JP2010232190A - Negative electrode for secondary battery, and secondary battery - Google Patents

Negative electrode for secondary battery, and secondary battery Download PDF

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JP2010232190A
JP2010232190A JP2010132933A JP2010132933A JP2010232190A JP 2010232190 A JP2010232190 A JP 2010232190A JP 2010132933 A JP2010132933 A JP 2010132933A JP 2010132933 A JP2010132933 A JP 2010132933A JP 2010232190 A JP2010232190 A JP 2010232190A
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negative electrode
current collector
active material
secondary battery
material layer
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JP5206735B2 (en
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Isamu Konishiike
勇 小西池
Kenichi Kawase
賢一 川瀬
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Sony Corp
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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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Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative electrode for a secondary battery for improving cycle characteristics, and the secondary battery using it. <P>SOLUTION: A negative electrode active material layer 12 containing Si is provided in a negative electrode collector 11. The negative electrode collector 11 is roughened by providing a projecting part 11B in a base material 11A having ten-point average roughness Rz1 of 2.0 μm or less. The value of a difference Rz2-Rz1 obtained by subtracting the ten-point average roughness Rz1 of the base material 11A from the ten-point average roughness Rz2 of the negative electrode collector 11 is set to be not less than 0.2 μm and not more than 5.1 μm. Thereby, even if the negative electrode active material 12 expands and contracts by charge and discharge, rupture of the negative electrode collector 11 and peeling of the negative electrode active material 12 is suppressed. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、負極集電体に構成元素としてケイ素（Ｓｉ）を含む負極活物質層が設けられた二次電池用負極、およびそれを備えた二次電池に関する。   The present invention relates to a negative electrode for a secondary battery in which a negative electrode current collector is provided with a negative electrode active material layer containing silicon (Si) as a constituent element, and a secondary battery including the same.

近年、モバイル機器の高性能化および多機能化に伴い、それらの電源である二次電池の高容量化が要求されている。この要求に応える二次電池としてはリチウムイオン二次電池があるが、現在実用化されているものは負極に黒鉛を用いているので、電池容量は飽和状態にあり、大幅な高容量化は難しい。そこで、負極にケイ素などを用いることが検討されており、最近では、気相法などにより負極集電体に負極活物質層を形成することも報告されている。ケイ素などは充放電に伴う膨張収縮が大きいので、微粉化によるサイクル特性の低下が問題であったが、気相法などによれば、微細化を抑制することができると共に、負極集電体と負極活物質層とを一体化することができるので負極における電子伝導性が極めて良好となり、容量的にもサイクル寿命的にも高性能化が期待されている。   In recent years, as mobile devices have higher performance and more functions, there is a demand for higher capacities of secondary batteries serving as power sources thereof. Secondary batteries that meet this requirement include lithium ion secondary batteries, but those currently in practical use use graphite for the negative electrode, so the battery capacity is saturated and it is difficult to achieve significant increases in capacity. . Therefore, it has been studied to use silicon or the like for the negative electrode, and recently, it has been reported that a negative electrode active material layer is formed on the negative electrode current collector by a vapor phase method or the like. Since silicon and the like have a large expansion / contraction due to charging / discharging, deterioration of cycle characteristics due to pulverization has been a problem. However, according to a vapor phase method or the like, miniaturization can be suppressed and a negative electrode current collector and Since the negative electrode active material layer can be integrated, the electron conductivity in the negative electrode becomes extremely good, and high performance is expected in terms of capacity and cycle life.

しかし、このように負極集電体と負極活物質層とを一体化した負極においても、充放電を繰り返すと、負極活物質層の激しい膨張および収縮により負極集電体と負極活物質層との間に応力がかかり、負極活物質層の脱落などが生じてサイクル特性が低下するなど問題があった。そこで、負極集電体を粗化することにより、負極集電体との密着性を向上させることが検討されている（例えば、特許文献１，２参照）。これらの公知例には、凹凸を有する電解銅箔に、電解めっきにより突起部を形成した負極集電体が記載されている。   However, even in the negative electrode in which the negative electrode current collector and the negative electrode active material layer are integrated as described above, when the charge and discharge are repeated, the negative electrode current collector and the negative electrode active material layer are separated by vigorous expansion and contraction of the negative electrode active material layer. There was a problem in that stress was applied in the meantime, the negative electrode active material layer was dropped, and the cycle characteristics deteriorated. Then, improving the adhesiveness with a negative electrode collector by roughening a negative electrode collector is examined (for example, refer patent documents 1, 2). These known examples describe a negative electrode current collector in which protrusions are formed by electrolytic plating on an uneven copper foil.

国際公開第ＷＯ０１／０３１７２３号パンフレットInternational Publication No. WO01 / 031723 Pamphlet 特開２００２−３１３３１９号公報JP 2002-313319 A

しかしながら、このように凹凸を有する電解銅箔は、一般に、厚み方向に柱状結晶が配向した構造となっており、凹部に粒界が存在する場合が多いので、充放電に伴い負極活物質層が膨張収縮すると、この凹部の粒界に沿って負極が破断してしまうことが多いという問題があった。また、電解銅箔の表面粗さは、柱状結晶の粒径に応じたものとなるので、電解銅箔の厚みが大きく影響し、厚みに関係なく表面粗さを変化させることが難しいという問題もあった。更に、このような電解銅箔では表面粗さが目的とする値よりも大きくなってしまうことが多く、しかも、両面の表面粗さを同じ程度に調節することが難しかった。   However, the electrolytic copper foil having such irregularities generally has a structure in which columnar crystals are oriented in the thickness direction, and there are many cases where grain boundaries exist in the concave portions. When expanding and contracting, the negative electrode often breaks along the grain boundary of the recess. In addition, since the surface roughness of the electrolytic copper foil depends on the grain size of the columnar crystals, the thickness of the electrolytic copper foil has a great influence, and it is difficult to change the surface roughness regardless of the thickness. there were. Furthermore, in such an electrolytic copper foil, the surface roughness often becomes larger than the target value, and it is difficult to adjust the surface roughness on both sides to the same extent.

本発明はかかる問題点に鑑みてなされたもので、その目的は、負極集電体の破断および負極活物質層の剥離などを抑制し、サイクル特性などの電池特性を向上させることができる二次電池用負極および二次電池を提供することにある。   The present invention has been made in view of such problems, and its purpose is to suppress secondary electrode current collector breakage and negative electrode active material layer peeling, and to improve secondary battery characteristics such as cycle characteristics. The object is to provide a negative electrode for a battery and a secondary battery.

本発明による二次電池用負極は、負極集電体に構成元素としてケイ素を含む負極活物質層が設けられたものであって、負極集電体は、基材と、この基材に設けられた突起部とを有し、負極活物質層が設けられた面の基材の十点平均粗さＲｚ１は２．０μｍ以下であり、負極活物質層が設けられた面の負極集電体の十点平均粗さＲｚ２から基材の十点平均粗さＲｚ１を引いた差Ｒｚ２−Ｒｚ１は、０．２μｍ以上５．１μｍ以下であり、基材の厚みは１５μｍ以上１８μｍ以下のものである。   A negative electrode for a secondary battery according to the present invention includes a negative electrode current collector provided with a negative electrode active material layer containing silicon as a constituent element. The negative electrode current collector is provided on a base material and the base material. The ten-point average roughness Rz1 of the base material on the surface provided with the negative electrode active material layer is 2.0 μm or less, and the negative electrode current collector on the surface provided with the negative electrode active material layer. The difference Rz2−Rz1 obtained by subtracting the ten-point average roughness Rz1 of the base material from the ten-point average roughness Rz2 is 0.2 μm or more and 5.1 μm or less, and the thickness of the base material is 15 μm or more and 18 μm or less.

本発明による二次電池は、正極および負極と共に電解質を備えたものであって、負極は、負極集電体に構成元素としてケイ素を含む負極活物質層が設けられており、負極集電体は、基材と、この基材に設けられた突起部とを有し、負極活物質層が設けられた面の基材の十点平均粗さＲｚ１は２．０μｍ以下であり、負極活物質層が設けられた面の負極集電体の十点平均粗さＲｚ２から基材の十点平均粗さＲｚ１を引いた差Ｒｚ２−Ｒｚ１は、０．２μｍ以上５．１μｍ以下であり、基材の厚みは１５μｍ以上１８μｍ以下のものである。   A secondary battery according to the present invention is provided with an electrolyte together with a positive electrode and a negative electrode. The negative electrode is provided with a negative electrode active material layer containing silicon as a constituent element in the negative electrode current collector. The ten-point average roughness Rz1 of the base material on the surface having the base material and the protrusions provided on the base material and provided with the negative electrode active material layer is 2.0 μm or less, and the negative electrode active material layer The difference Rz2−Rz1 obtained by subtracting the ten-point average roughness Rz1 of the base material from the ten-point average roughness Rz2 of the negative electrode current collector on the surface provided with is 0.2 μm or more and 5.1 μm or less. The thickness is 15 μm or more and 18 μm or less.

