JP4850405B2 - Lithium ion secondary battery and manufacturing method thereof - Google Patents

Lithium ion secondary battery and manufacturing method thereof Download PDF

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JP4850405B2
JP4850405B2 JP2004322516A JP2004322516A JP4850405B2 JP 4850405 B2 JP4850405 B2 JP 4850405B2 JP 2004322516 A JP2004322516 A JP 2004322516A JP 2004322516 A JP2004322516 A JP 2004322516A JP 4850405 B2 JP4850405 B2 JP 4850405B2
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negative electrode
active material
current collector
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thin film
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JP2005183366A (en
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和義 本田
毅一郎 大石
靖彦 美藤
貴之 中本
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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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Description

本発明はリチウムイオン二次電池及びその製造方法に関する。 The present invention relates to a lithium ion secondary battery and a method for manufacturing the same.

リチウムイオン二次電池は、負極集電体、負極活物質、電解質、セパレーター、正極活物質、正極集電体を主な構成要素とする。このリチウムイオン二次電池は、移動体通信機器や各種ＡＶ機器のエネルギー源として大きな役割を果たしている。機器の小型化高性能化とあいまってリチウムイオン二次電池の小形化、高エネルギー密度化が進められており、電池を構成する各要素の改良に多くの努力が払われている。 Lithium ion secondary battery, the negative electrode current collector, the negative electrode active material, the electrolyte, the separator, the positive electrode active material, the main component of the positive electrode current collector. The lithium ion secondary battery plays a major role as an energy source for mobile communication devices and various types of AV equipment. Compact high-performance device coupled with miniaturization of the lithium ion secondary battery has higher energy density is advanced, much effort on improving the elements constituting the battery have been made.

例えば、特許文献１には、特定の遷移金属酸化物の混合粉末を加熱し溶融後、急冷して得たアモルファス化した酸化物を正極活物質として用いることにより、高エネルギー密度化を実現できることが開示されている。   For example, Patent Document 1 discloses that a high energy density can be realized by using, as a positive electrode active material, an amorphous oxide obtained by heating, melting, and rapidly cooling a mixed powder of a specific transition metal oxide. It is disclosed.

また、特許文献２には、正極活物質としてリチウムを含有する遷移金属酸化物を用い、負極活物質としてケイ素原子を含む化合物を用い、かつ正極活物質重量を負極活物質重量よりも多くすることによって電池容量とサイクル寿命を高めることができることが開示されている。   In Patent Document 2, a transition metal oxide containing lithium is used as a positive electrode active material, a compound containing a silicon atom is used as a negative electrode active material, and the weight of the positive electrode active material is larger than the weight of the negative electrode active material. Can increase battery capacity and cycle life.

更に、特許文献３には、負極活物質として非晶質シリコン薄膜を用いることが開示されている。これにより、カーボンを用いた場合に比べてリチウムイオンを多く吸蔵できるので大容量化が可能になると期待される。   Further, Patent Document 3 discloses using an amorphous silicon thin film as a negative electrode active material. As a result, more lithium ions can be occluded than when carbon is used, and it is expected that the capacity can be increased.

また、特許文献４には、負極集電体上に負極活物質を形成するに際して、負極集電体と負極活物質との界面近傍の負極活物質内に負極集電体成分が拡散した混合層が形成されるような温度で負極活物質を形成することが記載されている。混合層により負極集電体と負極活物質との密着性が良好となり、充放電容量が高く、充放電サイクル特性に優れたリチウムイオン二次電池用電極が得られるとされている。
特開平８−７８００２号公報 特開２０００−１２０９２号公報 特開２００２−８３５９４号公報 特開２００１−２６６８５１号公報 Patent Document 4 discloses a mixed layer in which a negative electrode current collector component is diffused in a negative electrode active material in the vicinity of the interface between the negative electrode current collector and the negative electrode active material when the negative electrode active material is formed on the negative electrode current collector. Forming a negative electrode active material at a temperature at which is formed. The mixed layer enables good adhesion between the anode current collector and the anode active material, charge and discharge capacity is high, excellent electrode for a lithium ion secondary battery in the charge-discharge cycle characteristics are to be obtained.
JP-A-8-78002 Japanese Unexamined Patent Publication No. 2000-12092 JP 2002-83594 A JP 2001-266851 A

リチウムイオン二次電池において、電池容量及びサイクル特性の向上は特に重要な課題であるが、上記の従来の技術ではいまだ十分とは言えない。 In lithium ion secondary batteries , improvement of battery capacity and cycle characteristics are particularly important issues, but the above-mentioned conventional techniques are still not sufficient.

サイクル特性は、集電体と活物質との界面における付着強度によって大きな影響を受ける。上記特許文献４ではこの界面に混合層を形成して付着強度を向上させるが、負極活物質を形成する際の温度制御が必要であり、これは生産上の制約となる。   The cycle characteristics are greatly affected by the adhesion strength at the interface between the current collector and the active material. In the above-mentioned Patent Document 4, a mixed layer is formed at this interface to improve the adhesion strength. However, temperature control when forming the negative electrode active material is necessary, which is a production restriction.

このように、優れたサイクル特性を実現する為の化学的なアプローチはいまだ十分とは言えず、高性能シリコン負極の確立が求められている。   Thus, the chemical approach for realizing excellent cycle characteristics is not yet sufficient, and establishment of a high-performance silicon negative electrode is required.

本発明は、簡単な手法により得ることができる、サイクル特性の良好なリチウムイオン二次電池とその製造方法を提供することを目的とする。 An object of the present invention is to provide a lithium ion secondary battery with good cycle characteristics, which can be obtained by a simple technique, and a method for producing the same.

上記目的を達成するため、本発明のリチウムイオン二次電池の製造方法は、基板上に正極集電体、正極活物質、及び固体電解質がこの順に形成された積層体の前記固体電解質上にシリコンを主成分として含む負極活物質薄膜及び集電体を真空成膜法により形成するリチウムイオン二次電池の製造方法であって、それぞれからの成膜粒子の一部が相互に混合されるように隣り合わせて配置された、前記負極活物質薄膜を形成するための負極活物質成膜源及び前記集電体を形成するための集電体成膜源に対して、前記積層体を、前記負極活物質成膜源側から前記集電体成膜源側に向かって相対的に移動させることを特徴とする。 To achieve the above object, manufacturing method of a lithium ion secondary battery of the present invention, the positive electrode current collector on the substrate, a positive electrode active material, and solid electrolyte on the solid electrolyte of the laminate formed in this order A method of manufacturing a lithium ion secondary battery in which a negative electrode active material thin film containing silicon as a main component and a current collector are formed by a vacuum film formation method, and a part of film formation particles from each is mixed with each other The negative electrode active material film forming source for forming the negative electrode active material thin film and the current collector film forming source for forming the current collector are disposed adjacent to each other, and the laminate is connected to the negative electrode It is relatively moved from the active material film forming source side toward the current collector film forming source side.

本発明のリチウムイオン二次電池は、基板と、正極集電体と、正極活物質と、固体電解質と、シリコンを主成分として含む負極活物質薄膜と、集電体とをこの順に備える。前記負極活物質薄膜及び前記集電体は、それぞれからの成膜粒子の一部が相互に混合されるように隣り合わせて配置された、前記負極活物質薄膜を形成するための負極活物質成膜源及び前記集電体を形成するための集電体成膜源に対して、前記基板上に前記正極集電体、前記正極活物質、及び前記固体電解質がこの順に形成された積層体を、前記負極活物質成膜源側から前記集電体成膜源側に向かって相対的に移動させることにより、前記固体電解質上に真空成膜法により形成されたものであることを特徴とする。 The lithium ion secondary battery of the present invention includes a substrate, a positive electrode current collector, a positive electrode active material, a solid electrolyte, a negative electrode active material thin film containing silicon as a main component, and a current collector in this order . The negative electrode active material thin film and the current collector are arranged adjacent to each other so that a part of the film formation particles from each other are mixed with each other, and a negative electrode active material film for forming the negative electrode active material thin film is formed A stacked body in which the positive electrode current collector, the positive electrode active material, and the solid electrolyte are formed in this order on the substrate with respect to the current collector film forming source for forming the source and the current collector, It is formed on the solid electrolyte by a vacuum film formation method by relatively moving from the negative electrode active material film formation source side to the current collector film formation source side.

本発明のリチウムイオン二次電池及びその製造方法によれば、サイクル特性の良好なリチウムイオン二次電池を提供することができる。 According to the lithium ion secondary battery及beauty its manufacturing method of the present invention, it is possible to provide a good lithium ion secondary battery cycle characteristics.

上記の製造方法のように、２つの成膜源を用いた連続混合成膜を行うことにより、負極活物質薄膜と集電体との界面に、集電体の主成分元素及び負極活物質を構成するシリコンの組成分布がなだらかに変化する組成傾斜層が形成される。従って、充放電時に負極活物質がイオンを吸蔵／放出することによって負極活物質内のシリコン粒子が膨張／収縮しても、組成傾斜層がこれに伴う歪みを緩和するので、負極活物質薄膜と集電体との界面での剥離が抑制される。このようにして負極活物質薄膜と集電体との界面での付着強度が向上するので、サイクル特性が向上したリチウムイオン二次電池を提供することができる。 As the above manufacturing method, by performing the continuous mixing film formation using the two film forming source, the interface between the negative electrode active material thin film and the current collector, major element and the negative electrode active material of the current collector Thus, a composition gradient layer in which the composition distribution of silicon constituting the layer changes gently is formed. Therefore, even if silicon particles in the negative electrode active material expand / contract due to the negative electrode active material occluding / releasing ions during charging / discharging, the composition gradient layer relaxes the strain associated therewith. Separation at the interface with the current collector is suppressed. Thus, since the adhesion strength at the interface between the negative electrode active material thin film and the current collector is improved, a lithium ion secondary battery with improved cycle characteristics can be provided.

負極活物質薄膜と集電体との界面近傍の、集電体の主成分元素及びシリコンの組成分布がなだらかに変化する組成傾斜層は、上記の連続混合成膜により形成される。負極活物質薄膜と集電体との間に単に第３の層を挿入しただけでは、第３の層と負極活物質薄膜との間、及び第３の層と集電体との間に組成が不連続な境界ができ、この境界にシリコン粒子が膨張／収縮したときの歪みにより生じる力が集中して良好なサイクル特性が得られない。   The composition gradient layer in which the composition distribution of the main components of the current collector and silicon in the vicinity of the interface between the negative electrode active material thin film and the current collector changes gently is formed by the continuous mixed film formation. By simply inserting the third layer between the negative electrode active material thin film and the current collector, the composition between the third layer and the negative electrode active material thin film and between the third layer and the current collector. However, a discontinuous boundary is formed, and the force generated by the strain when silicon particles expand / contract is concentrated on this boundary, and good cycle characteristics cannot be obtained.

