180134887A (en) 2016-04-13 2018-12-19 신에쓰 가가꾸 고교 가부시끼가이샤 Method for producing negative electrode active material for non-aqueous electrolyte secondary battery and method for manufacturing negative electrode for non-aqueous electrolyte secondary battery
WO2019026550A1 (en) 2017-08-03 2019-02-07 信越化学工業株式会社 Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method for manufacturing negative electrode material for non-aqueous electrolyte secondary battery
KR20190011739A (en) 2016-05-30 2019-02-07 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material and a negative electrode active material production method
KR20190012169A (en) 2016-05-30 2019-02-08 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material and a negative electrode active material production method
KR20190017785A (en) 2016-06-13 2019-02-20 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, and a method for manufacturing a negative electrode active material
KR20190024906A (en) 2016-07-04 2019-03-08 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, negative electrode, lithium ion secondary battery, method of using lithium ion secondary battery, manufacturing method of negative electrode active material, and manufacturing method of lithium ion secondary battery
KR20190049683A (en) 2016-09-16 2019-05-09 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, and a method for manufacturing a negative electrode active material
KR20190059906A (en) 2016-09-30 2019-05-31 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material and a negative electrode active material production method
KR20190062448A (en) 2016-10-21 2019-06-05 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a negative electrode, a lithium ion secondary battery, a manufacturing method of a negative electrode active material, and a manufacturing method of a lithium ion secondary battery
CN110247102A (en) * 2018-03-09 2019-09-17 松下知识产权经营株式会社 Lithium secondary battery
CN110556590A (en) * 2018-05-31 2019-12-10 松下知识产权经营株式会社 Lithium secondary battery
CN110556540A (en) * 2018-05-31 2019-12-10 松下知识产权经营株式会社 Lithium secondary battery
US10535872B2 (en) 2015-06-02 2020-01-14 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode active material particles
KR20200013661A (en) 2017-06-02 2020-02-07 신에쓰 가가꾸 고교 가부시끼가이샤 Manufacturing method of negative electrode active material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and negative electrode material for nonaqueous electrolyte secondary battery
US10637053B2 (en) 2015-09-10 2020-04-28 Shin-Etsu Chemical Co., Ltd. Production method of negative electrode active material for nonaqueous electrolyte secondary battery, production method of nonaqueous electrolyte secondary battery, production method of negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
WO2020095558A1 (en) 2018-11-07 2020-05-14 信越化学工業株式会社 Negative electrode active material, mixed negative electrode active material, aqueous negative electrode slurry composition, and method for producing negative electrode active material
WO2020110625A1 (en) 2018-11-28 2020-06-04 信越化学工業株式会社 Negative-electrode active material and method for producing same
US10686190B2 (en) 2015-11-18 2020-06-16 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and, production method of negative electrode active material
WO2020149079A1 (en) 2019-01-15 2020-07-23 信越化学工業株式会社 Negative electrode active material for nonaqueous electrolyte secondary battery and method for producing same
US10811681B2 (en) 2015-11-20 2020-10-20 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, negative electrode, lithium ion secondary battery, method for producing negative electrode material for non-aqueous electrolyte secondary battery and method for producing lithium ion secondary battery
US10833323B2 (en) 2016-02-24 2020-11-10 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method for producing negative electrode material for non-aqueous electrolyte secondary battery
WO2021053951A1 (en) 2019-09-18 2021-03-25 信越化学工業株式会社 Negative electrode active substance, negative electrode, and methods for producing these
WO2021065200A1 (en) 2019-10-03 2021-04-08 信越化学工業株式会社 Negative electrode active material, negative electrode, and method for manufacturing negative electrode active material
US10998544B2 (en) 2016-09-16 2021-05-04 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method of producing negative electrode active material
US11165058B2 (en) 2016-09-30 2021-11-02 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method of producing negative electrode active material
US11316147B2 (en) 2016-02-15 2022-04-26 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and method for producing negative electrode active material
WO2022158150A1 (en) 2021-01-25 2022-07-28 信越化学工業株式会社 Negative electrode active material for nonaqueous electrolyte secondary batteries, and method for producing negative electrode active material for nonaqueous electrolyte secondary batteries