本発明の二次電池用負極によれば、十点平均粗さＲｚ１が２．０μｍ以下の比較的平滑な基材に突起部を設けて粗化すると共に基材の厚みを１５μｍ以上１８μｍ以下にしたので、充放電に伴い負極活物質層が大きく膨張収縮しても、負極集電体の破断を抑制することができる。また、負極集電体の表面粗さを自由に決定することができ、負極活物質層の密着性を容易に向上させることができる。更に、負極集電体の表面粗さを両面について容易に制御することもできる。よって、この二次電池用負極を用いた本発明の二次電池によれば、容量およびサイクル特性などの電池特性を向上させることができる。   According to the negative electrode for a secondary battery of the present invention, the ten-point average roughness Rz1 is roughened by providing a protrusion on a relatively smooth base material having a thickness of 2.0 μm or less, and the thickness of the base material is 15 μm or more and 18 μm or less. Therefore, even if the negative electrode active material layer expands and contracts greatly due to charge / discharge, breakage of the negative electrode current collector can be suppressed. Further, the surface roughness of the negative electrode current collector can be freely determined, and the adhesion of the negative electrode active material layer can be easily improved. Furthermore, the surface roughness of the negative electrode current collector can be easily controlled on both sides. Therefore, according to the secondary battery of the present invention using this negative electrode for a secondary battery, battery characteristics such as capacity and cycle characteristics can be improved.

特に、負極集電体の十点平均粗さＲｚ２を１．３μｍ以上３．５μｍ以下とするようにすれば、より高い効果を得ることができる。   In particular, if the ten-point average roughness Rz2 of the negative electrode current collector is set to 1.3 μm or more and 3.5 μm or less, a higher effect can be obtained.

本発明の一実施の形態に係る負極の構成を表す断面図である。It is sectional drawing showing the structure of the negative electrode which concerns on one embodiment of this invention. 図１に示した負極を用いた二次電池の構成を表す断面図である。It is sectional drawing showing the structure of the secondary battery using the negative electrode shown in FIG. 図１に示した負極を用いた他の二次電池の構成を表す分解斜視図である。It is a disassembled perspective view showing the structure of the other secondary battery using the negative electrode shown in FIG. 図３に示した二次電池のＩ−Ｉ線に沿った構造を表す断面図である。It is sectional drawing showing the structure along the II line of the secondary battery shown in FIG. 実施例１−４に係る負極集電体の表面構造を表すＳＥＭ写真である。It is a SEM photograph showing the surface structure of the negative electrode collector which concerns on Example 1-4. 図５に示した負極集電体の断面構造を表すＳＥＭ写真である。6 is a SEM photograph showing a cross-sectional structure of the negative electrode current collector shown in FIG. 5. 図５に示した負極集電体の断面構造を表すＳＩＭ写真である。6 is a SIM photograph showing a cross-sectional structure of the negative electrode current collector shown in FIG. 5. 比較例１−１に係る負極集電体の表面構造を表すＳＥＭ写真である。It is a SEM photograph showing the surface structure of the negative electrode collector which concerns on the comparative example 1-1. 比較例１−４に係る負極集電体の表面構造を表すＳＥＭ写真である。It is a SEM photograph showing the surface structure of the negative electrode collector which concerns on Comparative Example 1-4. 比較例１−１０に係る負極集電体の表面構造を表すＳＥＭ写真である。It is a SEM photograph showing the surface structure of the negative electrode collector which concerns on Comparative Example 1-10. 図１０に示した負極集電体の断面構造を表すＳＥＭ写真である。It is a SEM photograph showing the cross-sectional structure of the negative electrode collector shown in FIG. 図１０に示した負極集電体の断面構造を表すＳＩＭ写真である。It is a SIM photograph showing the cross-sectional structure of the negative electrode current collector shown in FIG.

以下、本発明の実施の形態について、図面を参照して詳細に説明する。なお、説明する順序は以下の通りである。

１．二次電池用負極
２．二次電池
２−１．コイン型
２−２．ラミネートフィルム型
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The order of explanation is as follows.

1. Negative electrode for secondary battery Secondary battery 2-1. Coin type 2-2. Laminate film type

＜１．二次電池用負極＞
図１は、本発明の一実施の形態に係る負極１０（二次電池用負極）の構成を表すものである。負極１０は、例えば、負極集電体１１に構成元素としてケイ素を含む負極活物質層１２が設けられた構造を有している。ケイ素はリチウム（Ｌｉ）を吸蔵および放出する能力が大きく、高いエネルギー密度を得ることができるからである。ケイ素は、単体で含まれていてもよく、合金で含まれていてもよく、化合物で含まれていてもよい。なお、図１では負極集電体１１の片面に負極活物質層１２が設けられた場合を示したが、負極活物質層１２は負極集電体１１の両面に設けられていてもよい。 <1. Secondary battery negative electrode>
FIG. 1 shows a configuration of a negative electrode 10 (a negative electrode for a secondary battery) according to an embodiment of the present invention. The negative electrode 10 has, for example, a structure in which a negative electrode current collector 11 is provided with a negative electrode active material layer 12 containing silicon as a constituent element. This is because silicon has a large ability to occlude and release lithium (Li), and a high energy density can be obtained. Silicon may be contained as a simple substance, may be contained as an alloy, or may be contained as a compound. Although FIG. 1 shows the case where the negative electrode active material layer 12 is provided on one surface of the negative electrode current collector 11, the negative electrode active material layer 12 may be provided on both surfaces of the negative electrode current collector 11.

負極集電体１１は、基材１１Ａと、基材１１Ａに設けられた粒子状の突起部１１Ｂとを有している。突起部１１Ｂによるアンカー効果により、負極集電体１１と負極活物質層１２との密着性を向上させることができるからである。   The negative electrode current collector 11 has a base material 11A and particulate projections 11B provided on the base material 11A. This is because the adhesion between the negative electrode current collector 11 and the negative electrode active material layer 12 can be improved by the anchor effect of the protrusion 11B.

基材１１Ａは、リチウムと金属間化合物を形成しない金属元素を含む金属材料により構成されていることが好ましい。リチウムと金属間化合物を形成すると、充放電に伴い膨張および収縮し、構造破壊が起こって、集電性が低下する他、負極活物質層１２を支える能力が小さくなるからである。なお、本明細書において金属材料には、金属元素の単体だけでなく、２種以上の金属元素あるいは１種以上の金属元素と１種以上の半金属元素とからなる合金も含める。リチウムと金属間化合物を形成しない金属元素としては、例えば、銅（Ｃｕ），ニッケル（Ｎｉ），チタン（Ｔｉ），鉄（Ｆｅ）あるいはクロム（Ｃｒ）が挙げられる。   The base material 11A is preferably made of a metal material containing a metal element that does not form an intermetallic compound with lithium. This is because when lithium and an intermetallic compound are formed, they expand and contract with charge / discharge, structural breakdown occurs, current collection performance decreases, and the ability to support the negative electrode active material layer 12 decreases. Note that in this specification, the metal material includes not only a single metal element but also an alloy composed of two or more metal elements or one or more metal elements and one or more metalloid elements. Examples of the metal element that does not form an intermetallic compound with lithium include copper (Cu), nickel (Ni), titanium (Ti), iron (Fe), and chromium (Cr).

また、基材１１Ａは、負極活物質層１２と合金化することが可能な金属元素を含む方がより好ましい場合もある。合金化により負極集電体１１と負極活物質層１２との密着性をより向上させることができるからである。リチウムと金属間化合物を形成せず、負極活物質層１２と合金化する金属元素、すなわちケイ素と合金化する金属元素としては、銅，ニッケルあるいは鉄が挙げられる。   Further, it may be more preferable that the base material 11 </ b> A contains a metal element that can be alloyed with the negative electrode active material layer 12. This is because the adhesion between the negative electrode current collector 11 and the negative electrode active material layer 12 can be further improved by alloying. Examples of the metal element that forms an alloy with lithium and does not form an intermetallic compound with lithium, that is, the metal element that forms an alloy with silicon, include copper, nickel, and iron.

基材１１Ａは、単層により構成してもよいが、複数層により構成してもよい。その場合、負極活物質層１２と接する層を負極活物質層１２と合金化しやすい金属材料により構成し、他の層を他の金属材料により構成するようにしてもよい。   The base material 11A may be composed of a single layer, but may be composed of a plurality of layers. In that case, the layer in contact with the negative electrode active material layer 12 may be made of a metal material that is easily alloyed with the negative electrode active material layer 12, and the other layers may be made of another metal material.

