JP6212305B2 - Composite current collector, and electrode and secondary battery using the same - Google Patents
Composite current collector, and electrode and secondary battery using the same Download PDFInfo
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- JP6212305B2 JP6212305B2 JP2013139359A JP2013139359A JP6212305B2 JP 6212305 B2 JP6212305 B2 JP 6212305B2 JP 2013139359 A JP2013139359 A JP 2013139359A JP 2013139359 A JP2013139359 A JP 2013139359A JP 6212305 B2 JP6212305 B2 JP 6212305B2
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、電気デバイス用複合集電体、およびそれを用いた電極と二次電池に関するものである。 The present invention relates to a composite current collector for an electric device, and an electrode and a secondary battery using the same.
近年、環境・エネルギー問題の高まりから、化石燃料への依存度を減らす低炭素社会の実現に向けた技術の開発が盛んに行われている。このような技術開発の例としては、ハイブリッド電気自動車や電気自動車等の低公害車の開発、太陽光発電や風力発電等の自然エネルギー発電システムの開発、電力を効率よく供給し、送電ロスを減らす次世代送電網の開発等があり、多岐に渡っている。
これらの技術に共通して必要となるキーデバイスの一つが電池であり、このような電池に対しては、システムを小型化するための高いエネルギー密度が求められる。また、使用環境温度に左右されずに安定した電力の供給を可能にするための高い出力特性が求められる。さらに、長期間の使用に耐えうる良好なサイクル特性を有すること等も求められている。そのため、従来の鉛蓄電池、ニッケル−カドミウム電池、ニッケル−水素電池から、より高いエネルギー密度、出力特性およびサイクル特性を有するリチウムイオン二次電池への置き換えが急速に進んでいる。
In recent years, due to increasing environmental and energy problems, technology has been actively developed to realize a low-carbon society that reduces dependence on fossil fuels. Examples of such technology development include the development of low-emission vehicles such as hybrid electric vehicles and electric vehicles, the development of natural energy power generation systems such as solar power generation and wind power generation, and the efficient supply of power to reduce transmission loss There are various developments such as next-generation power grids.
One of the key devices required in common with these technologies is a battery, and such a battery requires a high energy density for downsizing the system. In addition, high output characteristics are required to enable stable power supply regardless of the ambient temperature. Furthermore, it is required to have good cycle characteristics that can withstand long-term use. Therefore, the replacement of the conventional lead storage battery, nickel-cadmium battery, and nickel-hydrogen battery with a lithium ion secondary battery having higher energy density, output characteristics, and cycle characteristics is rapidly progressing.
このようなリチウムイオン二次電池の基本構成は、正極、負極、セパレータ、非水系電解液からなり、正極としては、リチウムイオンを吸蔵・放出可能な正極活物質、導電助材および結着剤を含む正極合材をアルミニウム箔集電体上に製膜したものが用いられる。また、負極としては、リチウムイオンを吸蔵・放出可能な負極活物質、導電助材および結着材を含む負極合材を銅箔集電体上に製膜したものが用いられる。
前記の導電助材としては、サーマルブラック、ファーネスブラック、ランプブラック、チャンネルブラック、ロールブラック、ディスクブラック、アセチレンブラック、ケッチェンブラック、黒鉛等の導電性炭素材料が用いられており、なかでも、アセチレンブラックは、優れた電子伝導性と適度な分散性を有し、正極・負極内部に良好な導電経路を形成できることから、導電助材として好適に用いられている。
The basic configuration of such a lithium ion secondary battery is composed of a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte solution. As the positive electrode, a positive electrode active material capable of occluding and releasing lithium ions, a conductive additive, and a binder are used. What formed the positive electrode compound material containing on an aluminum foil electrical power collector is used. As the negative electrode, a negative electrode active material capable of occluding and releasing lithium ions, a negative electrode mixture containing a conductive additive and a binder is formed on a copper foil current collector.
As the conductive aid, conductive carbon materials such as thermal black, furnace black, lamp black, channel black, roll black, disc black, acetylene black, ketjen black, and graphite are used, and among them, acetylene. Black is suitably used as a conductive aid because it has excellent electronic conductivity and moderate dispersibility and can form a good conductive path inside the positive electrode and the negative electrode.