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WO2022172815A1 (en) 2021-02-15 2022-08-18 信越化学工業株式会社 Negative electrode active material for nonaqueous electrolyte secondary batteries, method for producing same, and nonaqueous electrolyte secondary battery
WO2022239676A1 (en) 2021-05-13 2022-11-17 信越化学工業株式会社 Negative electrode active material and method for producing same
WO2022259920A1 (en) 2021-06-08 2022-12-15 信越化学工業株式会社 Negative electrode active material, negative electrode and lithium ion secondary battery
WO2022259914A1 (en) 2021-06-08 2022-12-15 信越化学工業株式会社 Negative electrode active material, negative electrode, and lithium ion secondary battery
WO2023008094A1 (en) 2021-07-27 2023-02-02 信越化学工業株式会社 Negative electrode and method for producing same
WO2023008093A1 (en) 2021-07-27 2023-02-02 信越化学工業株式会社 Negative electrode active material and method for producing same
WO2023017689A1 (en) 2021-08-11 2023-02-16 信越化学工業株式会社 Negative electrode
WO2023021861A1 (en) 2021-08-16 2023-02-23 信越化学工業株式会社 Negative electrode and method for producing negative electrode

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002313319A (en) * 2001-04-09 2002-10-25 Sanyo Electric Co Ltd Electrode for lithium secondary battery and lithium secondary battery
JP2006228468A (en) * 2005-02-15 2006-08-31 Sii Micro Parts Ltd Electrolyte secondary battery
WO2007015419A1 (en) * 2005-08-02 2007-02-08 Matsushita Electric Industrial Co., Ltd. Negative electrode for lithium secondary battery and method for producing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002313319A (en) * 2001-04-09 2002-10-25 Sanyo Electric Co Ltd Electrode for lithium secondary battery and lithium secondary battery
JP2006228468A (en) * 2005-02-15 2006-08-31 Sii Micro Parts Ltd Electrolyte secondary battery
WO2007015419A1 (en) * 2005-08-02 2007-02-08 Matsushita Electric Industrial Co., Ltd. Negative electrode for lithium secondary battery and method for producing same

Cited By (145)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8999583B2 (en) 2009-12-24 2015-04-07 Sony Corporation Lithium-ion secondary battery, anode for lithium-ion secondary battery, power tool, electric vehicle and energy storage system
EP2343758A1 (en) 2009-12-24 2011-07-13 Sony Corporation Lithium-ion secondary battery, anode for lithium-ion secondary battery, power tool, electric vehicle and energy storage system
US9893351B2 (en) 2011-06-24 2018-02-13 Murata Manufacturing Co., Ltd. Battery, negative electrode active material, and electric tool
US9048485B2 (en) 2011-06-24 2015-06-02 Sony Corporation Lithium-ion secondary battery, negative electrode for lithium-ion secondary battery, battery pack, electric vehicle, power storage system, electric tool, and electronic device
US9083054B2 (en) 2011-06-24 2015-07-14 Sony Corporation Lithium ion secondary battery, lithium ion secondary battery negative electrode, battery pack, electric vehicle, electricity storage system, power tool, and electronic apparatus
US9225014B2 (en) 2011-06-24 2015-12-29 Sony Corporation Battery, negative electrode active material, and electric tool
US9780368B2 (en) 2011-06-24 2017-10-03 Sony Corporation Lithium-ion secondary battery, negative electrode for lithium-ion secondary battery, battery pack, electric vehicle, power storage system, electric tool, and electronic device
KR20140105460A (en) 2011-12-20 2014-09-01 소니 주식회사 Active material for secondary batteries, secondary battery, and electronic device
WO2013094404A1 (en) 2011-12-20 2013-06-27 ソニー株式会社 Active material for secondary batteries, secondary battery, and electronic device
US10096820B2 (en) 2012-08-06 2018-10-09 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, method preparing the same and rechargeable lithium battery including the same
US10566607B2 (en) 2013-08-21 2020-02-18 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, raw material for a negative electrode active material, negative electrode, lithium ion secondary battery, method for producing a negative electrode active material, and method for producing a lithium ion secondary battery
US9935309B2 (en) 2013-08-21 2018-04-03 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, raw material for a negative electrode active material, negative electrode, lithium ion secondary battery, method for producing a negative electrode active material, and method for producing a lithium ion secondary battery
KR20160044478A (en) 2013-08-21 2016-04-25 신에쓰 가가꾸 고교 가부시끼가이샤 Negative-electrode active substance, negative electrode active substance material, negative electrode, lithium ion secondary battery, negative electrode active substance manufacturing method, and lithium ion secondary battery manufacturing method