突起部１１Ｂは、基材１１Ａの負極活物質層１２が形成される面に少なくとも設けられていればよく、負極活物質層１２と合金化することが可能な元素を含むことが好ましい。合金化により負極活物質層１２との密着性をより向上させることができるからである。ケイ素と合金化しやすい元素としては、例えば、銅，ニッケル，鉄，アルミニウム（Ａｌ），インジウム（Ｉｎ），コバルト（Ｃｏ），マンガン（Ｍｎ），亜鉛（Ｚｎ），銀（Ａｇ），スズ（Ｓｎ），ゲルマニウム（Ｇｅ）あるいは鉛（Ｐｂ）が挙げられる。突起部１１Ｂの構成元素は、基材１１Ａと同一でも異なっていてもよい。   The protrusion 11B only needs to be provided at least on the surface of the base 11A where the negative electrode active material layer 12 is formed, and preferably includes an element that can be alloyed with the negative electrode active material layer 12. This is because the adhesion with the negative electrode active material layer 12 can be further improved by alloying. Examples of elements that are easily alloyed with silicon include copper, nickel, iron, aluminum (Al), indium (In), cobalt (Co), manganese (Mn), zinc (Zn), silver (Ag), and tin (Sn). ), Germanium (Ge) or lead (Pb). The constituent elements of the protrusion 11B may be the same as or different from those of the base 11A.

また、基材１１Ａの負極活物質層１２が設けられた面における十点平均粗さＲｚ１は、２．０μｍ以下であることが好ましい。基材１１Ａの粗度が大きいと負極活物質層１２の膨張収縮により凹部から破断が生じやすく、また、このように比較的平滑な基材１１Ａに突起部１１Ｂを形成することにより、負極集電体１１の表面形状および粗度を容易に制御することができるからである。   Moreover, it is preferable that 10-point average roughness Rz1 in the surface in which the negative electrode active material layer 12 of the base material 11A was provided is 2.0 micrometers or less. If the roughness of the base material 11A is large, the negative electrode active material layer 12 is likely to break from the recess due to expansion and contraction. Also, by forming the protrusion 11B on the relatively smooth base material 11A, the negative electrode current collector is formed. This is because the surface shape and roughness of the body 11 can be easily controlled.

更に、負極集電体１１の負極活物質層１２が設けられた面における十点平均粗さＲｚ２から基材１１Ａの十点平均粗さＲｚ１を引いた差Ｒｚ２−Ｒｚ１は、０．２μｍ以上５．１μｍ以下であることが好ましく、負極集電体１１の十点平均粗さＲｚ２が１．３μｍ以上３．５μｍ以下であればより好ましい。この範囲内において負極集電体１１と負極活物質層１２との密着性をより向上させることができるからである。   Further, the difference Rz2−Rz1 obtained by subtracting the ten-point average roughness Rz1 of the base 11A from the ten-point average roughness Rz2 on the surface of the negative electrode current collector 11 on which the negative electrode active material layer 12 is provided is 0.2 μm or more. The 10-point average roughness Rz2 of the negative electrode current collector 11 is more preferably 1.3 μm or more and 3.5 μm or less. This is because the adhesion between the negative electrode current collector 11 and the negative electrode active material layer 12 can be further improved within this range.

これら基材１１Ａの十点平均粗さＲｚ１および負極集電体１１の十点平均粗さＲｚ２は、例えば、断面を切り出したのち、断面の像を画像処理することにより求めることができる。なお、十点平均粗さはＪＩＳ Ｂ０６０１に規定されているものである。   The ten-point average roughness Rz1 of the substrate 11A and the ten-point average roughness Rz2 of the negative electrode current collector 11 can be obtained, for example, by image processing of the image of the cross section after cutting out the cross section. The 10-point average roughness is defined in JIS B0601.

負極活物質層１２は、例えば、気相法により形成されたものであることが好ましい。充放電に伴う負極活物質層１２の膨張・収縮による破壊を抑制することができると共に、負極集電体１１と負極活物質層１２とを一体化することができ、負極活物質層１２における電子伝導性を向上させることができるからである。   The negative electrode active material layer 12 is preferably formed by, for example, a vapor phase method. Breakage due to expansion / contraction of the negative electrode active material layer 12 due to charge / discharge can be suppressed, the negative electrode current collector 11 and the negative electrode active material layer 12 can be integrated, and electrons in the negative electrode active material layer 12 can be integrated. This is because the conductivity can be improved.

負極活物質層１２は、また、負極集電体１１との界面の少なくとも一部において負極集電体１１と合金化していることが好ましい。具体的には、界面において負極集電体１１の構成元素が負極活物質層１２に、または負極活物質層１２の構成元素が負極集電体１１に、またはそれらが互いに拡散していることが好ましい。密着性を向上させることができ、負極活物質層１２Ｂが膨張収縮により負極集電体１２Ａから脱落してしまうことを抑制することができるからである。   The negative electrode active material layer 12 is preferably alloyed with the negative electrode current collector 11 at least at a part of the interface with the negative electrode current collector 11. Specifically, the constituent elements of the negative electrode current collector 11 are diffused in the negative electrode active material layer 12, the constituent elements of the negative electrode active material layer 12 are diffused in the negative electrode current collector 11, or they are mutually diffused at the interface. preferable. This is because the adhesion can be improved and the negative electrode active material layer 12B can be prevented from falling off the negative electrode current collector 12A due to expansion and contraction.

負極１０は、例えば、次のようにして製造することができる。   The negative electrode 10 can be manufactured as follows, for example.

まず、基材１１Ａとして、例えば十点平均粗さＲｚ１が２．０μｍ以下の金属箔を用意し、これに電解めっきなどにより突起部１１Ｂを形成して負極集電体１１を作製する。その際、電流値または時間などを制御することにより、突起部１１Ｂの大きさを調節し、負極集電体１１の十点平均粗さＲｚ２を調節する。   First, as the base material 11A, for example, a metal foil having a ten-point average roughness Rz1 of 2.0 μm or less is prepared, and a protruding portion 11B is formed on the metal foil by electrolytic plating or the like to produce the negative electrode current collector 11. At that time, by controlling the current value or time, the size of the protrusion 11B is adjusted, and the ten-point average roughness Rz2 of the negative electrode current collector 11 is adjusted.

次いで、負極集電体１１に気相法により負極活物質層１２を成膜する。気相法としては、例えば、物理堆積法あるいは化学堆積法が挙げられ、具体的には、真空蒸着法，スパッタ法，イオンプレーティング法，レーザーアブレーション法，ＣＶＤ（Chemical Vapor Deposition ；化学気相成長）法あるいは溶射法などが挙げられる。   Next, the negative electrode active material layer 12 is formed on the negative electrode current collector 11 by a vapor phase method. Examples of the vapor phase method include a physical deposition method and a chemical deposition method. Specifically, a vacuum deposition method, a sputtering method, an ion plating method, a laser ablation method, a CVD (Chemical Vapor Deposition; chemical vapor deposition). ) Method or thermal spraying method.

なお、負極活物質層１２の成膜時に、負極活物質層１２と負極集電体１１との合金化が同時に起こる場合もあるが、負極活物質層１２を成膜したのちに、真空雰囲気下または非酸化性雰囲気下で熱処理を行い、合金化するようにしてもよい。これにより図１に示した負極１０が得られる。   Note that although the negative electrode active material layer 12 and the negative electrode current collector 11 may be alloyed at the same time when the negative electrode active material layer 12 is formed, the negative electrode active material layer 12 is formed in a vacuum atmosphere after forming the negative electrode active material layer 12. Alternatively, heat treatment may be performed in a non-oxidizing atmosphere to form an alloy. Thereby, the negative electrode 10 shown in FIG. 1 is obtained.

＜２．二次電池＞
この負極１０は、例えば、次のような二次電池に用いられる。 <2. Secondary battery>
This negative electrode 10 is used for the following secondary batteries, for example.

［２−１．コイン型］
図２は、その二次電池の構成を表すものである。この二次電池は、いわゆるコイン型といわれるものであり、外装カップ２１に収容された負極１０と、外装缶２２の内に収容された正極２３とが、セパレータ２４を介して積層されたものである。 [2-1. Coin type]
FIG. 2 shows the configuration of the secondary battery. This secondary battery is a so-called coin-type battery, in which the negative electrode 10 accommodated in the exterior cup 21 and the positive electrode 23 accommodated in the exterior can 22 are stacked via a separator 24. is there.