上述したように、特許文献４には、負極集電体上に負極活物質を形成するに際して、負極集電体と負極活物質との界面近傍の負極活物質内に負極集電体成分が拡散した混合層が形成されるような温度で負極活物質を形成することが記載されているが、基板温度条件が高温に制限され、且つ、厳密な温度制御が必要である。これに対して、本発明のリチウムイオン二次電池の製造方法では負極活物質薄膜を連続混合成膜により形成するだけでよいので、生産性が良好である。 As described above, in Patent Document 4, when the negative electrode active material is formed on the negative electrode current collector, the negative electrode current collector component diffuses into the negative electrode active material in the vicinity of the interface between the negative electrode current collector and the negative electrode active material. Although it is described that the negative electrode active material is formed at a temperature at which the mixed layer is formed, the substrate temperature condition is limited to a high temperature, and strict temperature control is required. On the other hand, in the method for producing a lithium ion secondary battery of the present invention, the negative electrode active material thin film only needs to be formed by continuous mixed film formation, so that the productivity is good.

更に、上記の製造方法によれば、集電体も真空成膜法により負極活物質薄膜と同時に形成することができるので、極めて効率がよい。 Furthermore, according to the manufacturing method described above, it is possible to collector is formed at the same time as the negative electrode active material thin film by a vacuum deposition method, it is extremely efficient.

上記の製造方法において、「シリコンを主成分として含む」とは、シリコンの含有量が５０ａｔ％以上であることを意味し、望ましくは７０ａｔ％以上、更に望ましくは８０ａｔ％以上、最も望ましくは９０ａｔ％以上である。負極活物質薄膜におけるシリコン含有量が高いほど電池容量を向上できる。 In manufacturing method described above, the "silicon containing as a main component" means that the content of silicon is not less than 50at%, preferably 70 at% or more, more preferably 80at% or more, and most preferably 90at % Or more. The higher the silicon content in the negative electrode active material thin film, the better the battery capacity.

上記の製造方法において、「真空成膜法」とは、蒸着法、スパッタ法、ＣＶＤ法、イオンプレーティング法、レーザーアブレーション法などの各種真空薄膜製造プロセスを含む。薄膜の種類に応じて最適な成膜法を選択することができる。真空成膜法により薄い負極活物質薄膜を効率よく製造できる。その結果、小型薄型のリチウムイオン二次電池が得られる。また、「成膜粒子」とは、これら真空成膜法における成膜源（ソース）から放出され被成膜面に付着して薄膜を形成する原子、分子、又はクラスタなどの粒子を意味する。 In manufacturing method described above, the "vacuum deposition" includes vapor deposition, sputtering, CVD, ion plating method, the various vacuum thin film manufacturing processes such as laser ablation method. An optimum film formation method can be selected according to the type of the thin film. A thin negative electrode active material thin film can be efficiently produced by a vacuum film formation method. As a result, a small and thin lithium ion secondary battery can be obtained. The “film formation particles” mean particles such as atoms, molecules, or clusters that are emitted from a film formation source (source) in these vacuum film formation methods and adhere to the film formation surface to form a thin film.

上記の製造方法において、前記真空成膜法が真空蒸着法であることが好ましい。これにより、高品位の負極活物質薄膜を安定して効率よく形成できる。 In manufacturing method described above, it is preferable that the vacuum deposition method is vacuum deposition method. Thereby, a high quality negative electrode active material thin film can be formed stably and efficiently.

また、上記の製造方法において、前記集電体成膜源が銅を主成分として含むことが好ましい。これによりリチウムイオン二次電池を容易且つ安価に製造できる。ここで、「銅を主成分として含む」とは、銅の含有量が５０ａｔ％以上であることを意味し、望ましくは７０ａｔ％以上、更に望ましくは８０ａｔ％以上、最も望ましくは９０ａｔ％以上である。 Further, in the manufacturing method described above, it is preferable that the current collector film source comprises copper as a main component. Thereby, a lithium ion secondary battery can be manufactured easily and inexpensively. Here, “containing copper as a main component” means that the copper content is 50 at% or more, desirably 70 at% or more, more desirably 80 at% or more, and most desirably 90 at% or more. .

上記の製造方法において、前記負極活物質薄膜に含まれるシリコンの一部が酸化物であることが好ましい場合がある。ここでいうシリコンの酸化物とは、負極活物質薄膜と他の層との境界部分に含まれるシリコンの酸化物を含まない。厚さ方向において、上下の境界部分を除いた中間領域にシリコンの酸化物が含まれていることを意味する。負極活物質薄膜中のシリコンの含有量が多く、電池容量が大きい場合には、充放電時のシリコン粒子の膨張／収縮の程度が大きくなり、サイクル特性が低下する場合がある。負極活物質薄膜がシリコンの酸化物を含むと、シリコンの酸化物は充放電時の膨張／収縮が少ないから、充放電時のシリコン粒子の膨張／収縮を抑えることができ、サイクル特性を向上させることができる。 In manufacturing methods described above, a portion of the silicon contained in the negative electrode active material thin film it may be preferably an oxide. The silicon oxide here does not include silicon oxide contained in the boundary portion between the negative electrode active material thin film and other layers. It means that silicon oxide is contained in an intermediate region excluding the upper and lower boundary portions in the thickness direction. When the content of silicon in the negative electrode active material thin film is large and the battery capacity is large, the degree of expansion / contraction of silicon particles during charge / discharge increases, and the cycle characteristics may deteriorate. When the negative electrode active material thin film contains a silicon oxide, the silicon oxide has little expansion / contraction during charging / discharging, so that expansion / contraction of silicon particles during charging / discharging can be suppressed, and cycle characteristics are improved. be able to.

以下、図面を参照しながら本発明の実施の形態について説明する。   Hereinafter, embodiments of the present invention will be described with reference to the drawings.

（参考実施の形態１）
参考実施の形態１にかかるリチウムイオン二次電池を説明する。 ( Reference Embodiment 1)
A lithium ion secondary battery according to Reference Embodiment 1 will be described.

本参考実施の形態１のリチウムイオン二次電池は、両面に正極活物質が形成された正極集電体と、セパレータと、両面に負極活物質が形成された負極集電体とを、正極集電体と負極集電体との間にセパレータが介在するようにして巻回した円筒状巻回物を電池缶に収め、この電池缶を電解液で満たしてなる。 The lithium ion secondary battery of the present first reference embodiment includes a positive electrode current collector where the positive electrode active material formed on both surfaces, a separator and a negative electrode current collector where the anode active material formed on both surfaces, the positive electrode current A cylindrical roll wound with the separator interposed between the electric current collector and the negative electrode current collector is housed in a battery can, and the battery can is filled with an electrolytic solution.

正極集電体としては、Ａｌ、Ｃｕ、Ｎｉ、ステンレススチールの厚さ１０〜８０μｍの箔、網などを用いることが出来る。あるいは、表面に金属薄膜が形成されたポリエチレンテレフタレート、ポリエチレンナフタレートなどの高分子基板を用いることも出来る。   As the positive electrode current collector, Al, Cu, Ni, stainless steel foil or net having a thickness of 10 to 80 μm can be used. Alternatively, a polymer substrate such as polyethylene terephthalate or polyethylene naphthalate having a metal thin film formed on the surface can be used.

正極活物質はリチウムイオンの出入が出来ることが必要であり、Ｃｏ、Ｎｉ、Ｍｏ、Ｔｉ、Ｍｎ、Ｖなどの遷移金属を含むリチウム含有遷移金属酸化物や、これにアセチレンブラックなどの導電性補助剤とニトリルゴム、ブチルゴム、ポリテトラフルオロエチレン、ポリフッ化ビニリデンなどの結着剤とを混合した混合ペーストを用いることも出来る。   The positive electrode active material needs to be able to enter and exit lithium ions, and includes lithium-containing transition metal oxides including transition metals such as Co, Ni, Mo, Ti, Mn, and V, and conductivity aids such as acetylene black. It is also possible to use a mixed paste in which an agent and a binder such as nitrile rubber, butyl rubber, polytetrafluoroethylene, and polyvinylidene fluoride are mixed.

負極集電体としては、Ｃｕ、Ｎｉ、ステンレススチールの厚さ１０〜８０μｍの箔、網などを用いることが出来る。あるいは、表面に金属薄膜が形成されたポリエチレンテレフタレート、ポリエチレンナフタレートなどの高分子基板を用いることも出来る。   As the negative electrode current collector, a foil, net, or the like of Cu, Ni, stainless steel having a thickness of 10 to 80 μm can be used. Alternatively, a polymer substrate such as polyethylene terephthalate or polyethylene naphthalate having a metal thin film formed on the surface can be used.

セパレーターは機械的強度とイオン透過性とに優れることが好ましく、ポリエチレン、ポリプロピレン、ポリフッ化ビニリデンなどを用いることが出来る。セパレーターの孔径は例えば０．０１〜１０μｍであり、その厚さは例えば５〜２００μｍである。   The separator is preferably excellent in mechanical strength and ion permeability, and polyethylene, polypropylene, polyvinylidene fluoride, and the like can be used. The pore diameter of the separator is, for example, 0.01 to 10 μm, and the thickness thereof is, for example, 5 to 200 μm.

電解液としては、エチレンカーボネート、プロピレンカーボネート、メチルエチルカーボネート、６フッ化メチルアセテート、又はテトロヒドロフラン等の溶媒に、ＬｉＰＦ6
、ＬｉＢＦ4、ＬｉＣｌＯ4などの電解質塩を溶解させた溶液を用いることが出来る。 As an electrolytic solution, a solvent such as ethylene carbonate, propylene carbonate, methyl ethyl carbonate, hexafluoromethyl acetate, or tetrohydrofuran, LiPF6 is used.
A solution in which an electrolyte salt such as LiBF4 or LiClO4 is dissolved can be used.

電池缶としては、ステンレススチール、鉄、アルミニウム、ニッケルメッキスチールなどの金属材料を用いることができるが、電池用途に応じてプラスチック材料を用いることもできる。   As the battery can, a metal material such as stainless steel, iron, aluminum, or nickel-plated steel can be used, but a plastic material can also be used depending on the battery application.

負極活物質は、シリコンを主成分とするシリコン薄膜である。シリコン薄膜はアモルファスまたは微結晶であることが好ましく、スパッタリング法、蒸着法、ＣＶＤ法をはじめとする真空成膜法で形成することができる。   The negative electrode active material is a silicon thin film containing silicon as a main component. The silicon thin film is preferably amorphous or microcrystalline, and can be formed by a vacuum film formation method such as sputtering, vapor deposition, or CVD.

［参考実施例１、２、参考比較例１］
参考実施の形態１に対応する参考実施例を説明する。 [ Reference Examples 1 and 2, Reference Comparative Example 1]
A reference example corresponding to the reference embodiment 1 will be described.