KR20200124329A (en) 2013-08-21 2020-11-02 신에쓰 가가꾸 고교 가부시끼가이샤 Negative-electrode active substance, negative electrode active substance material, negative electrode, lithium ion secondary battery, negative electrode active substance manufacturing method, and lithium ion secondary battery manufacturing method
US9929399B2 (en) 2013-10-29 2018-03-27 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, method for producing a negative electrode active material, and lithium ion secondary battery
US10283756B2 (en) 2013-10-29 2019-05-07 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, method for producing a negative electrode active material, and lithium ion secondary battery
KR20160077075A (en) 2013-10-29 2016-07-01 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, production method for negative electrode active material, and lithium ion secondary battery
US10396351B2 (en) 2014-01-16 2019-08-27 Shin-Etsu Chemical Co., Ltd. Negative electrode material for non-aqueous electrolyte secondary battery and method of producing negative electrode active material particles
KR20160110380A (en) 2014-01-16 2016-09-21 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material for nonaqueous electrolyte secondary batteries and method for producing negative electrode active material particles
KR20210124504A (en) 2014-01-16 2021-10-14 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material for nonaqueous electrolyte secondary batteries and method for producing negative electrode active material particles
WO2015107581A1 (en) 2014-01-16 2015-07-23 信越化学工業株式会社 Negative electrode material for nonaqueous electrolyte secondary batteries and method for producing negative electrode active material particles
KR20160118260A (en) 2014-02-07 2016-10-11 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode for non-aqueous electrolyte secondary batteries, and non-aqueous electrolyte secondary battery
US10388950B2 (en) 2014-02-07 2019-08-20 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for negative electrode material of non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
KR20160118261A (en) 2014-02-07 2016-10-11 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for negative electrode material of non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
WO2015118846A1 (en) 2014-02-07 2015-08-13 信越化学工業株式会社 Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, production method therefor, and non-aqueous electrolyte secondary battery
US10199678B2 (en) 2014-02-07 2019-02-05 Shin-Etsu Chemical Co., Ltd. Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery and method of producing the same, and non-aqueous electrolyte secondary battery
KR20160118258A (en) 2014-02-07 2016-10-11 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, production method therefor, and non-aqueous electrolyte secondary battery
KR20150114902A (en) 2014-04-02 2015-10-13 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode for nonaqueous electrolytic secondary battery and nonaqueous electrolytic secondary battery
US9728779B2 (en) 2014-04-02 2017-08-08 Shin-Etsu Chemical Co., Ltd. Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery
US10686189B2 (en) 2014-04-22 2020-06-16 Shin-Etsu Chemical Co., Ltd. Negative electrode material for non-aqueous electrolyte secondary battery, method of producing the same, negative electrode active material layer for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
KR20150122072A (en) 2014-04-22 2015-10-30 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material for nonaqueous electrolytic secondary battery and method for making the same, negative electrode active material layer for nonaqueous electrolytic secondary battery, negative electrode for nonaqueous electrolytic secondary battery, and nonaqueous electrolytic secondary battery
KR20170023832A (en) 2014-06-23 2017-03-06 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material for nonaqueous electrolyte secondary batteries, negative electrode for nonaqueous electrolyte secondary batteries, nonaqueous electrolyte secondary battery and method for producing negative electrode active material particles
KR20220005639A (en) 2014-06-23 2022-01-13 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material for nonaqueous electrolyte secondary batteries, negative electrode for nonaqueous electrolyte secondary batteries, nonaqueous electrolyte secondary battery and method for producing negative electrode active material particles
US10629890B2 (en) 2014-06-23 2020-04-21 Shin-Etsu Chemical Co., Ltd. Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode active material particles
US10529984B2 (en) 2014-07-15 2020-01-07 Shin-Etsu Chemical Co., Ltd. Negative electrode material for non-aqueous electrolyte secondary battery and method of producing negative electrode active material particles