外装カップ２１および外装缶２２の周縁部は絶縁性のガスケット２５を介してかしめることにより密閉されている。外装カップ２１および外装缶２２は、例えば、ステンレスあるいはアルミニウムなどの金属によりそれぞれ構成されている。   The peripheral portions of the outer cup 21 and the outer can 22 are sealed by caulking through an insulating gasket 25. The exterior cup 21 and the exterior can 22 are made of, for example, a metal such as stainless steel or aluminum.

正極２３は、例えば、正極集電体２３Ａと、正極集電体２３Ａに設けられた正極活物質層２３Ｂとを有しており、正極活物質層２３Ｂの側が負極活物質層１２と対向するように配置されている。正極集電体２３Ａは、例えば、アルミニウム，ニッケルあるいはステンレスなどにより構成されている。   The positive electrode 23 includes, for example, a positive electrode current collector 23A and a positive electrode active material layer 23B provided on the positive electrode current collector 23A so that the positive electrode active material layer 23B side faces the negative electrode active material layer 12. Is arranged. The positive electrode current collector 23A is made of, for example, aluminum, nickel, stainless steel, or the like.

正極活物質層２３Ｂは、例えば、正極活物質としてリチウムを吸蔵および放出することが可能な正極材料のいずれか１種または２種以上を含んでおり、必要に応じて炭素材料などの導電材およびポリフッ化ビニリデンなどのバインダーを含んでいてもよい。リチウムを吸蔵および放出することが可能な正極材料としては、例えば、一般式Ｌｉx ＭＩＯ2 で表されるリチウム含有金属複合酸化物が好ましい。リチウム含有金属複合酸化物は、高電圧を発生可能であると共に、高密度であるため、二次電池の更なる高容量化を図ることができるからである。なお、ＭＩは１種類以上の遷移金属であり、例えばコバルトおよびニッケルのうちの少なくとも一方が好ましい。ｘは電池の充放電状態によって異なり、通常０．０５≦ｘ≦１．１０の範囲内の値である。このようなリチウム含有金属複合酸化物の具体例としては、ＬｉＣｏＯ2 あるいはＬｉＮｉＯ2 などが挙げられる。 The positive electrode active material layer 23B includes, for example, any one or more of positive electrode materials capable of inserting and extracting lithium as a positive electrode active material, and a conductive material such as a carbon material and the like as necessary. A binder such as polyvinylidene fluoride may be included. As a positive electrode material capable of inserting and extracting lithium, for example, a lithium-containing metal composite oxide represented by a general formula Li x MIO 2 is preferable. This is because the lithium-containing metal composite oxide can generate a high voltage and has a high density, so that the capacity of the secondary battery can be further increased. MI is one or more kinds of transition metals, and for example, at least one of cobalt and nickel is preferable. x varies depending on the charge / discharge state of the battery and is usually a value in the range of 0.05 ≦ x ≦ 1.10. Specific examples of such a lithium-containing metal composite oxide include LiCoO 2 and LiNiO 2 .

なお、正極２３は、例えば、正極活物質と導電材とバインダーとを混合して合剤を調製し、この合剤をＮ−メチル−２−ピロリドンなどの分散媒に分散させて合剤スラリーを作製し、この合剤スラリーを金属箔よりなる正極集電体２３Ａに塗布し乾燥させたのち、圧縮成型し正極活物質層２３Ｂを形成することにより作製することができる。   The positive electrode 23 is prepared, for example, by mixing a positive electrode active material, a conductive material, and a binder to prepare a mixture, and dispersing the mixture in a dispersion medium such as N-methyl-2-pyrrolidone. This mixture slurry is applied to the positive electrode current collector 23A made of a metal foil, dried, and then compression molded to form the positive electrode active material layer 23B.

セパレータ２４は、負極１０と正極２３とを隔離し、両極の接触による電流の短絡を防止しつつ、リチウムイオンを通過させるものである。このセパレータ２４は、例えば、ポリエチレンやポリプロピレンにより構成されている。   The separator 24 separates the negative electrode 10 and the positive electrode 23 and allows lithium ions to pass through while preventing a short circuit of current due to contact between both electrodes. The separator 24 is made of, for example, polyethylene or polypropylene.

セパレータ２４には、液状の電解質である電解液が含浸されている。この電解液は、例えば、溶媒と、この溶媒に溶解された電解質塩とを含んでおり、必要に応じて添加剤を含んでいてもよい。溶媒としては、例えば、炭酸エチレン，炭酸プロピレン，炭酸ジメチル，炭酸ジエチルあるいは炭酸エチルメチルなどの非水溶媒が挙げられる。溶媒はいずれか１種を単独で用いてもよいが、２種以上を混合して用いてもよい。   The separator 24 is impregnated with an electrolytic solution that is a liquid electrolyte. This electrolytic solution contains, for example, a solvent and an electrolyte salt dissolved in this solvent, and may contain an additive as necessary. Examples of the solvent include nonaqueous solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. Any one of the solvents may be used alone, or two or more may be mixed and used.

電解質塩としては、例えば、ＬｉＰＦ6 ，ＬｉＣＦ3 ＳＯ3 あるいはＬｉＣｌＯ4 などのリチウム塩が挙げられる。電解質塩は、いずれか１種を単独で用いてもよいが、２種以上を混合して用いてもよい。 Examples of the electrolyte salt include lithium salts such as LiPF 6 , LiCF 3 SO 3, and LiClO 4 . Any one electrolyte salt may be used alone, or two or more electrolyte salts may be mixed and used.

この二次電池は、例えば、負極１０、電解液が含浸されたセパレータ２４および正極２３を積層して、外装カップ２１と外装缶２２との中に入れ、それらをかしめることにより製造することができる。   This secondary battery can be manufactured, for example, by laminating the negative electrode 10, the separator 24 impregnated with the electrolytic solution, and the positive electrode 23, placing them in the outer cup 21 and the outer can 22, and caulking them. it can.

この二次電池では、充電を行うと、例えば、正極２３からリチウムイオンが放出され、電解液を介して負極１０に吸蔵される。放電を行うと、例えば、負極１０からリチウムイオンが放出され、電解液を介して正極２３に吸蔵される。本実施の形態では、十点平均粗さＲｚ１が２．０μｍ以下の基材１１Ａに突起部１１Ｂを設けて粗化した負極集電体１１を用いているので、充放電により負極活物質層１２が膨張収縮しても、負極集電体が破断したり、負極活物質層１２が負極集電体１１から脱落することが抑制される。   In the secondary battery, when charged, for example, lithium ions are released from the positive electrode 23 and inserted in the negative electrode 10 through the electrolytic solution. When discharging is performed, for example, lithium ions are released from the negative electrode 10 and inserted in the positive electrode 23 through the electrolytic solution. In the present embodiment, the negative electrode current collector 11 that is roughened by providing the protrusions 11B on the base material 11A having a ten-point average roughness Rz1 of 2.0 μm or less is used. Even if the material expands and contracts, the negative electrode current collector is prevented from being broken or the negative electrode active material layer 12 is prevented from falling off the negative electrode current collector 11.

本実施の形態に係る負極１０は、次のような二次電池に用いてもよい。   The negative electrode 10 according to the present embodiment may be used for the following secondary battery.

［２−２．ラミネートフィルム型］
図３は、その二次電池の構成を表すものである。この二次電池は、リード３１，３２が取り付けられた電極巻回体３０をフィルム状の外装部材４１内部に収容したものであり、小型化，軽量化および薄型化が可能となっている。 [2-2. Laminate film type]
FIG. 3 shows the configuration of the secondary battery. In this secondary battery, the wound electrode body 30 to which the leads 31 and 32 are attached is housed in a film-like exterior member 41, and can be reduced in size, weight, and thickness.

リード３１，３２は、それぞれ、外装部材４１の内部から外部に向かい例えば同一方向に導出されている。リード３１，３２は、例えば、アルミニウム，銅，ニッケルあるいはステンレスなどの金属材料によりそれぞれ構成されており、それぞれ薄板状または網目状とされている。   The leads 31 and 32 are led out from the inside of the exterior member 41 to the outside, for example, in the same direction. The leads 31 and 32 are made of a metal material such as aluminum, copper, nickel, or stainless steel, respectively, and have a thin plate shape or a mesh shape, respectively.