まず、正極の作製方法を述べる。Ｌｉ2ＣＯ3とＣｏＣＯ3とを所定のモル比で混合し、大気中において９００℃で加熱することによって合成してＬｉＣｏＯ2を得た。これを１００メッシュ以下に分級して正極活物質を得た。この正極活物質１００ｇ、導電剤として炭素粉末１０ｇ、結着剤としてポリ４フッ化エチレンディスパージョン８ｇ、及び純水を混ぜ合わせてペースト状にした。この正極活物質含有ペーストを、正極集電体としての厚さ１５μｍの帯状のアルミニウム箔の両面に塗布し、乾燥して正極を得た。 First, a method for manufacturing a positive electrode will be described. Li 2 CO 3 and CoCO 3 were mixed at a predetermined molar ratio and synthesized by heating at 900 ° C. in the atmosphere to obtain LiCoO 2 . This was classified to 100 mesh or less to obtain a positive electrode active material. 100 g of this positive electrode active material, 10 g of carbon powder as a conductive agent, 8 g of polytetrafluoroethylene dispersion as a binder, and pure water were mixed to form a paste. This positive electrode active material-containing paste was applied to both sides of a 15 μm-thick strip-shaped aluminum foil as a positive electrode current collector and dried to obtain a positive electrode.

負極集電体として厚さ３０μｍの帯状の銅箔を用い、その両面に負極活物質としてシリコン薄膜をスパッタリング法により形成した。詳細は後述する。   A strip-shaped copper foil having a thickness of 30 μm was used as the negative electrode current collector, and a silicon thin film was formed as a negative electrode active material on both surfaces by sputtering. Details will be described later.

セパレ−タとして、厚さ２５μｍで、正極集電体及び負極集電体よりも広幅の帯状の多孔性ポリエチレンを用いた。   As the separator, a belt-like porous polyethylene having a thickness of 25 μm and wider than the positive electrode current collector and the negative electrode current collector was used.

正極集電体にこれと同材質の正極リードをスポット溶接にて取り付けた。また、負極集電体にこれと同材質の負極リードをスポット溶接にて取り付けた。   A positive electrode lead made of the same material was attached to the positive electrode current collector by spot welding. Further, a negative electrode lead made of the same material as the negative electrode current collector was attached by spot welding.

上記によって得た正極と負極との間にセパレータが介在するようにこれらを重ね合わせて渦巻き状に巻回した。この円筒状巻回物の上下面に、ポリプロピレン製の絶縁板をそれぞれ配して有底の円筒状電池缶内に収納し、電池缶の開口近傍に段部を形成した後、非水電解液として、ＬｉＰＦ6を濃度１×１０3モル／ｍ3で溶解したエチレンカーボネートとジエチルカーボネートの等比体積混合溶液を電池缶に注入し、封口板で開口を密閉してリチウムイオン二次電池を得た。 These were overlapped so that a separator was interposed between the positive electrode and the negative electrode obtained as described above, and wound in a spiral shape. Polypropylene insulation plates are arranged on the upper and lower surfaces of this cylindrical wound product, respectively, and housed in a bottomed cylindrical battery can, and a step is formed in the vicinity of the opening of the battery can. Then, an equal volume mixed solution of ethylene carbonate and diethyl carbonate in which LiPF 6 was dissolved at a concentration of 1 × 10 3 mol / m 3 was poured into a battery can, and the opening was sealed with a sealing plate to obtain a lithium ion secondary battery. It was.

負極活物質としてのシリコン薄膜の形成方法を図１を用いて説明する。   A method for forming a silicon thin film as a negative electrode active material will be described with reference to FIG.

図１に示す真空成膜装置１０は、隔壁１ａにより上下に仕切られた真空槽１を備える。隔壁１ａより上側の部屋（搬送室）１ｂには、捲き出しロール１１、円筒状のキャンロール１３、捲き取りロール１４、搬送ロール１２ａ、１２ｂが配置される。隔壁１ａより下側の部屋（薄膜形成室）１ｃには、スパッタ成膜源５１、補助スパッタ成膜源５２、可動遮蔽板５５が配置されている。隔壁１ａの中央部にはマスク４が設けられ、マスク４の開口を介してキャンロール１３の下面が薄膜形成室１ｃ側に露出している。真空槽１内は、真空ポンプ１６により所定の真空度に維持される。   A vacuum film forming apparatus 10 shown in FIG. 1 includes a vacuum chamber 1 that is partitioned vertically by a partition wall 1a. In a room (conveying chamber) 1b above the partition wall 1a, a separating roll 11, a cylindrical can roll 13, a separating roll 14, and conveying rolls 12a and 12b are arranged. A sputter film forming source 51, an auxiliary sputter film forming source 52, and a movable shielding plate 55 are disposed in a room (thin film forming chamber) 1c below the partition wall 1a. A mask 4 is provided at the center of the partition wall 1a, and the lower surface of the can roll 13 is exposed to the thin film formation chamber 1c through the opening of the mask 4. The inside of the vacuum chamber 1 is maintained at a predetermined degree of vacuum by a vacuum pump 16.

捲き出しロール１１から捲き出された帯状の負極集電体５は、搬送ロール１２ａ、キャンロール１３、搬送ロール１２ｂによって順に搬送され、捲き取りロール１４に捲き取られる。この過程で、補助スパッタ成膜源５２及びスパッタ成膜源５１から生成された原子、分子、又はクラスタなどの粒子（成膜粒子、以下、「スパッタ粒子」という）が隔壁１ａのマスク４を通過して、キャンロール１３上を走行している負極集電体５の表面上に付着して薄膜６を形成する。負極集電体５に対向して、その搬送方向の上流側から下流側に向かって、補助スパッタ成膜源５２、可動遮蔽板５５、スパッタ成膜源５１が配置されている。可動遮蔽板５５は、キャンロール１３の回転中心軸に対して半径方向に沿って移動可能である。補助スパッタ成膜源５２からのスパッタ粒子の一部とスパッタ成膜源５１からのスパッタ粒子の一部とが、キャンロール１３の外周面の近傍にて相互に混ざり合うように、可動遮蔽板５５のキャンロール１３の外周面からの距離を調整した。従って、負極集電体５の表面には、最初に補助スパッタ成膜源５２からスパッタ粒子が主として堆積し、その後、徐々にスパッタ成膜源５１からのスパッタ粒子の比率が増加し、最後には、スパッタ成膜源５１からのスパッタ粒子が主として堆積する。   The strip-shaped negative electrode current collector 5 squeezed out from the scooping roll 11 is sequentially transported by the transporting roll 12 a, the can roll 13, and the transporting roll 12 b, and scraped off by the scooping roll 14. In this process, particles such as atoms, molecules, or clusters (film formation particles, hereinafter referred to as “sputter particles”) generated from the auxiliary sputter film formation source 52 and the sputter film formation source 51 pass through the mask 4 of the partition wall 1a. Then, the thin film 6 is formed on the surface of the negative electrode current collector 5 running on the can roll 13. Opposite the negative electrode current collector 5, an auxiliary sputter film formation source 52, a movable shielding plate 55, and a sputter film formation source 51 are arranged from the upstream side to the downstream side in the transport direction. The movable shielding plate 55 is movable along the radial direction with respect to the rotation center axis of the can roll 13. The movable shielding plate 55 is arranged such that a part of the sputtered particles from the auxiliary sputter film forming source 52 and a part of the sputtered particles from the sputter film forming source 51 are mixed with each other in the vicinity of the outer peripheral surface of the can roll 13. The distance from the outer peripheral surface of the can roll 13 was adjusted. Accordingly, first, sputtered particles mainly accumulate from the auxiliary sputter film forming source 52 on the surface of the negative electrode current collector 5, and thereafter, the ratio of sputtered particles from the sputter film forming source 51 gradually increases, and finally, The sputtered particles from the sputter deposition source 51 are mainly deposited.

参考実施例１では、このような装置を用いて、スパッタ成膜源５１においてアルゴンイオンによりシリコンをスパッタして、負極集電体５としての銅箔上に、厚さ８μｍのシリコン薄膜を形成した。シリコン薄膜の堆積速度を概ね２ｎｍ／ｓに設定した。スパッタ成膜源５１として直流マグネトロンスパッタを使用した。同時に、補助スパッタ成膜源５２においてはアルゴンイオンにより銅をスパッタした。銅の堆積量は、銅のみをスパッタしたときに厚み５０ｎｍの薄膜が形成されるのと同等とした。 In Reference Example 1, using such an apparatus, silicon was sputtered by argon ions in the sputter deposition source 51 to form a silicon thin film having a thickness of 8 μm on the copper foil as the negative electrode current collector 5. . The deposition rate of the silicon thin film was set to approximately 2 nm / s. A direct current magnetron sputtering was used as the sputtering film forming source 51. At the same time, copper was sputtered with argon ions in the auxiliary sputter deposition source 52. The amount of copper deposited was equivalent to the formation of a thin film having a thickness of 50 nm when only copper was sputtered.

参考実施例２では、補助スパッタ成膜源５２に代えて抵抗加熱方式の補助蒸発源を用いて銅を蒸発させた。銅の堆積量は、銅のみを蒸着したときに厚み２μｍの薄膜が形成されるのと同等とした。上記以外は参考実施例１と同様にして負極活物質薄膜を形成した。 In Reference Example 2, copper was evaporated using a resistance heating type auxiliary evaporation source instead of the auxiliary sputter deposition source 52. The amount of copper deposited was equivalent to the formation of a thin film having a thickness of 2 μm when only copper was deposited. A negative electrode active material thin film was formed in the same manner as Reference Example 1 except for the above.

参考比較例１では、補助スパッタ成膜源５２を用いない以外は参考実施例１と同様にして負極活物質薄膜を形成した。 In Reference Comparative Example 1, a negative electrode active material thin film was formed in the same manner as Reference Example 1 except that the auxiliary sputter deposition source 52 was not used.

図２、図３、図４は、順に、参考実施例１、参考実施例２、参考比較例１のシリコン薄膜（負極活物質薄膜）のオージェデプスプロファイルを示す図である。オージェデプスプロファイルは、フィリップス社製のＳＡＭ６７０を用いて測定した。電子銃の加速電圧を１０ｋＶ、照射電流１０ｎＡとし、エッチング用のイオンガンの加速電圧３ｋＶ、スパッタレート０．１７ｎｍ／ｓにて測定した。図の横軸の「膜表面からの深さ」は、サンプルと同一のＳｉ膜とＣｕ膜をスパッタエッチングして形成された段差を段差計で測定して得たスパッタレートを用いて、サンプルのスパッタエッチング時間を厚さ方向のエッチング深さに換算して得た。 2, 3, 4, in turn, Reference Example 1, Reference Example 2, a diagram illustrating the Auger depth profile of the silicon thin film of Comparative Reference Example 1 (negative electrode active material thin film). The Auger depth profile was measured using a SAM670 manufactured by Philips. The acceleration voltage of the electron gun was 10 kV, the irradiation current was 10 nA, and the measurement was performed with the acceleration voltage of the ion gun for etching being 3 kV and the sputtering rate of 0.17 nm / s. The “depth from the film surface” on the horizontal axis in the figure is the same as the sample, using the sputter rate obtained by measuring the step formed by sputter etching of the same Si film and Cu film with the step meter. The sputter etching time was obtained by converting into the etching depth in the thickness direction.