KR20170031141A (en) 2014-07-15 2017-03-20 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material for nonaqueous electrolyte secondary battery and method for producing negative electrode active material particle
US10396353B2 (en) 2014-10-08 2019-08-27 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode material for non-aqueous electrolyte secondary battery
KR20170057309A (en) 2014-10-08 2017-05-24 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active substance for nonaqueous electrolyte secondary cell, negative electrode for nonaqueous electrolyte secondary cell, nonaqueous electrolyte secondary cell, and method for producing negative electrode material for nonaqueous electrolyte secondary cell
KR20160100830A (en) 2015-02-16 2016-08-24 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery, and producing method of negative electrode material for non-aqueous electrolyte secondary battery
EP3057157A1 (en) 2015-02-16 2016-08-17 Shin-Etsu Chemical Co., Ltd Negative electrode active material for non-aqueous electrolyte secondary battery containing the same, non-aqueous electrolyte secondary battery, and method of producing said electrode material
US9831495B2 (en) 2015-02-16 2017-11-28 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode material for a non-aqueous electrolyte secondary battery
US10446837B2 (en) 2015-02-26 2019-10-15 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode material for a non-aqueous electrolyte secondary battery
EP3062371A1 (en) 2015-02-26 2016-08-31 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing said negative electrode material
KR20160104560A (en) 2015-02-26 2016-09-05 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery, and producing method of negative electrode material for non-aqueous electrolyte secondary battery
KR20160125895A (en) 2015-04-22 2016-11-01 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for non-aqueous electrolyte secondary battery and method for making the same, and non-aqueous electrolyte secondary battery using the negative electrode active material and method for making negative electrode material for non-aqueous electrolyte secondary battery
EP3086386A1 (en) 2015-04-22 2016-10-26 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, method of producing the same, non-aqueous electrolyte secondary battery using the negative electrode active material, and method of producing negative electrode material for non-aqueous electrolyte secondary battery
US10535872B2 (en) 2015-06-02 2020-01-14 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode active material particles
KR20180019569A (en) 2015-06-17 2018-02-26 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method for manufacturing negative electrode material for non-aqueous electrolyte secondary battery
US10418627B2 (en) 2015-06-17 2019-09-17 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode material for non-aqueous electrolyte secondary battery
US11177501B2 (en) 2015-07-07 2021-11-16 Shin-Etsu Chemical Co., Ltd. Production method for non-aqueous electrolyte secondary battery active material providing lithium insertion and solution contact
KR20180026717A (en) 2015-07-07 2018-03-13 신에쓰 가가꾸 고교 가부시끼가이샤 Method for producing negative electrode active material for non-aqueous electrolyte secondary battery, method for manufacturing negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
US10637053B2 (en) 2015-09-10 2020-04-28 Shin-Etsu Chemical Co., Ltd. Production method of negative electrode active material for nonaqueous electrolyte secondary battery, production method of nonaqueous electrolyte secondary battery, production method of negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
KR20180066070A (en) 2015-10-08 2018-06-18 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, method of manufacturing negative electrode material for non-aqueous electrolyte secondary battery, and method of manufacturing non-aqueous electrolyte secondary battery
US10707482B2 (en) 2015-10-08 2020-07-07 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, method for producing negative electrode material for non-aqueous secondary battery, and method for producing non-aqueous electrolyte secondary battery
US10991971B2 (en) 2015-11-17 2021-04-27 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and, production method of negative electrode active material
KR20180071296A (en) 2015-11-17 2018-06-27 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, a nonaqueous electrolyte secondary battery, a lithium ion secondary battery, and a manufacturing method of a negative electrode active material
US10559822B2 (en) 2015-11-17 2020-02-11 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, negative electrode for non-aqueous electrolyte secondary battery, lithium ion secondary battery, method for producing negative electrode active material, and method for producing lithium ion secondary battery