外装部材４１は、例えば、ナイロンフィルム，アルミニウム箔およびポリエチレンフィルムをこの順に貼り合わせた矩形状のアルミラミネートフィルムにより構成されている。外装部材４１は、例えば、ポリエチレンフィルム側と電極巻回体３０とが対向するように配設されており、各外縁部が融着あるいは接着剤により互いに密着されている。外装部材４１とリード３１，３２との間には、外気の侵入を防止するための密着フィルム４２が挿入されている。密着フィルム４２は、リード３１，３２に対して密着性を有する材料、例えば、ポリエチレン，ポリプロピレン，変性ポリエチレンあるいは変性ポリプロピレンなどのポリオレフィン樹脂により構成されている。   The exterior member 41 is made of, for example, a rectangular aluminum laminated film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order. The exterior member 41 is disposed, for example, so that the polyethylene film side and the electrode winding body 30 face each other, and the outer edge portions are in close contact with each other by fusion or an adhesive. An adhesion film 42 for preventing the entry of outside air is inserted between the exterior member 41 and the leads 31 and 32. The adhesion film 42 is made of a material having adhesion to the leads 31 and 32, for example, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, or modified polypropylene.

なお、外装部材４１は、上述したアルミラミネートフィルムに代えて、他の構造を有するラミネートフィルム，ポリプロピレンなどの高分子フィルムあるいは金属フィルムにより構成するようにしてもよい。   The exterior member 41 may be made of a laminated film having another structure, a polymer film such as polypropylene, or a metal film instead of the above-described aluminum laminated film.

図４は、図３に示した電極巻回体３０のＩ−Ｉ線に沿った断面構造を表すものである。電極巻回体３０は、負極１０と正極３３とをセパレータ３４および電解質層３５を介して積層し、巻回したものであり、最外周部は保護テープ３６により保護されている。   FIG. 4 shows a cross-sectional structure taken along line II of the electrode winding body 30 shown in FIG. The electrode winding body 30 is obtained by laminating and winding the negative electrode 10 and the positive electrode 33 with the separator 34 and the electrolyte layer 35 interposed therebetween, and the outermost peripheral portion is protected by a protective tape 36.

負極１０は、負極集電体１１の両面に負極活物質層１２が設けられた構造を有している。正極３３も、正極集電体３３Ａの両面に正極活物質層３３Ｂが設けられた構造を有しており、正極活物質層３３Ｂと負極活物質層１２とが対向するように配置されている。正極集電体３３Ａ，正極活物質層３３Ｂおよびセパレータ３４の構成は、それぞれ上述した正極集電体２３Ａ，正極活物質層２３Ｂおよびセパレータ２４と同様である。   The negative electrode 10 has a structure in which a negative electrode active material layer 12 is provided on both surfaces of a negative electrode current collector 11. The positive electrode 33 also has a structure in which the positive electrode active material layer 33B is provided on both surfaces of the positive electrode current collector 33A, and the positive electrode active material layer 33B and the negative electrode active material layer 12 are arranged to face each other. The configurations of the positive electrode current collector 33A, the positive electrode active material layer 33B, and the separator 34 are the same as those of the positive electrode current collector 23A, the positive electrode active material layer 23B, and the separator 24 described above.

電解質層３５は、高分子化合物よりなる保持体に電解液を保持させたいわゆるゲル状の電解質により構成されている。ゲル状の電解質は高いイオン伝導率を得ることができると共に、電池の漏液を防止することができるので好ましい。電解液の構成は、図２に示したコイン型の二次電池と同様である。高分子材料としては、例えばポリフッ化ビニリデンが挙げられる。   The electrolyte layer 35 is configured by a so-called gel electrolyte in which an electrolytic solution is held in a holding body made of a polymer compound. A gel electrolyte is preferable because high ion conductivity can be obtained and battery leakage can be prevented. The configuration of the electrolytic solution is the same as that of the coin-type secondary battery shown in FIG. An example of the polymer material is polyvinylidene fluoride.

この二次電池は、例えば、次のようにして製造することができる。   For example, the secondary battery can be manufactured as follows.

まず、負極１０および正極３３のそれぞれに、保持体に電解液を保持させた電解質層３５を形成し、リード３１，３２を取り付ける。次いで、電解質層３５が形成された負極１０と正極３３とをセパレータ３４を介して積層し、巻回して、最外周部に保護テープ３６を接着して電極巻回体３０を形成する。続いて、例えば、外装部材４１の間に電極巻回体３０を挟み込み、外装部材４１の外縁部同士を熱融着などにより密着させて封入する。その際、リード３１，３２と外装部材４１との間には密着フィルム４２を挿入する。これにより、図３および図４に示した二次電池が完成する。   First, on each of the negative electrode 10 and the positive electrode 33, an electrolyte layer 35 in which an electrolytic solution is held in a holding body is formed, and leads 31 and 32 are attached. Next, the negative electrode 10 on which the electrolyte layer 35 is formed and the positive electrode 33 are laminated via the separator 34 and wound, and the protective tape 36 is adhered to the outermost peripheral portion to form the electrode winding body 30. Subsequently, for example, the electrode winding body 30 is sandwiched between the exterior members 41, and the outer edge portions of the exterior members 41 are sealed and sealed by thermal fusion or the like. At that time, the adhesion film 42 is inserted between the leads 31 and 32 and the exterior member 41. Thereby, the secondary battery shown in FIGS. 3 and 4 is completed.

また、次のようにして製造してもよい。まず、負極１０および正極３３のそれぞれにリード３１，３２を取り付けたのち、負極１０と正極３３とをセパレータ３４を介して積層して巻回し、最外周部に保護テープ３６を接着して、電極巻回体３０の前駆体である巻回体を形成する。次いで、この巻回体を外装部材４１に挟み、一辺を除く外周縁部を熱融着して袋状としたのち、電解液と、高分子化合物の原料であるモノマーと、重合開始剤と、必要に応じて重合禁止剤などの他の材料とを含む電解質用組成物を、外装部材４１の内部に注入する。続いて、外装部材４１の開口部を真空雰囲気下で熱融着して密封し、熱を加えてモノマーを重合させて高分子化合物とすることによりゲル状の電解質層３５を形成する。これにより、図３および図４に示した二次電池が完成する。   Moreover, you may manufacture as follows. First, after the leads 31 and 32 are attached to the negative electrode 10 and the positive electrode 33, the negative electrode 10 and the positive electrode 33 are laminated and wound via the separator 34, and the protective tape 36 is adhered to the outermost peripheral portion to A wound body that is a precursor of the wound body 30 is formed. Next, the wound body is sandwiched between exterior members 41, and the outer peripheral edge except for one side is heat-sealed into a bag shape, and then the electrolyte, the monomer that is the raw material of the polymer compound, the polymerization initiator, An electrolyte composition containing another material such as a polymerization inhibitor is injected into the exterior member 41 as necessary. Subsequently, the opening of the exterior member 41 is heat-sealed and sealed in a vacuum atmosphere, and heat is applied to polymerize the monomer to form a polymer compound, thereby forming the gel electrolyte layer 35. Thereby, the secondary battery shown in FIGS. 3 and 4 is completed.

この二次電池の作用は、図２に示したコイン型の二次電池と同様である。   The operation of this secondary battery is the same as that of the coin-type secondary battery shown in FIG.

このように本実施の形態によれば、十点平均粗さＲｚ１が２．０μｍ以下の比較的平滑な基材１１Ａに突起部１１Ｂを設けて粗化するようにしたので、充放電に伴い負極活物質層１２が大きく膨張収縮しても、負極集電体１１の破断を抑制することができる。また、負極集電体１１の厚みおよび表面粗さを自由に決定することができ、負極活物質層１２の密着性を容易に向上させることができる。更に、負極集電体１１の表面粗さを両面について容易に制御することもできる。よって、容量およびサイクル特性などの電池特性を向上させることができる。   As described above, according to the present embodiment, the protrusion 11B is provided on the relatively smooth base material 11A having a ten-point average roughness Rz1 of 2.0 μm or less so as to be roughened. Even if the active material layer 12 expands and contracts greatly, the breakage of the negative electrode current collector 11 can be suppressed. In addition, the thickness and surface roughness of the negative electrode current collector 11 can be freely determined, and the adhesion of the negative electrode active material layer 12 can be easily improved. Furthermore, the surface roughness of the negative electrode current collector 11 can be easily controlled on both sides. Therefore, battery characteristics such as capacity and cycle characteristics can be improved.

特に、負極集電体１１の十点平均粗さＲｚ２を１．３μｍ以上３．５μｍ以下とするようにすれば、より高い効果を得ることができる。   In particular, if the ten-point average roughness Rz2 of the negative electrode current collector 11 is set to 1.3 μm or more and 3.5 μm or less, a higher effect can be obtained.

更に、本発明の具体的な実施例について図面を参照して詳細に説明する。   Further, specific embodiments of the present invention will be described in detail with reference to the drawings.

（実施例１−１〜１−１９）
図３，４に示した構造の二次電池を作製した。 (Examples 1-1 to 1-19)
A secondary battery having the structure shown in FIGS.