図２〜図４から分かるように、参考実施例１及び参考実施例２（図２、図３）では、負極活物質薄膜の形成の初期段階において、２つの成膜源を用いた連続混合成膜を行うことにより、負極集電体と負極活物質との界面に、シリコンと負極集電体の主成分元素（銅）とが混合され、且つ各組成分布がなだらかに変化する組成傾斜層が形成されている。 As can be seen from FIGS. 2 to 4, in Reference Example 1 and Reference Example 2 (FIGS. 2 and 3), in the initial stage of formation of the negative electrode active material thin film, continuous mixing is performed using two film forming sources. By performing the film, there is a composition gradient layer in which silicon and the main component element (copper) of the negative electrode current collector are mixed at the interface between the negative electrode current collector and the negative electrode active material, and each composition distribution changes gently. Is formed.

参考実施例１、参考実施例２、及び参考比較例１で形成したリチウムイオン二次電池に対し、試験温度２０℃、充放電電流３ｍＡ／ｃｍ2、充放電電圧範囲４．２Ｖ〜２．５Ｖで充放電サイクル試験を行った。初回放電容量に対する、５０サイクル後、及び２００サイクル後の放電容量の割合を電池容量維持率（サイクル特性）として求めた。結果を表１に示す。 For the lithium ion secondary batteries formed in Reference Example 1, Reference Example 2, and Reference Comparative Example 1, the test temperature was 20 ° C., the charge / discharge current was 3 mA / cm 2 , and the charge / discharge voltage range was 4.2 V to 2.5 V. A charge / discharge cycle test was conducted. The ratio of the discharge capacity after 50 cycles and after 200 cycles with respect to the initial discharge capacity was determined as the battery capacity retention rate (cycle characteristics). The results are shown in Table 1.

Figure 0004850405
Figure 0004850405

表１から分かるように、負極集電体と負極活物質との界面に組成変化がなだらかな組成傾斜層が形成されている参考実施例１、参考実施例２においては、５０サイクル後、および２００サイクル後の電池容量維持率を、界面において組成が急峻に変化し組成傾斜層が実質的に形成されていない参考比較例１に比べて大きくすることが出来る。 As can be seen from Table 1, Reference Example composition change at the interface between the anode current collector and the anode active material is formed gentle composition gradient layer 1, in Reference Example 2, after 50 cycles, and 200 The battery capacity retention rate after the cycle can be increased compared to Reference Comparative Example 1 in which the composition changes sharply at the interface and the composition gradient layer is not substantially formed.

なお、銅の堆積量を種々に変える以外は参考実施例１と同様にして負極活物質薄膜を形成すると、銅の堆積量が、銅のみをスパッタしたときの厚み換算値（化学定量平均厚み）で１０ｎｍ未満では、サイクル特性の向上程度は参考実施例１の３０％程度にまで低下した。従って、銅の堆積量は、銅のみをスパッタしたときの厚み換算値（化学定量平均厚み）で５０ｎｍ以上であることが好ましい。 When the negative electrode active material thin film was formed in the same manner as in Reference Example 1 except that the amount of copper deposited was variously changed, the amount of copper deposited was a thickness converted value (chemically determined average thickness) when only copper was sputtered. When the thickness was less than 10 nm, the improvement in cycle characteristics was reduced to about 30% of that in Reference Example 1. Therefore, the amount of copper deposited is preferably 50 nm or more in terms of thickness (chemically determined average thickness) when only copper is sputtered.

一方、銅の堆積量を種々に変える以外は参考実施例２と同様にして負極活物質薄膜を形成すると、銅の堆積量が、銅のみを蒸着したときの厚み換算値（化学定量平均厚み）で１０μｍ超えると、生産性の低下や蒸着粒子の異常成長が顕著であった。従って、銅の堆積量は、銅のみを蒸着したときの厚み換算値（化学定量平均厚み）で１０μｍ以下であることが好ましい。 On the other hand, when the negative electrode active material thin film was formed in the same manner as in Reference Example 2 except that the amount of copper deposited was variously changed, the amount of copper deposited was a thickness converted value (chemically determined average thickness) when only copper was deposited. When the thickness exceeds 10 μm, productivity reduction and abnormal growth of vapor deposition particles are remarkable. Therefore, the amount of copper deposited is preferably 10 μm or less in terms of thickness (chemical quantitative average thickness) when only copper is deposited.

以上のように、真空成膜法により負極集電体上にシリコンを主成分として含む負極活物質を形成するに際して、負極集電体の被形成面を、負極集電体の主成分元素粒子が堆積する第１領域から、シリコン粒子が堆積する第２領域へ相対的に移動させる。しかも、堆積する粒子の元素濃度が徐々に変化するように、第１領域の一部と第２領域の一部とを重ね合わせて、負極集電体の主成分元素粒子とシリコン粒子とが混合して堆積する領域（混合成膜領域）を設ける。これにより、負極集電体と負極活物質との界面に、負極集電体の主成分元素及びシリコンの組成がなだらかに変化する組成傾斜層が形成される。この組成傾斜層が負極集電体と負極活物質との界面で物理的特性をなだらかに変化させるために、充放電時に負極活物質内のシリコン粒子が膨張／収縮しても、組成傾斜層がこれに伴う歪みを緩和する。従って、負極集電体と負極活物質との付着強度が向上し、その結果、上記の参考実施例１、２のようにサイクル特性が改善される。 As described above, when a negative electrode active material containing silicon as a main component is formed on a negative electrode current collector by a vacuum film forming method, the main component element particles of the negative electrode current collector are formed on the surface on which the negative electrode current collector is formed. The first region where the particles are deposited is moved relatively to the second region where the silicon particles are deposited. In addition, the main component element particles and the silicon particles of the negative electrode current collector are mixed by superimposing a part of the first region and a part of the second region so that the element concentration of the deposited particles gradually changes. Thus, a region for deposition (mixed film formation region) is provided. As a result, a composition gradient layer in which the composition of the main component element and silicon of the negative electrode current collector gently changes is formed at the interface between the negative electrode current collector and the negative electrode active material. Since the composition gradient layer gently changes the physical characteristics at the interface between the negative electrode current collector and the negative electrode active material, the composition gradient layer is not affected even if the silicon particles in the negative electrode active material expand / contract during charge / discharge. This alleviates distortion. Therefore, the adhesion strength between the negative electrode current collector and the negative electrode active material is improved, and as a result, the cycle characteristics are improved as in Reference Examples 1 and 2 above.

（実施の形態１）
本発明の実施の形態１にかかるリチウムイオン二次電池を説明する。 (Embodiment 1 )
A lithium ion secondary battery according to Embodiment 1 of the present invention will be described.

本発明の実施の形態１にかかるリチウムイオン二次電池の概略構成の一例を図５に示す。本実施の形態のリチウムイオン二次電池は、基板２２上に、電池要素２０が積層されてなる。電池要素２０は、正極集電体２７、正極活物質２６、固体電解質２５、負極活物質２４、負極集電体２３がこの順に形成されている。図５では、基板２２は、電池要素２０の正極集電体２７側に配されているが、負極集電体２３側に配されていてもよい。 An example of a schematic configuration of the lithium ion secondary battery according to Embodiment 1 of the present invention is shown in FIG. In the lithium ion secondary battery of the present embodiment, the battery element 20 is laminated on the substrate 22. In the battery element 20, a positive electrode current collector 27, a positive electrode active material 26, a solid electrolyte 25, a negative electrode active material 24, and a negative electrode current collector 23 are formed in this order. In FIG. 5, the substrate 22 is disposed on the positive electrode current collector 27 side of the battery element 20, but may be disposed on the negative electrode current collector 23 side.

基板２２としては、例えばポリイミド（ＰＩ）、ポリアミド（ＰＡ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエチレンテレフタレート（ＰＥＴ）やその他の高分子フィルム、又はステンレス金属箔、又はニッケル、銅、アルミニウムやその他の金属元素を含む金属箔などの可撓性を有する材料を用いることが出来る。更に、各種形状のシリコン、ガラス、セラミック、プラスチックなどを用いることも出来、本発明では基板の材質や形状に特に限定はない。リチウムイオン二次電池に求められる特性に応じて適宜選択すればよい。 Examples of the substrate 22 include polyimide (PI), polyamide (PA), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), other polymer films, stainless metal foil, nickel, copper, aluminum, and other metals. A flexible material such as a metal foil containing an element can be used. Furthermore, various shapes of silicon, glass, ceramic, plastic, and the like can be used, and in the present invention, the material and shape of the substrate are not particularly limited. What is necessary is just to select suitably according to the characteristic calculated | required by a lithium ion secondary battery .

正極集電体２７としては、例えばニッケル、銅、アルミニウム、白金、白金−パラジウム、金、銀、チタン、ＩＴＯ（インジウム−スズ酸化物）で代表される金属を用いることが出来る。リチウムイオン二次電池の最終形態によっては、正極側に基板２２を配置し、且つ基板２２として導電性材料を用いる場合には、正極集電体２７を省略し、基板２２を正極集電体２７としても機能させることができる。 As the positive electrode current collector 27, for example, a metal represented by nickel, copper, aluminum, platinum, platinum-palladium, gold, silver, titanium, or ITO (indium-tin oxide) can be used. Depending on the final form of the lithium ion secondary battery , when the substrate 22 is disposed on the positive electrode side and a conductive material is used as the substrate 22, the positive electrode current collector 27 is omitted, and the substrate 22 is replaced with the positive electrode current collector 27. Can also function.

正極活物質２６としては、例えばコバルト酸リチウム、ニッケル酸リチウムなどを用いることが出来る。但し、本発明の正極活物質２６の材料は上記に限定されず、その他の材料を用いることも出来る。   As the positive electrode active material 26, for example, lithium cobaltate, lithium nickelate, or the like can be used. However, the material of the positive electrode active material 26 of the present invention is not limited to the above, and other materials can also be used.