KR20180071297A (en) 2015-11-17 2018-06-27 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, a nonaqueous electrolyte secondary battery negative electrode, a lithium ion secondary battery, a manufacturing method of a negative electrode active material, and a manufacturing method of a lithium ion secondary battery
US10686190B2 (en) 2015-11-18 2020-06-16 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and, production method of negative electrode active material
WO2017085908A1 (en) 2015-11-18 2017-05-26 信越化学工業株式会社 Negative electrode active material, mixed negative electrode active material, negative electrode for non-aqueous electrolyte secondary battery, lithium ion secondary battery, method for producing negative electrode active material, and method for producing lithium ion secondary battery
US11430980B2 (en) 2015-11-18 2022-08-30 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, production method of negative electrode active material, and production method of lithium ion secondary battery
US10811681B2 (en) 2015-11-20 2020-10-20 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, negative electrode, lithium ion secondary battery, method for producing negative electrode material for non-aqueous electrolyte secondary battery and method for producing lithium ion secondary battery
US10559812B2 (en) 2016-01-04 2020-02-11 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and production method of negative electrode active material for nonaqueous electrolyte secondary battery
KR20180093005A (en) 2016-01-04 2018-08-20 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and method for manufacturing negative active material for nonaqueous electrolyte secondary battery
KR20180093014A (en) 2016-01-07 2018-08-20 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, a nonaqueous electrolyte secondary battery negative electrode, a lithium ion secondary battery, a manufacturing method of a negative electrode active material, and a manufacturing method of a lithium ion secondary battery
US11316147B2 (en) 2016-02-15 2022-04-26 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and method for producing negative electrode active material
WO2017145853A1 (en) 2016-02-23 2017-08-31 信越化学工業株式会社 Negative electrode active material, negative electrode active material mixed material, negative electrode for nonaqueous electrolyte secondary batteries, lithium ion secondary battery, method for producing negative electrode active material, and method for manufacturing lithium ion secondary battery
KR20180117106A (en) 2016-02-23 2018-10-26 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, a nonaqueous electrolyte secondary battery negative electrode, a lithium ion secondary battery, a manufacturing method of a negative electrode active material, and a manufacturing method of a lithium ion secondary battery
US10868303B2 (en) 2016-02-23 2020-12-15 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, material of mixed negative electrode active material, negative electrode for non-aqueous electrolyte secondary battery, lithium ion secondary battery, method for producing negative electrode active material and method for producing lithium ion secondary battery
US10833323B2 (en) 2016-02-24 2020-11-10 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method for producing negative electrode material for non-aqueous electrolyte secondary battery
KR20180134887A (en) 2016-04-13 2018-12-19 신에쓰 가가꾸 고교 가부시끼가이샤 Method for producing negative electrode active material for non-aqueous electrolyte secondary battery and method for manufacturing negative electrode for non-aqueous electrolyte secondary battery
US11024838B2 (en) 2016-04-13 2021-06-01 Shin-Etsu Chemical Co., Ltd. Production method of negative electrode active material for non-aqueous electrolyte secondary battery and production method of negative electrode for non-aqueous electrolyte secondary battery
WO2017183286A1 (en) 2016-04-18 2017-10-26 信越化学工業株式会社 Negative electrode active substance, mixed negative electrode active substance material, and method for producing negative electrode active substance
US10862122B2 (en) 2016-04-18 2020-12-08 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, method for producing negative electrode active material
KR20210037741A (en) 2016-05-30 2021-04-06 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
US11139469B2 (en) 2016-05-30 2021-10-05 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
US10991937B2 (en) 2016-05-30 2021-04-27 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
US11658289B2 (en) 2016-05-30 2023-05-23 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
KR20190011739A (en) 2016-05-30 2019-02-07 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material and a negative electrode active material production method
KR20190013774A (en) 2016-05-30 2019-02-11 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material and a negative electrode active material production method