まず、基材１１Ａとして、実施例１−１〜１−９では、厚みが１８μｍ、十点平均粗さＲｚ１が０．８μｍの電解銅箔を用意し、実施例１−１０〜１−１９では、厚みが１５μｍ、十点平均粗さＲｚ１が０．５μｍの圧延銅箔を用意した。次いで、基材１１Ａに電解めっきにより銅の突起部１１Ｂを形成し、負極集電体１１を作製した。その際、突起部１１Ｂの大きさを変化させることにより、負極集電体１１の十点平均粗さＲｚ２を実施例１−１〜１−１９で表１に示したように変化させた。続いて、負極集電体１１に電子ビーム真空蒸着法によりケイ素よりなる厚み約５．５μｍの負極活物質層１２を成膜した。   First, as the base material 11A, in Examples 1-1 to 1-9, an electrolytic copper foil having a thickness of 18 μm and a ten-point average roughness Rz1 of 0.8 μm was prepared. In Examples 1-10 to 1-19, A rolled copper foil having a thickness of 15 μm and a ten-point average roughness Rz1 of 0.5 μm was prepared. Next, a copper protrusion 11B was formed on the base 11A by electrolytic plating, and a negative electrode current collector 11 was produced. At that time, the ten-point average roughness Rz2 of the negative electrode current collector 11 was changed as shown in Table 1-1 in Examples 1-1 to 1-19 by changing the size of the protrusion 11B. Subsequently, a negative electrode active material layer 12 made of silicon and having a thickness of about 5.5 μm was formed on the negative electrode current collector 11 by an electron beam vacuum deposition method.

また、正極活物質である平均粒径５μｍのコバルト酸リチウム（ＬｉＣｏＯ2 ）粉末９２質量部と、導電材であるカーボンブラック３質量部と、バインダーであるポリフッ化ビニリデン５質量部とを混合し、これを分散媒であるＮ−メチル−２−ピロリドンに投入してスラリーとした。次いで、これを厚み１５μｍのアルミニウム箔よりなる正極集電体３３Ａに塗布して乾燥させたのちプレスを行って正極活物質層３３Ｂを形成した。 Also, 92 parts by mass of lithium cobaltate (LiCoO 2 ) powder having an average particle diameter of 5 μm as a positive electrode active material, 3 parts by mass of carbon black as a conductive material, and 5 parts by mass of polyvinylidene fluoride as a binder are mixed. This was put into N-methyl-2-pyrrolidone as a dispersion medium to form a slurry. Next, this was applied to a positive electrode current collector 33A made of an aluminum foil having a thickness of 15 μm, dried, and then pressed to form a positive electrode active material layer 33B.

続いて、炭酸エチレン３７．５質量％と、炭酸プロピレン３７．５質量％と、炭酸ビニレン１０質量％と、ＬｉＰＦ6 １５質量％とを混合して電解液を調整し、この電解液３０質量％と、重量平均分子量６０万のブロック共重合体であるポリフッ化ビニリデン１０質量％と、炭酸ジメチル６０質量％とを混合した前駆溶液を負極１０および正極３３の両面にそれぞれ塗布し、炭酸ジメチルを揮発させることにより電解質層３５を形成した。 Subsequently, 37.5% by mass of ethylene carbonate, 37.5% by mass of propylene carbonate, 10% by mass of vinylene carbonate, and 15% by mass of LiPF 6 were prepared to prepare an electrolyte solution, and this electrolyte solution was 30% by mass. And a precursor solution obtained by mixing 10% by mass of polyvinylidene fluoride, which is a block copolymer having a weight average molecular weight of 600,000, and 60% by mass of dimethyl carbonate, was applied to both surfaces of the negative electrode 10 and the positive electrode 33, and dimethyl carbonate was volatilized. Thus, the electrolyte layer 35 was formed.

そののち、リード３１，３２を取り付け、負極１０と正極３３とをセパレータ３４を介して積層して巻回し、アルミラミネートフィルムよりなる外装部材４１に封入した。これにより実施例１−１〜１−１９の二次電池を得た。   After that, the leads 31 and 32 were attached, the negative electrode 10 and the positive electrode 33 were laminated via a separator 34 and wound, and sealed in an exterior member 41 made of an aluminum laminate film. Thus, secondary batteries of Examples 1-1 to 1-19 were obtained.

実施例１−１〜１−１９に対する比較例１−１〜１−１３として、表２に示したように負極集電体の構成を変えたことを除き、他は実施例１−１〜１−１９と同様にして二次電池を作製した。なお、比較例１−１では実施例１−１〜１−９と同一の電解銅箔を用い、突起部を形成しなかった。比較例１−２では厚みが１８μｍ、十点平均粗さＲｚ１が１．２μｍである電解銅箔を用い、突起部を形成しなかった。比較例１−３〜１−５では厚みが１５μｍ、十点平均粗さＲｚ１が０．５μｍの圧延銅箔を用い、比較例１−３では突起部を形成せず、他は突起部の大きさを変化させて形成した。比較例１−６〜１−１３では、十点平均粗さＲｚ１が大きい電解銅箔を用い、比較例１−６，１−９では突起部を形成せず、他は突起部の大きさを変化させて形成した。   As Comparative Examples 1-1 to 1-13 with respect to Examples 1-1 to 1-19, except that the configuration of the negative electrode current collector was changed as shown in Table 2, other examples 1-1 to 1 were used. A secondary battery was made in the same manner as -19. In Comparative Example 1-1, the same electrolytic copper foil as in Examples 1-1 to 1-9 was used, and no protrusion was formed. In Comparative Example 1-2, an electrolytic copper foil having a thickness of 18 μm and a ten-point average roughness Rz1 of 1.2 μm was used, and no protrusion was formed. In Comparative Examples 1-3 to 1-5, a rolled copper foil having a thickness of 15 μm and a ten-point average roughness Rz1 of 0.5 μm is used. In Comparative Example 1-3, no protrusion is formed, and the others are the size of the protrusion. It was formed by changing the thickness. In Comparative Examples 1-6 to 1-13, an electrolytic copper foil having a large ten-point average roughness Rz1 is used, and in Comparative Examples 1-6 and 1-9, no protrusion is formed, and the size of the protrusion is the other. Changed and formed.

作製した実施例１−１〜１−１９および比較例１−１〜１−１３の二次電池について、２５℃の条件下で充放電試験を行い、２サイクル目に対する１０１サイクル目の容量維持率を求めた。その際、充電は、１ｍＡ／ｃｍ2 の定電流密度で電池電圧が４．２Ｖに達するまで行ったのち、４．２Ｖの定電圧で電流密度が０．０５ｍＡ／ｃｍ2 に達するまで行い、放電は、１ｍＡ／ｃｍ2 の定電流密度で電池電圧が２．５Ｖに達するまで行った。なお、充電を行う際には、負極１０の容量の利用率が９０％となるようにし、負極１０に金属リチウムが析出しないようにした。容量維持率は、２サイクル目の放電容量に対する１０１サイクル目の放電容量の比率、すなわち（１０１サイクル目の放電容量／２サイクル目の放電容量）×１００として算出した。それらの結果を表１，２に示す。 The fabricated secondary batteries of Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-13 were subjected to a charge / discharge test under the condition of 25 ° C., and the capacity retention rate at the 101st cycle with respect to the 2nd cycle. Asked. At that time, charging is performed at a constant current density of 1 mA / cm 2 until the battery voltage reaches 4.2 V, and then at a constant voltage of 4.2 V until the current density reaches 0.05 mA / cm 2. Was performed at a constant current density of 1 mA / cm 2 until the battery voltage reached 2.5V. In addition, when performing charging, the utilization factor of the capacity of the negative electrode 10 was set to 90% so that metallic lithium was not deposited on the negative electrode 10. The capacity retention ratio was calculated as the ratio of the discharge capacity at the 101st cycle to the discharge capacity at the 2nd cycle, that is, (discharge capacity at the 101st cycle / discharge capacity at the 2nd cycle) × 100. The results are shown in Tables 1 and 2.

また、図５〜１２に実施例１−４，比較例１−１，１−４，１−１０で用いた負極集電体１１の走査電子顕微鏡（Scanning Electron Microscope；ＳＥＭ）写真および走査イオン顕微鏡（Scanning Ion Microscope ；ＳＩＭ）写真を示す。図５は実施例１−４の表面構造、図６，７はその断面構造である。図８は比較例１−１の表面構造、図９は比較例１−４の表面構造、図１０は比較例１−１０の表面構造、図１１，１２はその断面構造である。図７，１２に示したように、基材１１Ａと突起部１１Ｂとで結晶粒子が異なっているので、その結晶構造から基材１１Ａの十点平均粗さＲｚ１および負極集電体１１の十点平均粗さＲｚ２を算出することができる。   5 to 12 are scanning electron microscope (SEM) photographs and a scanning ion microscope of the negative electrode current collector 11 used in Examples 1-4 and Comparative Examples 1-1, 1-4, and 1-10. (Scanning Ion Microscope; SIM) A photograph is shown. FIG. 5 shows the surface structure of Example 1-4, and FIGS. 8 shows the surface structure of Comparative Example 1-1, FIG. 9 shows the surface structure of Comparative Example 1-4, FIG. 10 shows the surface structure of Comparative Example 1-10, and FIGS. As shown in FIGS. 7 and 12, since the crystal particles are different between the base material 11A and the protrusion 11B, the ten point average roughness Rz1 of the base material 11A and the ten points of the negative electrode current collector 11 are determined from the crystal structure. The average roughness Rz2 can be calculated.