固体電解質２５としては、イオン伝導性があり、電子伝導性が無視できるほど小さい材料を用いることが出来る。特にリチウムイオン二次電池では、リチウムイオンが可動イオンであるため、Ｌｉ3ＰＯ4や、Ｌｉ3ＰＯ4に窒素を混ぜて（あるいはＬｉ3ＰＯ4の元素の一部を窒素で置換して）得られる材料（ＬｉＰＯＮ：代表的な組成はＬｉ2.9ＰＯ3.3Ｎ0.36）などからなる固体電解質はリチウムイオン伝導性に優れるので好ましい。同様に、Ｌｉ2Ｓ−ＳｉＳ2、Ｌｉ2Ｓ−Ｐ2Ｓ5、Ｌｉ2Ｓ−Ｂ2Ｓ3などの硫化物からなる固体電解質も有効である。更にこれらの固体電解質にＬｉＩなどのハロゲン化リチウムや、Ｌｉ3ＰＯ4等のリチウム酸素酸塩をドープした固体電解質も有効である。本発明の固体電解質２５の材料は上記に限定されず、その他の材料を固体電解質２５として用いることも出来る。電解質として固体電解質を用いることにより、従来の液型電解質で必須の液漏れ対策が不要となり、リチウムイオン二次電池の小型化、薄型化が容易になる。 As the solid electrolyte 25, a material having ionic conductivity and small enough to have negligible electronic conductivity can be used. Especially in a lithium ion secondary battery, since lithium ions are mobile ions, and Li 3 PO 4, and mixed with nitrogen to Li 3 PO 4 and a portion of (or the elements of Li 3 PO 4 was replaced with nitrogen ) A solid electrolyte made of a material (LiPON: a typical composition is Li 2.9 PO 3.3 N 0.36 ) or the like is preferable because it is excellent in lithium ion conductivity. Similarly, a solid electrolyte made of a sulfide such as Li 2 S—SiS 2 , Li 2 S—P 2 S 5 , Li 2 S—B 2 S 3 is also effective. Furthermore, solid electrolytes obtained by doping these solid electrolytes with lithium halides such as LiI and lithium oxyacid salts such as Li 3 PO 4 are also effective. The material of the solid electrolyte 25 of the present invention is not limited to the above, and other materials can be used as the solid electrolyte 25. By using a solid electrolyte as the electrolyte, it is not necessary to take countermeasures against liquid leakage that are necessary for conventional liquid electrolytes, and the lithium ion secondary battery can be easily reduced in size and thickness.

負極活物質２４としては、シリコンを主成分として含むシリコン薄膜を用いることが出来る。負極集電体２３との界面近傍には組成傾斜層を有している。   As the negative electrode active material 24, a silicon thin film containing silicon as a main component can be used. A composition gradient layer is provided in the vicinity of the interface with the negative electrode current collector 23.

負極集電体２３としては、正極集電体２７と同様に、例えばニッケル、銅、アルミニウム、白金、白金−パラジウム、金、銀、ＩＴＯ（インジウム−スズ酸化物）で代表される金属を用いることが出来る。リチウムイオン二次電池の最終形態によっては、負極側に基板２２を配置し、且つ基板２２として導電性材料を用いる場合には、負極集電体２３を省略し、基板２２を負極集電体２３としても機能させることができる。 As the negative electrode current collector 23, a metal represented by, for example, nickel, copper, aluminum, platinum, platinum-palladium, gold, silver, ITO (indium-tin oxide) is used similarly to the positive electrode current collector 27. I can do it. Depending on the final form of the lithium ion secondary battery , when the substrate 22 is disposed on the negative electrode side and a conductive material is used as the substrate 22, the negative electrode current collector 23 is omitted and the substrate 22 is replaced with the negative electrode current collector 23. Can also function.

リチウムイオン二次電池の製品形態としては特に制限されず、種々のものが考えられる。例えば、可撓性の長尺の基板２２上に図５に示した電池要素２０を積層したものを図６に示すようにして平板状に巻回しても良い。このとき、巻回体３０の内周に平板状の内芯３１を配置しても良い。 The product form of the lithium ion secondary battery is not particularly limited, and various types can be considered. For example, what laminated | stacked the battery element 20 shown in FIG. 5 on the flexible long board | substrate 22 may be wound by flat form as shown in FIG. At this time, a plate-shaped inner core 31 may be disposed on the inner periphery of the wound body 30.

図７は図６に示した平板状リチウムイオン二次電池の斜視図である。図７において、３２は巻回体３０の両端に設けられる一対の外部電極である。外部電極３２の材料としては、ニッケル、亜鉛、スズ、はんだ合金、導電性樹脂などの各種導電材料を用いることが出来る。その形成方法としては、溶射、メッキ、塗布などを用いることが出来る。一方の外部電極３２には負極集電体２３が電気的に接続され、他方の外部電極３２には正極集電体２７が電気的に接合される。このとき、一対の外部電極３２が相互に絶縁されるように、負極集電体２３及び正極集電体２７の幅方向（巻回中心方向）の形成領域をパターニングしておく必要がある。 7 is a perspective view of the flat lithium ion secondary battery shown in FIG. In FIG. 7, 32 is a pair of external electrodes provided at both ends of the wound body 30. As the material of the external electrode 32, various conductive materials such as nickel, zinc, tin, solder alloy, and conductive resin can be used. As the formation method, thermal spraying, plating, coating, or the like can be used. The negative electrode current collector 23 is electrically connected to one external electrode 32, and the positive electrode current collector 27 is electrically bonded to the other external electrode 32. At this time, it is necessary to pattern the formation regions in the width direction (winding center direction) of the negative electrode current collector 23 and the positive electrode current collector 27 so that the pair of external electrodes 32 are insulated from each other.

図８は、リチウムイオン二次電池の別の製品形態を示す断面図である。図８において、３５は一対の外部電極であり、一方の外部電極３５には負極集電体２３が電気的に接続され、他方の外部電極３５には正極集電体２７が電気的に接合される。その材料及び形成方法は図７に示した外部電極３２と同様である。 FIG. 8 is a cross-sectional view showing another product form of the lithium ion secondary battery . In FIG. 8, reference numeral 35 denotes a pair of external electrodes. The negative electrode current collector 23 is electrically connected to one external electrode 35, and the positive electrode current collector 27 is electrically bonded to the other external electrode 35. The The material and the formation method are the same as those of the external electrode 32 shown in FIG.

３６は、負極集電体２３の外部電極３５との接続部近傍、及び正極集電体２７の外部電極３５との接続部近傍に設けられたヒューズ部である。ヒューズ部３６は、過電流が流れたときに溶断して過電流を遮断して発火などに至るのを事前に防止する安全装置として機能する。本実施の形態では、ヒューズ部３６は、負極集電体２３及び正極集電体２７に設けられているが、いずれか一方のみであっても良い。   Reference numeral 36 denotes a fuse portion provided in the vicinity of the connection portion between the negative electrode current collector 23 and the external electrode 35 and in the vicinity of the connection portion between the positive electrode current collector 27 and the external electrode 35. The fuse part 36 functions as a safety device that prevents the occurrence of ignition or the like by cutting off the overcurrent when the overcurrent flows and preventing the ignition. In the present embodiment, the fuse portion 36 is provided in the negative electrode current collector 23 and the positive electrode current collector 27, but only one of them may be provided.

図９（Ａ）はヒューズ部３６の一例を示した平面図、図９（Ｂ）は、図９（Ａ）における９Ｂ−９Ｂ線での矢視断面図である。集電体２３、２７を、電流が流れる部分の幅が狭くなるようなパターンを付与してヒューズ部３６を形成している。過電流が流れると、ヒューズ部３６がジュール熱により発熱し、溶断して、過電流を遮断する。従って、発火などの重大な事態に至るのを未然に防止することができる。なお、ヒューズ部３６の構成は図９（Ａ）及び図９（Ｂ）に限定されない。例えば、負極集電体２３及び正極集電体２７の厚みを部分的に薄くすることによりヒューズ部３６を構成しても良い。あるいは、負極集電体２３及び正極集電体２７内に、電気抵抗の温度係数の大きな異種材料を特定パターンで形成することによりヒューズ部を形成しても良い。異種材料の電気抵抗の温度係数が、負極集電体２３及び正極集電体２７の電気抵抗の温度係数よりも大きいので、過電流時にヒューズ部３６がわずかに温度上昇すると異種材料の抵抗値が急激に増大する。よって、ヒューズ部３６内の異種材料以外の負極集電体２３及び正極集電体２７の材料内に電流が集中して流れる結果、ヒューズ部３６がジュール熱により発熱し、溶断して、過電流を遮断する。   9A is a plan view showing an example of the fuse portion 36, and FIG. 9B is a cross-sectional view taken along line 9B-9B in FIG. 9A. The current collectors 23 and 27 are provided with a pattern that narrows the width of the portion through which current flows to form the fuse portion 36. When an overcurrent flows, the fuse portion 36 generates heat due to Joule heat and melts to cut off the overcurrent. Therefore, it is possible to prevent a serious situation such as ignition from occurring. The configuration of the fuse portion 36 is not limited to FIGS. 9A and 9B. For example, the fuse portion 36 may be configured by partially reducing the thickness of the negative electrode current collector 23 and the positive electrode current collector 27. Alternatively, the fuse part may be formed by forming a different material having a large temperature coefficient of electrical resistance in a specific pattern in the negative electrode current collector 23 and the positive electrode current collector 27. Since the temperature coefficient of the electric resistance of the dissimilar material is larger than the temperature coefficient of the electric resistance of the negative electrode current collector 23 and the positive electrode current collector 27, the resistance value of the dissimilar material increases if the temperature of the fuse portion 36 slightly increases during overcurrent. Increases rapidly. Therefore, as a result of current flowing in the material of the negative electrode current collector 23 and the positive electrode current collector 27 other than the dissimilar materials in the fuse part 36, the fuse part 36 generates heat due to Joule heat and melts, resulting in overcurrent. Shut off.

図８において、３７は、機械的保護、耐湿性向上、層間剥離の防止などを目的として設けられる保護層である。保護層３７の材料は特に限定されないが、例えばシランカップリング剤等の表面処理剤、光あるいは熱硬化性樹脂、金属、金属酸化物、金属窒化物などを用いることができる。形成方法としては、塗布、ディップ（浸漬）、スプレーなどの湿式プロセスや、蒸着、スパッタなどのドライプロセスを採ることができる。また、保護層３７は異種又は同種の材料からなる多層の複合膜であっても良い。保護層３７は、外部電極３５を除くリチウムイオン二次電池の外表面に形成することができる。基板２２の材料によっては、図８に示すように基板２２の表面には保護層３７を形成しなくてもよい。 In FIG. 8, 37 is a protective layer provided for the purpose of mechanical protection, improvement of moisture resistance, prevention of delamination, and the like. Although the material of the protective layer 37 is not specifically limited, For example, surface treatment agents, such as a silane coupling agent, light or a thermosetting resin, a metal, a metal oxide, a metal nitride etc. can be used. As a forming method, a wet process such as coating, dipping (dipping) or spraying, or a dry process such as vapor deposition or sputtering can be employed. Further, the protective layer 37 may be a multilayer composite film made of different or similar materials. The protective layer 37 can be formed on the outer surface of the lithium ion secondary battery excluding the external electrode 35. Depending on the material of the substrate 22, the protective layer 37 may not be formed on the surface of the substrate 22 as shown in FIG. 8.