WO2017208624A1 (en) 2016-05-30 2017-12-07 信越化学工業株式会社 Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
US11005095B2 (en) 2016-05-30 2021-05-11 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
KR20190012169A (en) 2016-05-30 2019-02-08 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material and a negative electrode active material production method
KR20210113444A (en) 2016-05-30 2021-09-15 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
KR20190017785A (en) 2016-06-13 2019-02-20 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, and a method for manufacturing a negative electrode active material
EP4120395A1 (en) 2016-06-13 2023-01-18 Shin-Etsu Chemical Co., Ltd. Negative-electrode active substance, mixed negative-electrode active substance material, and method for manufacturing negative-electrode active substance
US11335905B2 (en) 2016-06-13 2022-05-17 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method of producing negative electrode active material
KR20190024906A (en) 2016-07-04 2019-03-08 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, negative electrode, lithium ion secondary battery, method of using lithium ion secondary battery, manufacturing method of negative electrode active material, and manufacturing method of lithium ion secondary battery
US10873082B2 (en) 2016-07-04 2020-12-22 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, negative electrode, lithium ion secondary battery, method of using lithium ion secondary battery, method of producing negative electrode active material, and method of producing lithium ion secondary battery
KR20190049683A (en) 2016-09-16 2019-05-09 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material, and a method for manufacturing a negative electrode active material
US10998544B2 (en) 2016-09-16 2021-05-04 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method of producing negative electrode active material
KR20190059906A (en) 2016-09-30 2019-05-31 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a mixed negative electrode active material and a negative electrode active material production method
US11165058B2 (en) 2016-09-30 2021-11-02 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method of producing negative electrode active material
KR20190062448A (en) 2016-10-21 2019-06-05 신에쓰 가가꾸 고교 가부시끼가이샤 A negative electrode active material, a negative electrode, a lithium ion secondary battery, a manufacturing method of a negative electrode active material, and a manufacturing method of a lithium ion secondary battery
US11909038B2 (en) 2016-10-21 2024-02-20 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, negative electrode, lithium ion secondary battery, method of producing negative electrode active material, and method of producing lithium ion secondary battery
WO2018168196A1 (en) 2017-03-13 2018-09-20 信越化学工業株式会社 Negative-electrode active substance, mixed negative-electrode active substance material, and method for manufacturing negative-electrode active substance
KR20230149854A (en) 2017-03-13 2023-10-27 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material, method for producing said negative electrode material, and mixed negative electrode material
KR20190125981A (en) 2017-03-13 2019-11-07 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode material, manufacturing method of the negative electrode material, and mixed negative electrode material
WO2018168411A1 (en) 2017-03-13 2018-09-20 信越化学工業株式会社 Negative electrode material, method for producing said negative electrode material, and mixed negative electrode material
KR20190123282A (en) 2017-03-13 2019-10-31 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, mixed negative electrode active material, and manufacturing method of negative electrode active material
US11594716B2 (en) 2017-03-13 2023-02-28 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method of producing negative electrode active material
KR20200014300A (en) 2017-06-01 2020-02-10 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material particles
US11283060B2 (en) 2017-06-01 2022-03-22 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material particle
KR20240029100A (en) 2017-06-01 2024-03-05 신에쓰 가가꾸 고교 가부시끼가이샤 Negative-electrode active substance, mixed negative-electrode active substance material, and method for manufacturing negative-electrode active substance particles
WO2018221268A1 (en) 2017-06-01 2018-12-06 信越化学工業株式会社 Negative-electrode active substance, mixed negative-electrode active substance material, and method for manufacturing negative-electrode active substance particles
US11901545B2 (en) 2017-06-01 2024-02-13 Shin-Etsu Chemical Co., Ltd. Method for producing negative electrode active material particle