Figure 2010232190
Figure 2010232190

Figure 2010232190
Figure 2010232190

表１に示したように、十点平均粗さＲｚ１が２．０μｍ以下の基材１１Ａに突起部１１Ｂを形成し、Ｒｚ２−Ｒｚ１を０．２μｍ以上５．１μｍ以下とした実施例１−１〜１−１９では、６５％以上の高い容量維持率が得られた。   As shown in Table 1, Example 1-1 in which a protrusion 11B was formed on a base material 11A having a ten-point average roughness Rz1 of 2.0 μm or less, and Rz2-Rz1 was 0.2 μm or more and 5.1 μm or less. In ˜1-19, a high capacity retention rate of 65% or more was obtained.

これに対して、表２に示したように、十点平均粗さＲｚ１が２．０μｍ以下の基材を用い、突起部を形成していない比較例１−１〜１−３、および十点平均粗さＲｚ１が２．０μｍ以下の基材に突起部を形成し、Ｒｚ２−Ｒｚ１を０．１μｍとした比較例１−４では、負極集電体と負極活物質層との密着性が低く、容量維持率は５０％以下と低かった。また、十点平均粗さＲｚ１が２．０μｍ以下の基材に突起部を形成し、Ｒｚ２−Ｒｚ１を５．１μｍよりも大きくした比較例１−５では、突起部の脱落により負極集電体と負極活物質層との密着性を向上させることができず、容量維持率は１８％と低かった。   On the other hand, as shown in Table 2, Comparative Examples 1-1 to 1-3 in which a ten-point average roughness Rz1 is 2.0 μm or less and no protrusion is formed, and ten points In Comparative Example 1-4 in which protrusions are formed on a substrate having an average roughness Rz1 of 2.0 μm or less and Rz2-Rz1 is 0.1 μm, the adhesion between the negative electrode current collector and the negative electrode active material layer is low. The capacity retention rate was as low as 50% or less. Further, in Comparative Example 1-5 in which a protrusion was formed on a base material having a ten-point average roughness Rz1 of 2.0 μm or less, and Rz2-Rz1 was larger than 5.1 μm, the negative electrode current collector was removed due to the protrusion being dropped. The adhesion between the negative electrode active material layer and the negative electrode active material layer could not be improved, and the capacity retention rate was as low as 18%.

更に、十点平均粗さＲｚ１が２．０μｍよりも大きい基材を用い、突起部を形成していない比較例１−６，１−９、および十点平均粗さＲｚ１が２．０μｍよりも大きい基材に突起部を形成し、Ｒｚ２−Ｒｚ１を０．２μｍ以上５．１μｍ以下とした比較例１−７，１−８，１−１０〜１−１３でも、容量維持率は５６％以下と低かった。   Furthermore, using the base material whose ten-point average roughness Rz1 is larger than 2.0 μm, Comparative Examples 1-6 and 1-9 in which no protrusions are formed, and the ten-point average roughness Rz1 is more than 2.0 μm Even in Comparative Examples 1-7, 1-8, 1-10 to 1-13 in which protrusions were formed on a large substrate and Rz2-Rz1 was 0.2 μm or more and 5.1 μm or less, the capacity retention rate was 56% or less. It was low.

また、負極集電体１１の十点平均粗さＲｚ２が近い値を有する実施例１−４（容量維持率９０％）と比較例１−７（容量維持率４３％）、または実施例１−１７（容量維持率６８％）と比較例１−８（容量維持率４１％）とを比較すれば分かるように、負極集電体１１の表面粗度が同じでも、表面状態により容量維持率は大きく異なっていた。   In addition, Example 1-4 (capacity maintenance ratio 90%) and Comparative Example 1-7 (capacity maintenance ratio 43%), or Example 1 in which the ten-point average roughness Rz2 of the negative electrode current collector 11 is close. 17 (capacity retention ratio 68%) and Comparative Example 1-8 (capacity retention ratio 41%), as can be seen, even if the surface roughness of the negative electrode current collector 11 is the same, the capacity retention ratio depends on the surface condition. It was very different.

すなわち、十点平均粗さＲｚ１が２μｍ以下の基材１１Ａを用い、突起部１１Ｂを形成することにより、負極集電体１１の十点平均粗さＲｚ２と基材１１Ａの十点平均粗さＲｚ１との差Ｒｚ２−Ｒｚ１を０．２μｍ以上５．１μｍ以下とするようにすれば、サイクル特性を向上させることができることが分かった。   That is, by using the base material 11A having a 10-point average roughness Rz1 of 2 μm or less and forming the protrusion 11B, the 10-point average roughness Rz2 of the negative electrode current collector 11 and the 10-point average roughness Rz1 of the base material 11A It was found that the cycle characteristics can be improved by setting the difference Rz2−Rz1 to 0.2 μm or more and 5.1 μm or less.

また、負極集電体１１の十点平均粗さＲｚ２を１．３μｍ以上３．５μｍ以下とした実施例１−２〜１−６，１−１２〜１−１６によれば、７０％以上の容量維持率が得られた。すなわち、負極集電体１１の十点平均粗さＲｚ２を１．３μｍ以上３．５μｍ以下とすれば、より好ましいことが分かった。   Further, according to Examples 1-2 to 1-6 and 1-12 to 1-16 in which the ten-point average roughness Rz2 of the negative electrode current collector 11 was 1.3 μm or more and 3.5 μm or less, 70% or more A capacity retention rate was obtained. In other words, it was found that the ten-point average roughness Rz2 of the negative electrode current collector 11 was more preferably 1.3 μm or more and 3.5 μm or less.

（実施例２−１〜２−８）
スパッタリング法により負極活物質層１２を成膜したことを除き、他は実施例１−２〜１−９と同様にして二次電池を作製した。また、実施例２−１〜２−８に対する比較例２−１〜２−５として、比較例１−１０〜１−１３と同様の負極集電体を用いたことを除き、他は実施例２−１〜２−８と同様にして二次電池を作製した。実施例２−１〜２−８および比較例２−１〜２−５の二次電池についても、実施例１−２〜１−９と同様にして容量維持率を求めた。それらの結果を表３に示す。 (Examples 2-1 to 2-8)
A secondary battery was fabricated in the same manner as in Examples 1-2 to 1-9, except that the negative electrode active material layer 12 was formed by sputtering. Further, as Comparative Examples 2-1 to 2-5 with respect to Examples 2-1 to 2-8, except that the negative electrode current collector similar to Comparative Examples 1-10 to 1-13 was used, other examples were used. Secondary batteries were fabricated in the same manner as in 2-1 to 2-8. For the secondary batteries of Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-5, the capacity retention ratio was determined in the same manner as in Examples 1-2 to 1-9. The results are shown in Table 3.

Figure 2010232190
Figure 2010232190

表３に示したように、負極活物質層１２をスパッタリング法により形成した場合においても同様の結果が得られた。   As shown in Table 3, the same result was obtained when the negative electrode active material layer 12 was formed by sputtering.

以上、実施の形態および実施例を挙げて本発明を説明したが、本発明は上記実施の形態および実施例に限定されるものではなく、種々変形可能である。例えば、上記実施の形態および実施例では、液状の電解質である電解液、またはいわゆるゲル状の電解質を用いる場合について説明したが、他の電解質を用いるようにしてもよい。他の電解質としては、イオン伝導性を有する固体電解質、固体電解質と電解液とを混合したもの、あるいは固体電解質とゲル状の電解質とを混合したものが挙げられる。   Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the above embodiments and examples, and various modifications can be made. For example, in the above-described embodiments and examples, the case where an electrolytic solution which is a liquid electrolyte or a so-called gel electrolyte is used has been described, but another electrolyte may be used. Examples of other electrolytes include solid electrolytes having ionic conductivity, a mixture of a solid electrolyte and an electrolyte solution, and a mixture of a solid electrolyte and a gel electrolyte.