さらに、電池要素２０を必要な数だけ繰り返して積層してリチウムイオン二次電池を構成してもよい。 Furthermore, a lithium ion secondary battery may be configured by repeatedly stacking the battery elements 20 as many times as necessary.

［実施例１，２、比較例１］
実施の形態１に対応する実施例を説明する。 [Examples 1 and 2 and Comparative Example 1 ]
The example corresponding to the first embodiment will be described.

基板２２として厚さ２５μｍのポリイミドフィルムを用い、この上に、正極集電体２７として厚さ０．５μｍのニッケル、正極活物質２６として厚さ８μｍのコバルト酸リチウムをそれぞれ真空蒸着法により積層し、更に、厚さ２μｍのリン酸リチウム系の固体電解質２５を真空蒸着法により積層した。   A polyimide film with a thickness of 25 μm is used as the substrate 22, and a nickel film with a thickness of 0.5 μm is stacked as the positive electrode current collector 27 and a lithium cobalt oxide with a thickness of 8 μm is stacked as the positive electrode active material 26 on the polyimide film. Further, a lithium phosphate solid electrolyte 25 having a thickness of 2 μm was laminated by a vacuum deposition method.

その後、固体電解質２５の表面にシリコン及び銅を順に蒸着し、厚さ約３μｍのシリコン薄膜からなる負極活物質２４及び厚さ約１μｍの銅薄膜からなる負極集電体２３を形成した。詳細は後述する。   Thereafter, silicon and copper were sequentially deposited on the surface of the solid electrolyte 25 to form a negative electrode active material 24 made of a silicon thin film having a thickness of about 3 μm and a negative electrode current collector 23 made of a copper thin film having a thickness of about 1 μm. Details will be described later.

かくして、図５に示す積層構造を有する帯状の積層物を得た。   Thus, a strip-like laminate having the laminate structure shown in FIG. 5 was obtained.

これを平板状に巻回し、正極集電体２７及び負極集電体２３にそれぞれ電気的に接続されるように一対の外部電極３２を形成して、図７に示すような平板状のリチウムイオン二次電池を得た。   This is wound into a flat plate shape, and a pair of external electrodes 32 are formed so as to be electrically connected to the positive electrode current collector 27 and the negative electrode current collector 23, respectively, and a flat plate lithium ion as shown in FIG. A secondary battery was obtained.

負極活物質２４及び負極集電体２３の形成方法を図１０を用いて説明する。   A method for forming the negative electrode active material 24 and the negative electrode current collector 23 will be described with reference to FIGS.

図１０の装置では、薄膜形成室１ｃに、スパッタ成膜源５１、補助スパッタ成膜源５２に代えて、負極活物質蒸着源７１及び負極集電体蒸着源７２が配置されている点で図１の装置と異なる。図１０において図１と同一の構成要素には同一の符号を付してそれらについての説明を省略する。   In the apparatus of FIG. 10, a negative electrode active material vapor deposition source 71 and a negative electrode current collector vapor deposition source 72 are arranged in the thin film formation chamber 1c in place of the sputter film deposition source 51 and the auxiliary sputter film deposition source 52. Different from the one device. 10, the same components as those in FIG. 1 are denoted by the same reference numerals, and description thereof will be omitted.

正極集電体２７、正極活物質２６、固体電解質２５が形成された帯状の上記基板２２は、捲き出しロール１１から捲き出され、搬送ロール１２ａ、キャンロール１３、搬送ロール１２ｂによって順に搬送され、捲き取りロール１４に捲き取られる。この過程で、負極活物質蒸着源７１及び負極集電体蒸着源７２から生成された原子、分子、又はクラスタなどの粒子（成膜粒子、以下、「蒸発粒子」という）が隔壁１ａのマスク４を通過して、キャンロール１３上を走行している基板２２の固体電解質２５の表面上に付着して薄膜６を形成する。基板２２に対向して、その搬送方向の上流側から下流側に向かって、負極活物質蒸着源７１及び負極集電体蒸着源７２が配置されている。可動遮蔽板５５は、キャンロール１３の回転中心軸に対して半径方向に沿って移動可能である。負極活物質蒸着源７１からの蒸発粒子の一部と負極集電体蒸着源７２からの蒸発粒子の一部とが、キャンロール１３の外周面の近傍にて相互に混ざり合うように、可動遮蔽板５５のキャンロール１３の外周面からの距離を調整した。従って、基板２２の固体電解質２５の表面には、最初に負極活物質蒸着源７１から蒸発粒子が主として堆積し、その後、徐々に負極集電体蒸着源７２からの蒸発粒子の比率が増加し、最後には、負極集電体蒸着源７２からの蒸発粒子が主
として堆積する。 The strip-shaped substrate 22 on which the positive electrode current collector 27, the positive electrode active material 26, and the solid electrolyte 25 are formed is squeezed out from the scooping roll 11, and transported in turn by the transporting roll 12a, the can roll 13, and the transporting roll 12b It is scraped off by the scraping roll 14. In this process, particles such as atoms, molecules, or clusters (deposition particles, hereinafter referred to as “evaporated particles”) generated from the negative electrode active material vapor deposition source 71 and the negative electrode current collector vapor deposition source 72 are mask 4 of the partition wall 1a. The thin film 6 is formed by adhering to the surface of the solid electrolyte 25 of the substrate 22 running on the can roll 13. A negative electrode active material vapor deposition source 71 and a negative electrode current collector vapor deposition source 72 are arranged facing the substrate 22 from the upstream side to the downstream side in the transport direction. The movable shielding plate 55 is movable along the radial direction with respect to the rotation center axis of the can roll 13. Movable shielding so that some of the evaporated particles from the negative electrode active material vapor deposition source 71 and some of the evaporated particles from the negative electrode current collector vapor deposition source 72 are mixed with each other in the vicinity of the outer peripheral surface of the can roll 13. The distance from the outer peripheral surface of the can roll 13 of the board 55 was adjusted. Accordingly, the evaporation particles are mainly deposited from the negative electrode active material vapor deposition source 71 first on the surface of the solid electrolyte 25 of the substrate 22, and then the ratio of the evaporation particles from the negative electrode current collector vapor deposition source 72 gradually increases. Finally, the evaporated particles from the negative electrode current collector evaporation source 72 are mainly deposited.

実施例１，２では、このような装置を用いて、負極活物質蒸着源７１からシリコンを蒸発させて厚さ約３μｍの負極活物質２４を形成し、負極集電体蒸着源７２から銅を蒸発させて厚さ約１μｍの負極集電体２３を形成した。この結果、負極活物質２４と負極集電体２３との界面には、シリコン及び銅の組成分布がなだらかに変化する組成傾斜層が形成される。 In Examples 1 and 2 , using such an apparatus, silicon was evaporated from the negative electrode active material vapor deposition source 71 to form the negative electrode active material 24 having a thickness of about 3 μm, and copper was removed from the negative electrode current collector vapor deposition source 72. The negative electrode current collector 23 having a thickness of about 1 μm was formed by evaporation. As a result, a composition gradient layer in which the composition distribution of silicon and copper changes gently is formed at the interface between the negative electrode active material 24 and the negative electrode current collector 23.

実施例１では、可動遮蔽板５５のキャンロール１３の外周面からの距離を小さくして、負極活物質蒸着源７１からのシリコン粒子と負極集電体蒸着源７２からの銅粒子との混合を少なくした。 In Example 1 , the distance from the outer peripheral surface of the can roll 13 of the movable shielding plate 55 is reduced to mix the silicon particles from the negative electrode active material vapor deposition source 71 and the copper particles from the negative electrode current collector vapor deposition source 72. Less.

実施例２では、可動遮蔽板５５のキャンロール１３の外周面からの距離を大きくして、負極活物質蒸着源７１からのシリコン粒子と負極集電体蒸着源７２からの銅粒子との混合を多くした。 In Example 2 , the distance from the outer peripheral surface of the can roll 13 of the movable shielding plate 55 is increased to mix the silicon particles from the negative electrode active material vapor deposition source 71 and the copper particles from the negative electrode current collector vapor deposition source 72. A lot.

比較例１では、負極集電体蒸着源７２を使用せず、負極活物質蒸着源７１のみを使用してシリコンを蒸発させて厚さ約３μｍの負極活物質２４を形成して、基板２２を一旦巻き取りロール１４に巻き取った。次いで、この基材２２を巻き出しロール１１に設置して、負極活物質蒸着源７１を使用せず、負極集電体蒸着源７２のみを使用して負極活物質２４の表面に銅を蒸発させて厚さ約１μｍの負極集電体２３を形成した。 In Comparative Example 1 , the negative electrode current collector vapor deposition source 72 was not used, but only the negative electrode active material vapor deposition source 71 was used to evaporate silicon to form the negative electrode active material 24 having a thickness of about 3 μm. Once wound on the winding roll 14. Next, the base material 22 is placed on the unwinding roll 11, and the negative electrode active material deposition source 71 is not used, but only the negative electrode current collector deposition source 72 is used to evaporate copper on the surface of the negative electrode active material 24. Thus, a negative electrode current collector 23 having a thickness of about 1 μm was formed.

実施例１，２及び比較例１のオージェデプスプロファイルを測定した結果、２つの成膜源を用いた連続混合成膜を行った実施例１及び実施例２においては、比較例１と比較して、負極活物質２４と負極集電体２３との界面において、シリコン及び銅が混合され、且つ各組成分布がなだらかに変化する組成傾斜層が形成されていた。実施例１，２のように、負極活物質蒸着源７１及び負極集電体蒸着源７２を、それぞれからの蒸発粒子の一部が互いに混合し合うように隣り合わせて配置して負極活物質２４及び負極集電体２３を順に連続して成膜することによって、両者の界面に組成傾斜層が形成されることを確認した。 A result of measuring the Auger depth profile of Examples 1 and 2 and Comparative Example 1, in Example 1 and Example 2 were continuously mixed film formation using the two film forming source, as compared with Comparative Example 1 In addition, at the interface between the negative electrode active material 24 and the negative electrode current collector 23, silicon and copper were mixed, and a composition gradient layer in which each composition distribution changed gently was formed. As in Examples 1 and 2 , the negative electrode active material vapor deposition source 71 and the negative electrode current collector vapor deposition source 72 are arranged adjacent to each other so that some of the evaporated particles from each other are mixed with each other. It was confirmed that a composition gradient layer was formed at the interface between the negative electrode current collector 23 and the negative electrode current collector 23 formed in sequence.