KR20200013661A (en) 2017-06-02 2020-02-07 신에쓰 가가꾸 고교 가부시끼가이샤 Manufacturing method of negative electrode active material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and negative electrode material for nonaqueous electrolyte secondary battery
KR20200037221A (en) 2017-08-03 2020-04-08 신에쓰 가가꾸 고교 가부시끼가이샤 Non-aqueous electrolyte secondary battery negative electrode active material, non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery negative electrode material manufacturing method
US11316152B2 (en) 2017-08-03 2022-04-26 Shin-Etsu Chemical Co., Ltd. Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method for producing negative electrode material for non-aqueous electrolyte secondary battery
WO2019026550A1 (en) 2017-08-03 2019-02-07 信越化学工業株式会社 Negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method for manufacturing negative electrode material for non-aqueous electrolyte secondary battery
CN110247102A (en) * 2018-03-09 2019-09-17 松下知识产权经营株式会社 Lithium secondary battery
CN110247102B (en) * 2018-03-09 2024-03-08 松下知识产权经营株式会社 Lithium secondary battery
CN110556590A (en) * 2018-05-31 2019-12-10 松下知识产权经营株式会社 Lithium secondary battery
CN110556540A (en) * 2018-05-31 2019-12-10 松下知识产权经营株式会社 Lithium secondary battery
WO2020095558A1 (en) 2018-11-07 2020-05-14 信越化学工業株式会社 Negative electrode active material, mixed negative electrode active material, aqueous negative electrode slurry composition, and method for producing negative electrode active material
KR20210089653A (en) 2018-11-07 2021-07-16 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, mixed negative electrode active material, aqueous negative electrode slurry composition, and method for producing negative electrode active material
US11961997B2 (en) 2018-11-07 2024-04-16 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, aqueous negative electrode slurry composition, and method for producing negative electrode active material
KR20210095148A (en) 2018-11-28 2021-07-30 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material and manufacturing method thereof
WO2020110625A1 (en) 2018-11-28 2020-06-04 信越化学工業株式会社 Negative-electrode active material and method for producing same
KR20210110606A (en) 2019-01-15 2021-09-08 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material for nonaqueous electrolyte secondary battery and manufacturing method thereof
WO2020149079A1 (en) 2019-01-15 2020-07-23 信越化学工業株式会社 Negative electrode active material for nonaqueous electrolyte secondary battery and method for producing same
KR20220066052A (en) 2019-09-18 2022-05-23 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, negative electrode and manufacturing method thereof
WO2021053951A1 (en) 2019-09-18 2021-03-25 信越化学工業株式会社 Negative electrode active substance, negative electrode, and methods for producing these
KR20220075218A (en) 2019-10-03 2022-06-07 신에쓰 가가꾸 고교 가부시끼가이샤 Negative electrode active material, negative electrode and manufacturing method of negative electrode active material
WO2021065200A1 (en) 2019-10-03 2021-04-08 信越化学工業株式会社 Negative electrode active material, negative electrode, and method for manufacturing negative electrode active material
WO2022158150A1 (en) 2021-01-25 2022-07-28 信越化学工業株式会社 Negative electrode active material for nonaqueous electrolyte secondary batteries, and method for producing negative electrode active material for nonaqueous electrolyte secondary batteries
KR20230137311A (en) 2021-01-25 2023-10-04 신에쓰 가가꾸 고교 가부시끼가이샤 Method for manufacturing negative electrode active material for non-aqueous electrolyte secondary battery and negative electrode active material for non-aqueous electrolyte secondary battery
WO2022168474A1 (en) 2021-02-04 2022-08-11 信越化学工業株式会社 Negative electrode and method for producing negative electrode
KR20230142483A (en) 2021-02-04 2023-10-11 신에쓰 가가꾸 고교 가부시끼가이샤 Cathode and cathode manufacturing method
WO2022172815A1 (en) 2021-02-15 2022-08-18 信越化学工業株式会社 Negative electrode active material for nonaqueous electrolyte secondary batteries, method for producing same, and nonaqueous electrolyte secondary battery
KR20230145351A (en) 2021-02-15 2023-10-17 신에쓰 가가꾸 고교 가부시끼가이샤 Negative active material for non-aqueous electrolyte secondary battery, manufacturing method thereof, and non-aqueous electrolyte secondary battery
WO2022239676A1 (en) 2021-05-13 2022-11-17 信越化学工業株式会社 Negative electrode active material and method for producing same
KR20240007153A (en) 2021-05-13 2024-01-16 신에쓰 가가꾸 고교 가부시끼가이샤 Negative active material and method for producing the same
KR20240019114A (en) 2021-06-08 2024-02-14 신에쓰 가가꾸 고교 가부시끼가이샤 Negative active material, negative electrode and lithium ion secondary battery
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WO2023021861A1 (en) 2021-08-16 2023-02-23 信越化学工業株式会社 Negative electrode and method for producing negative electrode
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