上記の正極および負極は、充放電容量が活物質単体での充放電容量に近いところまで使われており、電池としてのエネルギー密度は、限界に近づいている。そのため、電極の利用率を向上させるために、導電助材の配合量を減らしたり、正極合材の厚みを増して、相対的に金属箔集電体の量を減らしたりすること等により、充放電容量に寄与しない成分を減らす試みがなされている。しかし、これらの方法では、良好な導電経路の形成が阻害され、電池の出力特性が不十分になる問題があった。 The positive electrode and the negative electrode are used up to the point where the charge / discharge capacity is close to the charge / discharge capacity of the active material alone, and the energy density of the battery is approaching its limit. Therefore, in order to improve the utilization factor of the electrode, the amount of the conductive additive is reduced, the thickness of the positive electrode mixture is increased, and the amount of the metal foil current collector is relatively reduced. Attempts have been made to reduce components that do not contribute to the discharge capacity. However, these methods have a problem that the formation of a good conductive path is hindered and the output characteristics of the battery become insufficient.
また、自動車や次世代送電網システムに使用される電池には、１０年間に及ぶ極めて長期間の稼働を想定したサイクル特性が求められているが、上記の従来の正極および負極では、充放電に伴う電極活物質の膨張・収縮のストレスにより、活物質と導電助材間、導電助材と金属箔集電体間、あるいは導電助材同士の結着が徐々に損なわれ、導電経路が分断されてしまうため、長期間のサイクル試験では、充放電容量が低下してしまう問題があった。 In addition, batteries used in automobiles and next-generation power grid systems are required to have cycle characteristics that are expected to operate for a very long period of 10 years. Due to the stress of expansion / contraction of the electrode active material, the connection between the active material and the conductive material, between the conductive material and the metal foil current collector, or between the conductive materials is gradually damaged, and the conductive path is broken. Therefore, in the long-term cycle test, there is a problem that the charge / discharge capacity decreases.
このような問題に対して、導電助材として、アセチレンブラックの替わりに分枝状の気相法炭素繊維（ＶＧＣＦ）を用いた負極が提案されている（例えば特許文献１）。前記の負極では、負極活物質間に連続した強固な電子伝導経路が形成されることにより、電池のサイクル特性が改善されるが、負極合材を作製する際に、分枝状気相法炭素繊維が毛玉状に凝集してしまい、不均一な導電経路を有する電極となるため、電池の放電容量や出力特性が不十分になってしまう問題があった。 In order to solve such a problem, a negative electrode using a branched vapor grown carbon fiber (VGCF) instead of acetylene black as a conductive additive has been proposed (for example, Patent Document 1). In the negative electrode, a continuous strong electron conduction path is formed between the negative electrode active materials, so that the cycle characteristics of the battery are improved. Since fibers aggregate in a fuzzy ball shape and become an electrode having a non-uniform conductive path, there is a problem that the discharge capacity and output characteristics of the battery become insufficient.
そこで、分岐状のＶＧＣＦを界面活性剤と水または有機溶媒の共存化で湿式粉砕し微細炭素繊維とすることで、分散性を改善する試みがなされている。（特許文献２）。この微細炭素繊維は、負極合材中での分散性が良く、少量で負極内に均一な導電経路を形成できることから、電池のエネルギー密度や出力特性が改善されるが、既述したアセチレンブラックの場合と同様の理由により、長期間のサイクル試験では、充放電容量が低下してしまう問題があった。 Thus, attempts have been made to improve dispersibility by wet-pulverizing branched VGCF into a fine carbon fiber by coexistence of a surfactant and water or an organic solvent. (Patent Document 2). This fine carbon fiber has good dispersibility in the negative electrode composite and can form a uniform conductive path in the negative electrode with a small amount, so that the energy density and output characteristics of the battery are improved. For the same reason as the case, there is a problem that the charge / discharge capacity decreases in the long-term cycle test.
さらに、電池のサイクル特性を改善する技術として、正極集電体の表面に複数の炭素繊維を固定化した正極体が提案されている。（特許文献３）このような構成にすることで、長期間に渡って充放電を繰り返しても電極の膨張・収縮のストレスにより、導電助材と金属箔集電体間の結着性が損なわれることがなく、良好なサイクル特性が得られる。しかし、正極集電体に対して水平方向には、十分な導電経路が形成されないため、良好な出力特性を有する電池が得られないという問題があった。 Furthermore, as a technique for improving the cycle characteristics of a battery, a positive electrode body in which a plurality of carbon fibers are fixed on the surface of a positive electrode current collector has been proposed. (Patent Document 3) With such a configuration, even when charging and discharging are repeated over a long period of time, the binding between the conductive additive and the metal foil current collector is impaired due to the stress of expansion / contraction of the electrode. And good cycle characteristics can be obtained. However, since a sufficient conductive path is not formed in the horizontal direction with respect to the positive electrode current collector, there has been a problem that a battery having good output characteristics cannot be obtained.