実施例１，２及び比較例１で得たリチウムイオン二次電池に対し、試験温度２０℃、充放電電流３ｍＡ／ｃｍ2、充放電電圧範囲４．２Ｖ〜２．５Ｖで充放電サイクル試験を行った。初回放電容量に対する、５０サイクル後、及び２００サイクル後の容量の割合を電池容量維持率（サイクル特性）として求めた。結果を表２に示す。 The lithium ion secondary batteries obtained in Examples 1 and 2 and Comparative Example 1 were subjected to a charge / discharge cycle test at a test temperature of 20 ° C., a charge / discharge current of 3 mA / cm 2 , and a charge / discharge voltage range of 4.2 V to 2.5 V. went. The ratio of the capacity after 50 cycles and after 200 cycles with respect to the initial discharge capacity was determined as the battery capacity retention rate (cycle characteristics). The results are shown in Table 2.

Figure 0004850405
Figure 0004850405

表２から分かるように、負極集電体２３と負極活物質２４との界面になだらかな組成傾斜層が形成されている実施例１、実施例２においては、５０サイクル後、および２００サイクル後の電池容量維持率を、界面において組成が急峻に変化し組成傾斜層が実質的に形成されていない比較例１に比べて大きくすることが出来る。 As can be seen from Table 2, in Example 1 and Example 2 in which a gentle composition gradient layer is formed at the interface between the negative electrode current collector 23 and the negative electrode active material 24, after 50 cycles and after 200 cycles The battery capacity retention rate can be increased as compared with Comparative Example 1 in which the composition changes sharply at the interface and the composition gradient layer is not substantially formed.

負極活物質２４と負極集電体２３との界面近傍において、シリコンの信号強度が界面近傍でのピーク値を有する地点から該ピーク値の１／２に低下する地点までの厚さ方向の距離は、実施例１で２μｍであった。但し、これは一例であり、この距離が例えば１００ｎｍの場合でもサイクル特性の向上が見られた。 In the vicinity of the interface between the negative electrode active material 24 and the negative electrode current collector 23, the distance in the thickness direction from the point where the silicon signal intensity has a peak value in the vicinity of the interface to a point where the peak value decreases to ½ of the peak value is In Example 1 , it was 2 μm. However, this is only an example, and even when this distance is, for example, 100 nm, an improvement in cycle characteristics was observed.

以上のように、電解質上に真空成膜法によりシリコンを主成分として含む負極活物質及び負極集電体を形成するに際して、被形成面を、シリコン粒子が堆積する第１領域から、負極集電体を形成するための元素粒子が堆積する第２領域へ相対的に移動させる。しかも、堆積する粒子の元素濃度が徐々に変化するように、第１領域の一部と第２領域の一部とを重ね合わせて、シリコン粒子と負極集電体を形成するための元素粒子とが混合して堆積する領域（混合成膜領域）を設ける。これにより、負極活物質と負極集電体との界面に組成がなだらかに変化する組成傾斜層が形成される。この組成傾斜層が負極活物質と負極集電体との界面で物理的特性をなだらかに変化させるために、充放電時に負極活物質内のシリコン粒子が膨張／収縮しても、組成傾斜層がこれに伴う歪みを緩和する。従って、負極活物質と負極集電体との付着強度が向上し、その結果、上記の実施例１，２のようにサイクル特性が改善される。 As described above, when forming the negative electrode active material and the negative electrode current collector containing silicon as a main component on the electrolyte by the vacuum film forming method, the formation surface is changed from the first region where silicon particles are deposited to the negative electrode current collector. It moves relatively to the 2nd field where element particles for forming a body accumulate. In addition, the element particles for forming the silicon particles and the negative electrode current collector are formed by superimposing a part of the first region and a part of the second region so that the element concentration of the deposited particles gradually changes. A region (mixed film formation region) in which the particles are mixed and deposited is provided. Thereby, a composition gradient layer whose composition changes gently at the interface between the negative electrode active material and the negative electrode current collector is formed. Since the composition gradient layer gently changes the physical characteristics at the interface between the negative electrode active material and the negative electrode current collector, the composition gradient layer is not affected even when the silicon particles in the negative electrode active material expand / contract during charge / discharge. This alleviates distortion. Therefore, the adhesion strength between the negative electrode active material and the negative electrode current collector is improved, and as a result, the cycle characteristics are improved as in Examples 1 and 2 above.

上記の参考実施例１、２では、負極活物質をスパッタ法又は蒸着法により形成し、実施例１，２では負極活物質及び負極集電体を蒸着法により形成する例を示したが、本発明はこれに限定されず、ＣＶＤ法をはじめとする他の真空成膜法を用いてもよく、その場合であっても同様の効果が得られる。 In the above Reference Examples 1 and 2, the negative electrode active material was formed by sputtering or vapor deposition, and in Examples 1 and 2 , the negative electrode active material and the negative electrode current collector were formed by vapor deposition. The invention is not limited to this, and other vacuum film forming methods such as a CVD method may be used, and even in this case, the same effect can be obtained.

また、参考実施例１、２において負極集電体として用いた銅箔には表面処理が施されていてもよい。銅箔に施すことができる表面処理としては、亜鉛メッキ、スズ、銅、ニッケル、若しくはコバルトと亜鉛との合金メッキ、ベンゾトリアゾールなどのアゾール誘導体を用いた被覆層の形成、クロム酸若しくは二クロム酸塩を含む溶液などによるクロム含有被膜の形成、またはこれらの組み合わせを用いることが出来る。あるいは、銅箔に代えて、他の基材の表面に銅被覆を施したものを用いることも出来る。この銅被覆の表面に上記の表面処理を施してもよい。 The copper foil used as the negative electrode current collector in Reference Examples 1 and 2 may be subjected to a surface treatment. Surface treatments that can be applied to the copper foil include zinc plating, tin, copper, nickel, or alloy plating of cobalt and zinc, formation of a coating layer using an azole derivative such as benzotriazole, chromic acid or dichromic acid Formation of a chromium-containing film by a solution containing a salt or a combination thereof can be used. Or it can replace with copper foil and what gave the copper coating to the surface of the other base material can also be used. You may perform said surface treatment on the surface of this copper coating.

上記の実施の形態及び実施例の説明では言及しなかったが、負極活物質薄膜の成膜を不活性ガス又は窒素雰囲気で行うことが望ましい。雰囲気ガスは、被成膜面（上記の実施例ではマスク４の開口）に向けて導入してもよく、あるいは、真空槽（上記の実施例では薄膜形成室１ｃ）内全体に行き渡るように導入してもよいが、被成膜面に向けて導入する方が効率的で好ましい。   Although not mentioned in the description of the above embodiments and examples, it is desirable to form the negative electrode active material thin film in an inert gas or nitrogen atmosphere. The atmospheric gas may be introduced toward the film formation surface (the opening of the mask 4 in the above embodiment), or introduced so as to reach the entire inside of the vacuum chamber (the thin film forming chamber 1c in the above embodiment). However, it is more efficient and preferable to introduce it toward the film formation surface.

負極活物質薄膜をこのような雰囲気ガス中で成膜することにより、被成膜面と平行な方向に隣り合うシリコン柱状粒子が合併して成長して、シリコン粒子径が粗大化するのを防止できる。その結果、充放電時にシリコン粒子の膨張／収縮の程度が激しくなり、サイクル特性が低下するのを抑制することができる。本発明者らの実験によれば、詳細な実験結果を示すグラフを省略するが、上記のガス雰囲気で負極活物質薄膜を成膜することにより、リチウムイオン二次電池の電池容量維持率を８０％にまで低下させる充放電サイクル数が例えば１５〜５０％増加した。 By depositing the negative electrode active material thin film in such an atmospheric gas, silicon columnar particles adjacent to each other in the direction parallel to the film formation surface are prevented from merging and growing to prevent the silicon particle diameter from becoming coarse. it can. As a result, the degree of expansion / contraction of silicon particles during charging / discharging becomes severe, and it is possible to suppress deterioration of cycle characteristics. According to the experiments by the present inventors, the graph showing the detailed experimental results is omitted, but the negative electrode active material thin film is formed in the above gas atmosphere, whereby the battery capacity maintenance rate of the lithium ion secondary battery is 80. For example, the number of charge / discharge cycles to be reduced to 15% increased by 15 to 50%.

ガスの好ましい導入量は負極活物質薄膜の成膜条件、特に薄膜堆積速度Ｒ（ｎｍ／ｓ）に応じて設定される。例えば、被成膜面に向けてガスを導入する場合には、成膜幅１００ｍｍあたりのガス導入量Ｑ（ｍ3／ｓ）は、１×１０-10×Ｒ〜１×１０-6×Ｒ、特に１×１０-9×Ｒ〜１×１０-7×Ｒであることが好ましい。ガス導入量が少なすぎると上記の効果が得られない。逆にガス導入量が多すぎると負極活物質薄膜の堆積速度が低下する。 A preferable introduction amount of the gas is set according to the film forming conditions of the negative electrode active material thin film, particularly the thin film deposition rate R (nm / s). For example, when the gas is introduced toward the film formation surface, the gas introduction amount Q (m 3 / s) per 100 mm of the film formation width is 1 × 10 −10 × R to 1 × 10 −6 × R. In particular, it is preferably 1 × 10 −9 × R to 1 × 10 −7 × R. If the amount of gas introduced is too small, the above effect cannot be obtained. Conversely, when the amount of introduced gas is too large, the deposition rate of the negative electrode active material thin film is reduced.

使用するガスとしては、実用性及び上記の効果の顕著性の観点から、アルゴンが最も好ましい。   As the gas to be used, argon is most preferable from the viewpoints of practicality and the remarkable effects described above.

また、負極活物質薄膜に含まれるシリコンの一部が酸化物であることが好ましい場合がある。負極活物質薄膜中のシリコンの含有量が多く、電池容量が大きい場合には、充放電時のシリコン粒子の膨張／収縮の程度が大きくなり、サイクル特性が低下する場合がある。負極活物質薄膜がシリコンの酸化物を含むと、シリコンの酸化物は充放電時の膨張／収縮が少ないから、充放電時のシリコン粒子の膨張／収縮を抑えることができ、サイクル特性を向上させることができる。例えば、負極活物質薄膜に含まれるシリコンの２０〜５０％が酸化物になるように成膜することが好ましい。本発明者らの実験によれば、詳細な実験結果を示すグラフを省略するが、負極活物質薄膜がシリコンの酸化物を含むことにより、負極活物質薄膜にもよるが、リチウムイオン二次電池の電池容量維持率を８０％にまで低下させる充放電サイクル数が例えば１０〜１４０％増加した。 Moreover, it may be preferable that a part of silicon contained in the negative electrode active material thin film is an oxide. When the content of silicon in the negative electrode active material thin film is large and the battery capacity is large, the degree of expansion / contraction of silicon particles during charge / discharge increases, and the cycle characteristics may deteriorate. When the negative electrode active material thin film contains a silicon oxide, the silicon oxide has little expansion / contraction during charging / discharging, so that expansion / contraction of silicon particles during charging / discharging can be suppressed, and cycle characteristics are improved. be able to. For example, it is preferable to form a film so that 20 to 50% of silicon contained in the negative electrode active material thin film becomes an oxide. According to the experiments of the present inventors, though not chart showing the detailed experimental results, by negative electrode active material thin film containing an oxide of silicon, depending on the negative electrode active material thin film, a lithium ion secondary battery The number of charge / discharge cycles for reducing the battery capacity retention rate to 80% increased, for example, by 10 to 140%.