なお、固体電解質には、例えば、イオン伝導性を有する高分子化合物に電解質塩を分散させた高分子固体電解質、またはイオン伝導性ガラスあるいはイオン性結晶などよりなる無機固体電解質を用いることができる。高分子固体電解質の高分子化合物としては、例えば、ポリエチレンオキサイドあるいはポリエチレンオキサイドを含む架橋体などのエーテル系高分子化合物、ポリメタクリレートなどのエステル系高分子化合物、アクリレート系高分子化合物を単独あるいは混合して、または共重合させて用いることができる。また、無機固体電解質としては、窒化リチウムあるいはリン酸リチウムなどを含むもの用いることができる。   As the solid electrolyte, for example, a polymer solid electrolyte in which an electrolyte salt is dispersed in a polymer compound having ion conductivity, or an inorganic solid electrolyte made of ion conductive glass or ionic crystals can be used. Examples of the polymer compound of the solid polymer electrolyte include, for example, an ether polymer compound such as polyethylene oxide or a crosslinked product containing polyethylene oxide, an ester polymer compound such as polymethacrylate, and an acrylate polymer compound. Or can be copolymerized. In addition, as the inorganic solid electrolyte, one containing lithium nitride or lithium phosphate can be used.

また、上記実施の形態および実施例では、コイン型および巻回ラミネート型の二次電池について説明したが、本発明は、円筒型，角型，ボタン型，薄型，大型あるいは積層ラミネート型などの他の形状を有する二次電池についても同様に適用することができる。   In the above embodiments and examples, the coin type and wound laminate type secondary batteries have been described. However, the present invention is not limited to a cylindrical type, a square type, a button type, a thin type, a large size, or a laminated laminate type. The present invention can be similarly applied to a secondary battery having the shape.

１０…負極、１１…負極集電体、１１Ａ…基材、１１Ｂ…突起部、１２…負極活物質層、２１…外装カップ、２２…外装缶、２３，３３…正極、２３Ａ，３３Ａ…正極集電体、２３Ｂ，３３Ｂ…正極活物質層、２４，３４…セパレータ、２５…ガスケット、３１，３２…リード、３０…電極巻回体、３５…電解質層、３６…保護テープ   DESCRIPTION OF SYMBOLS 10 ... Negative electrode, 11 ... Negative electrode collector, 11A ... Base material, 11B ... Projection part, 12 ... Negative electrode active material layer, 21 ... Exterior cup, 22 ... Exterior can, 23, 33 ... Positive electrode, 23A, 33A ... Positive electrode collection Electrical body, 23B, 33B ... positive electrode active material layer, 24, 34 ... separator, 25 ... gasket, 31, 32 ... lead, 30 ... wound electrode body, 35 ... electrolyte layer, 36 ... protective tape

Claims (10)

負極集電体に構成元素としてケイ素（Ｓｉ）を含む負極活物質層が設けられ、
前記負極集電体は、基材と、この基材に設けられた突起部とを有し、
前記負極活物質層が設けられた面の前記基材の十点平均粗さＲｚ１は２．０μｍ以下であり、
前記負極活物質層が設けられた面の前記負極集電体の十点平均粗さＲｚ２から前記基材の十点平均粗さＲｚ１を引いた差Ｒｚ２−Ｒｚ１は、０．２μｍ以上５．１μｍ以下であり、
前記基材の厚みは、１５μｍ以上１８μｍ以下である、
二次電池用負極。 A negative electrode active material layer containing silicon (Si) as a constituent element is provided on the negative electrode current collector,
The negative electrode current collector has a base material and a protrusion provided on the base material,
The ten-point average roughness Rz1 of the base material on the surface provided with the negative electrode active material layer is 2.0 μm or less,
The difference Rz2−Rz1 obtained by subtracting the ten-point average roughness Rz1 of the base material from the ten-point average roughness Rz2 of the negative electrode current collector on the surface provided with the negative electrode active material layer is 0.2 μm or more and 5.1 μm. And
The thickness of the substrate is 15 μm or more and 18 μm or less,
Negative electrode for secondary battery. 前記負極集電体の十点平均粗さＲｚ２は１．３μｍ以上３．５μｍ以下である、請求項１記載の二次電池用負極。   The negative electrode for a secondary battery according to claim 1, wherein the negative electrode current collector has a ten-point average roughness Rz2 of 1.3 μm or more and 3.5 μm or less. 前記Ｒｚ２−Ｒｚ１は、０．７μｍ以上２．６μｍ以下である、請求項１記載の二次電池用負極。   The negative electrode for a secondary battery according to claim 1, wherein the Rz2-Rz1 is 0.7 µm or more and 2.6 µm or less. 前記負極活物質層は蒸着法により形成され、前記基材は電解銅箔よりなり、前記負極集電体の十点平均粗さＲｚ２は２．５μｍ以上３．５μｍ以下である、請求項３記載の二次電池用負極。   The negative electrode active material layer is formed by a vapor deposition method, the substrate is made of an electrolytic copper foil, and the ten-point average roughness Rz2 of the negative electrode current collector is 2.5 μm or more and 3.5 μm or less. Negative electrode for secondary battery. 前記基材は、粒子状の結晶構造を有する、請求項１記載の二次電池用負極。   The negative electrode for a secondary battery according to claim 1, wherein the base material has a particulate crystal structure. 正極および負極と共に電解質を備え、
前記負極は、負極集電体に構成元素としてケイ素（Ｓｉ）を含む負極活物質層が設けられており、
前記負極集電体は、基材と、この基材に設けられた突起部とを有し、
前記負極活物質層が設けられた面の前記基材の十点平均粗さＲｚ１は２．０μｍ以下であり、
前記負極活物質層が設けられた面の前記負極集電体の十点平均粗さＲｚ２から前記基材の十点平均粗さＲｚ１を引いた差Ｒｚ２−Ｒｚ１は、０．２μｍ以上５．１μｍ以下であり、
前記基材の厚みは、１５μｍ以上１８μｍ以下である、
二次電池。 An electrolyte is provided with a positive electrode and a negative electrode,
The negative electrode is provided with a negative electrode active material layer containing silicon (Si) as a constituent element in a negative electrode current collector,
The negative electrode current collector has a base material and a protrusion provided on the base material,
The ten-point average roughness Rz1 of the substrate on the surface provided with the negative electrode active material layer is 2.0 μm or less,
The difference Rz2−Rz1 obtained by subtracting the ten-point average roughness Rz1 of the base material from the ten-point average roughness Rz2 of the negative electrode current collector on the surface provided with the negative electrode active material layer is 0.2 μm or more and 5.1 μm. And
The thickness of the substrate is 15 μm or more and 18 μm or less,
Secondary battery. 前記負極集電体の十点平均粗さＲｚ２は１．３μｍ以上３．５μｍ以下である、請求項６記載の二次電池。   The secondary battery according to claim 6, wherein the negative electrode current collector has a ten-point average roughness Rz2 of 1.3 μm or more and 3.5 μm or less. 前記Ｒｚ２−Ｒｚ１は、０．７μｍ以上２．６μｍ以下である、請求項６記載の二次電池。   The secondary battery according to claim 6, wherein Rz2−Rz1 is 0.7 μm or more and 2.6 μm or less. 前記負極活物質層は蒸着法により形成され、前記基材は電解銅箔よりなり、前記負極集電体の十点平均粗さＲｚ２は２．５μｍ以上３．５μｍ以下である、請求項８記載の二次電池。   The negative electrode active material layer is formed by a vapor deposition method, the substrate is made of an electrolytic copper foil, and the ten-point average roughness Rz2 of the negative electrode current collector is 2.5 μm or more and 3.5 μm or less. Secondary battery. 前記基材は、粒子状の結晶構造を有する、請求項６記載の二次電池。   The secondary battery according to claim 6, wherein the base material has a particulate crystal structure.
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Citations (4)

* 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
JP2002373647A (en) * 2000-09-20 2002-12-26 Sanyo Electric Co Ltd Electrode for lithium secondary battery and the lithium secondary battery
JP2003007295A (en) * 2001-03-06 2003-01-10 Sanyo Electric Co Ltd Electrode for lithium secondary battery, and the lithium secondary battery
JP2004087284A (en) * 2002-08-27 2004-03-18 Sanyo Electric Co Ltd Lithium secondary cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002373647A (en) * 2000-09-20 2002-12-26 Sanyo Electric Co Ltd Electrode for lithium secondary battery and the lithium secondary battery
JP2003007295A (en) * 2001-03-06 2003-01-10 Sanyo Electric Co Ltd Electrode for lithium secondary battery, and the lithium secondary battery
JP2002313319A (en) * 2001-04-09 2002-10-25 Sanyo Electric Co Ltd Electrode for lithium secondary battery and lithium secondary battery
JP2004087284A (en) * 2002-08-27 2004-03-18 Sanyo Electric Co Ltd Lithium secondary cell

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