本発明は、上記事情に鑑みてなされたものであり、強固で均一な導電経路を有する電気デバイス用複合集電体とそれを用いた電極、および高いエネルギー密度、高い出力特性および良好なサイクル特性を有する二次電池を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a composite current collector for an electric device having a strong and uniform conductive path, an electrode using the same, and a high energy density, a high output characteristic, and a good cycle characteristic. It aims at providing the secondary battery which has.
すなわち本発明は、以下に示されるものである。
（Ａ）導電性シートと繊維状炭素材料を含む複合集電体であり、前記繊維状炭素材料が、主幹と、主幹から分岐した側枝からなる分岐構造を有する繊維状炭素材料を含み、前記主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）が、２〜１０００であり、さらにその一部が前記導電性シートの少なくとも一面に結合されていることを特徴とする複合集電体。
（Ｂ）前記繊維状炭素材料の１０％以上が、分岐構造を有する繊維状炭素材料であることを特徴とする前記の複合集電体。
（Ｃ）前記分岐構造を有する繊維状炭素材料の主幹が、繊維状炭素材料の集合体である前記の複合集電体。
（Ｄ）前記分岐構造を有する繊維状炭素材料の主幹端部の、少なくとも一方が導電性シートに結合されていることを特徴とする前記の複合集電体。
（Ｅ）前記分岐構造を有する繊維状炭素材料の主幹と側枝の少なくとも一方が、繊維状中空炭素材料である前記の複合集電体。
（F）導電性シートが、アルミニウム箔、または銅箔である前記の複合集電体。
（Ｇ）前記分岐構造を有する繊維状炭素材料の主幹の中心間隔（Ｘ）が主幹の平均繊維径（Ｄ)の比｛主幹の中心間隔（Ｘ）/主幹の平均繊維径（Ｄ)｝が、１〜１００である前記の複合集電体。
（Ｈ）前記の複合集電体と、カチオンを吸蔵・放出することが可能な正極活物質、またはカチオンを吸蔵・放出することが可能な負極活物質を含むことを特徴とする二次電池用電極。
（Ｉ）カチオンを吸蔵・放出することが可能な正極および負極の間に介在して、カチオンを移動させる電解質層を有する二次電池であって、前記正極または負極の少なくとも一方が、前記の二次電池用電極であることを特徴とする二次電池。
That is, the present invention is as follows.
(A) A composite current collector including a conductive sheet and a fibrous carbon material, wherein the fibrous carbon material includes a fibrous carbon material having a branched structure composed of a main trunk and side branches branched from the main trunk, And the ratio of the average fiber diameter of the side branch (average fiber diameter of the main trunk) / (average fiber diameter of the side branch) is 2 to 1000, and a part thereof is bonded to at least one surface of the conductive sheet. Characteristic composite current collector.
(B) 10% or more of the said fibrous carbon material is a fibrous carbon material which has a branched structure, The said composite electrical power collector characterized by the above-mentioned.
(C) The composite current collector, wherein a main body of the fibrous carbon material having the branched structure is an aggregate of fibrous carbon materials.
(D) The composite current collector, wherein at least one of main trunk ends of the fibrous carbon material having the branched structure is bonded to a conductive sheet.
(E) The composite current collector, wherein at least one of a main trunk and a side branch of the fibrous carbon material having the branched structure is a fibrous hollow carbon material.
(F) The composite current collector, wherein the conductive sheet is an aluminum foil or a copper foil.
(G) The ratio of the center interval (X) of the main trunk of the fibrous carbon material having the branched structure is the ratio of the average fiber diameter (D) of the main trunk {center interval of main trunk (X) / average fiber diameter of main trunk (D)}. 1 to 100, the composite current collector.
(H) For a secondary battery comprising the composite current collector and a positive electrode active material capable of occluding and releasing cations, or a negative electrode active material capable of occluding and releasing cations electrode.
(I) A secondary battery having an electrolyte layer that moves between cations interposed between a positive electrode and a negative electrode capable of occluding and releasing cations, wherein at least one of the positive electrode and the negative electrode A secondary battery characterized by being an electrode for a secondary battery.