シリコンの一部を酸化物にするには、例えば真空雰囲気下で負極活物質薄膜の成膜中に、被成膜面の近傍に酸素系のガスを導入し、シリコン原子と反応させることによって可能である。反応性を高めるために、オゾンを用いたり、プラズマや基板電位などによってエネルギー付与を行うことは有効である。   Part of silicon can be converted to oxide by, for example, introducing an oxygen-based gas in the vicinity of the deposition surface and reacting with silicon atoms during the deposition of the negative electrode active material thin film in a vacuum atmosphere. It is. In order to enhance the reactivity, it is effective to use ozone, or to apply energy by plasma or substrate potential.

ガスの好ましい導入量は負極活物質薄膜の成膜条件、特に薄膜堆積速度Ｒ（ｎｍ／ｓ）に応じて設定される。例えば、被成膜面に向けてガスを導入する場合には、成膜幅１００ｍｍあたりのガス導入量Ｐ（ｍ3／ｓ）は、１×１０-11×Ｒ〜１×１０-5×Ｒ、特に１×１０-10×Ｒ〜１×１０-6×Ｒ、更には１×１０-9×Ｒ〜１×１０-7×Ｒであることが好ましい。但し、設備形態等によりガス導入量Ｐはこの限りではない。ガス導入量が少なすぎると上記の効果が得られない。逆にガス導入量が多すぎると負極活物質薄膜全体が酸化物となってしまい電池容量が低下する。 A preferable introduction amount of the gas is set according to the film forming conditions of the negative electrode active material thin film, particularly the thin film deposition rate R (nm / s). For example, when the gas is introduced toward the film formation surface, the gas introduction amount P (m 3 / s) per 100 mm of the film formation width is 1 × 10 −11 × R to 1 × 10 −5 × R. In particular, it is preferably 1 × 10 −10 × R to 1 × 10 −6 × R, more preferably 1 × 10 −9 × R to 1 × 10 −7 × R. However, the gas introduction amount P is not limited to this, depending on the equipment configuration. If the amount of gas introduced is too small, the above effect cannot be obtained. Conversely, if the amount of gas introduced is too large, the entire negative electrode active material thin film becomes an oxide, and the battery capacity decreases.

本発明のリチウムイオン二次電池の利用分野は特に限定されないが、例えば薄型、軽量の小型携帯機器の二次電池として利用することができる。 FIELD lithium ion secondary battery of the present invention is not particularly limited, for example, can be used thin, as a secondary battery of lightweight small portable devices.

リチウムイオン二次電池の製造に使用される装置の参考実施形態の概略構成を示した断面図である。It is sectional drawing which showed schematic structure of the reference embodiment of the apparatus used for manufacture of a lithium ion secondary battery . 参考実施例１の負極活物質薄膜の厚み方向の元素分布図である。 4 is an element distribution diagram in a thickness direction of a negative electrode active material thin film of Reference Example 1. FIG. 参考実施例２の負極活物質薄膜の厚み方向の元素分布図である。 5 is an element distribution diagram in the thickness direction of a negative electrode active material thin film of Reference Example 2. FIG. 参考比較例１の負極活物質薄膜の厚み方向の元素分布図である。 4 is an element distribution diagram in the thickness direction of a negative electrode active material thin film of Reference Comparative Example 1. FIG. 本発明の実施の形態１に係るリチウムイオン二次電池の主要部の構成の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of a structure of the principal part of the lithium ion secondary battery which concerns on Embodiment 1 of this invention. 本発明の実施の形態１に係るリチウムイオン二次電池の製品形態の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the product form of the lithium ion secondary battery which concerns on Embodiment 1 of this invention. 図６に示したリチウムイオン二次電池の製品形態の概略斜視図である。It is a schematic perspective view of the product form of the lithium ion secondary battery shown in FIG. 本発明の実施の形態１に係るリチウムイオン二次電池の製品形態の別の一例を示す概略断面図である。It is a schematic sectional drawing which shows another example of the product form of the lithium ion secondary battery which concerns on Embodiment 1 of this invention. 図９（Ａ）は、本発明のリチウムイオン二次電池におけるヒューズ部の一例を示した平面図、図９（Ｂ）は、図９（Ａ）における９Ｂ−９Ｂ線での矢視断面図である。9A is a plan view showing an example of the fuse portion in the lithium ion secondary battery of the present invention, and FIG. 9B is a cross-sectional view taken along line 9B-9B in FIG. 9A. is there. 本発明のリチウムイオン二次電池の製造に使用される装置の一実施形態の概略構成を示した断面図である。It is sectional drawing which showed schematic structure of one Embodiment of the apparatus used for manufacture of the lithium ion secondary battery of this invention.

１・・・真空槽
１ａ・・・隔壁
１ｂ・・・搬送室
１ｃ・・・薄膜形成室
４・・・・マスク
５・・・・負極集電体
６・・・・薄膜
１０・・・真空成膜装置
１１・・・巻き出しロール
１２ａ、１２ｂ・・・搬送ロール
１３・・・キャンロール
１４・・・巻き取りロール
１６・・・真空ポンプ
２０・・・電池要素
２２・・・基板
２３・・・負極集電体
２４・・・負極活物質
２５・・・固体電解質
２６・・・正極活物質
２７・・・正極集電体
３０・・・巻回体
３１・・・内芯
３２・・・外部電極
３５・・・外部電極
３６・・・ヒューズ部
３７・・・保護層
５１・・・スパッタ成膜源
５２・・・補助スパッタ成膜源
５５・・・可動遮蔽板
７１・・・負極活物質蒸着源
７２・・・負極集電体蒸着源 DESCRIPTION OF SYMBOLS 1 ... Vacuum chamber 1a ... Partition 1b ... Transfer chamber 1c ... Thin film formation chamber 4 ... Mask 5 ... Negative electrode collector 6 ... Thin film 10 ... Vacuum Film forming apparatus 11 ... unwinding rolls 12a, 12b ... transport roll 13 ... can roll 14 ... take-up roll 16 ... vacuum pump 20 ... battery element 22 ... substrate 23 .. Negative electrode current collector 24... Negative electrode active material 25... Solid electrolyte 26... Positive electrode active material 27. External electrode 35 ... External electrode 36 ... Fuse portion 37 ... Protective layer 51 ... Sputter film formation source 52 ... Auxiliary sputter film formation source 55 ... Movable shielding plate 71 ... Negative electrode Active material vapor deposition source 72 ... Negative electrode current collector vapor deposition source

Claims (5)

基板上に正極集電体、正極活物質、及び固体電解質がこの順に形成された積層体の前記固体電解質上にシリコンを主成分として含む負極活物質薄膜及び集電体を真空成膜法により形成するリチウムイオン二次電池の製造方法であって、
それぞれからの成膜粒子の一部が相互に混合されるように隣り合わせて配置された、前記負極活物質薄膜を形成するための負極活物質成膜源及び前記集電体を形成するための集電体成膜源に対して、前記積層体を、前記負極活物質成膜源側から前記集電体成膜源側に向かって相対的に移動させることを特徴とするリチウムイオン二次電池の製造方法。 A negative electrode active material thin film containing silicon as a main component and a current collector are formed by a vacuum film formation method on the solid electrolyte of a laminate in which a positive electrode current collector, a positive electrode active material, and a solid electrolyte are formed in this order on a substrate. A method for manufacturing a lithium ion secondary battery , comprising:
A negative electrode active material film forming source for forming the negative electrode active material thin film and a collector for forming the current collector, which are arranged adjacent to each other so that some of the film forming particles from each are mixed with each other. In the lithium ion secondary battery , the laminate is moved relative to the current source film forming source side from the negative electrode active material film source side with respect to the current source film forming source. Production method. 前記真空成膜法が真空蒸着法である請求項１に記載のリチウムイオン二次電池の製造方法。 The method for manufacturing a lithium ion secondary battery according to claim 1 , wherein the vacuum film formation method is a vacuum deposition method. 前記集電体成膜源が銅を主成分として含む請求項１に記載のリチウムイオン二次電池の製造方法。 The method for manufacturing a lithium ion secondary battery according to claim 1 , wherein the current collector film-formation source contains copper as a main component. 前記負極活物質薄膜に含まれるシリコンの一部が酸化物である請求項１に記載のリチウムイオン二次電池の製造方法。 The method for producing a lithium ion secondary battery according to claim 1 , wherein a part of silicon contained in the negative electrode active material thin film is an oxide. 基板と、正極集電体と、正極活物質と、固体電解質と、シリコンを主成分として含む負極活物質薄膜と、集電体とをこの順に備えるリチウムイオン二次電池であって、
前記負極活物質薄膜及び前記集電体は、それぞれからの成膜粒子の一部が相互に混合されるように隣り合わせて配置された、前記負極活物質薄膜を形成するための負極活物質成膜源及び前記集電体を形成するための集電体成膜源に対して、前記基板上に前記正極集電体、前記正極活物質、及び前記固体電解質がこの順に形成された積層体を、前記負極活物質成膜源側から前記集電体成膜源側に向かって相対的に移動させることにより、前記固体電解質上に真空成膜法により形成されたものであることを特徴とするリチウムイオン二次電池。 A lithium ion secondary battery comprising a substrate, a positive electrode current collector, a positive electrode active material, a solid electrolyte, a negative electrode active material thin film containing silicon as a main component, and a current collector in this order ,
The negative electrode active material thin film and the current collector are arranged adjacent to each other so that a part of the film formation particles from each other are mixed with each other, and a negative electrode active material film for forming the negative electrode active material thin film is formed A stacked body in which the positive electrode current collector, the positive electrode active material, and the solid electrolyte are formed in this order on the substrate with respect to the current collector film forming source for forming the source and the current collector, Lithium formed by vacuum film formation on the solid electrolyte by relatively moving from the negative electrode active material film formation source side toward the current collector film formation source side Ion secondary battery .
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