本発明の電気デバイス用複合集電体は、強固で均一な導電経路を有する。そして、それを用いた電極および電池は、高い出力特性、良好なサイクル特性、および高いエネルギー密度を有する。 The composite current collector for an electric device of the present invention has a strong and uniform conductive path. An electrode and a battery using the same have high output characteristics, good cycle characteristics, and high energy density.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
［導電性シート］
本発明で用いる導電性シートとは、電気を良く流す性質を有する材料のシート状成形物であり、成形物の電子抵抗率が１０-2Ω・ｃｍ以下であることが好ましい。このようなシート状成形物として使用することができる材料として、具体的には、金、銅、アルミニウム、ステンレス、ニッケルおよびそれらの合金等の金属材料、カーボンブラック、炭素繊維、カーボンナノチューブ、カーボンナノファイバー、グラッシーカーボン等の炭素材料が挙げられ、上記の材料は、箔、パンチングメタル、クロス、不織布及びメッシュ等のシート状に成形された状態で用いられる。これらの中では、強度、電気的・化学的な安定性とコスト等の面から、銅箔やアルミニウム箔が好ましい。
[Conductive sheet]
The conductive sheet used in the present invention is a sheet-like molded material made of a material having a property of flowing electricity, and the molded article preferably has an electronic resistivity of 10 −2 Ω · cm or less. Specific examples of materials that can be used as such a sheet-like molded product include metal materials such as gold, copper, aluminum, stainless steel, nickel, and alloys thereof, carbon black, carbon fiber, carbon nanotube, and carbon nano Examples thereof include carbon materials such as fiber and glassy carbon, and the above materials are used in a state of being formed into a sheet shape such as foil, punching metal, cloth, nonwoven fabric, and mesh. Among these, copper foil and aluminum foil are preferable from the viewpoints of strength, electrical / chemical stability and cost.
本発明で用いられる導電性シートの厚みに、特に制限はないが、薄すぎると強度が低下するため、後述する複合集電体の作製工程において、取扱いが難しくなる傾向がある。また、厚すぎると、電池中の充放電容量に寄与しない成分、すなわち導電性シートの質量と体積の割合が高くなるため、電池のエネルギー密度が低下する傾向がある。従って、導電性シートの厚みは、１〜１００μｍが好ましく、５〜５０μｍがより好ましい。 Although there is no restriction | limiting in particular in the thickness of the electroconductive sheet used by this invention, since intensity | strength will fall when too thin, in the preparation process of the composite electrical power collector mentioned later, there exists a tendency for handling to become difficult. Moreover, since the ratio of the component which does not contribute to the charging / discharging capacity | capacitance in a battery, ie, the mass of a conductive sheet, and a volume will become high when too thick, there exists a tendency for the energy density of a battery to fall. Therefore, 1-100 micrometers is preferable and, as for the thickness of an electroconductive sheet, 5-50 micrometers is more preferable.
［繊維状炭素材料］
本発明で用いる繊維状炭素材料とは、導電性を有する炭素材料を繊維状に加工したものであり、このような繊維状炭素材料として、具体的には、炭素繊維、気相成長炭素繊維、カーボンナノチューブ、カーボンナノファイバー等が挙げられ、後述する複合集電体への加工の容易さと、導電性のバランスの観点から、気相成長炭素繊維やカーボンナノチューブ等の繊維状中空炭素材料であることが好ましい。また、繊維状炭素材料内の電子伝導を効果的にするため、結晶性の高いものが好ましい。
[Fibrous carbon material]
The fibrous carbon material used in the present invention is obtained by processing a carbon material having conductivity into a fiber, and as such a fibrous carbon material, specifically, carbon fiber, vapor-grown carbon fiber, Carbon nanotubes, carbon nanofibers, etc. are mentioned, and from the viewpoint of ease of processing into a composite current collector, which will be described later, and the balance of conductivity, it should be a fibrous hollow carbon material such as vapor-grown carbon fiber or carbon nanotube Is preferred. Moreover, in order to make the electron conduction in a fibrous carbon material effective, a thing with high crystallinity is preferable.
前記の繊維状炭素材料は、主幹と主幹から分岐した側枝からなる分岐構造を有する繊維状炭素材料を含み、前記繊維状炭素材料の合計本数のうち、１０％以上が主幹と側枝からなる分岐構造を有していることが好ましく、３０％以上であることがより好ましく、５０％以上であることがさらに好ましい。また、前記繊維状炭素材料の主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）は２〜１０００の範囲であり、好ましくは５〜８００、さらに好ましくは１０〜５００である。この際、主幹は繊維状炭素材料の一部が物理的に融着、接触または絡み合った複数の繊維状炭素材料からなる集合体であっても構わない。 The fibrous carbon material includes a fibrous carbon material having a branched structure composed of a main trunk and a side branch branched from the main trunk, and 10% or more of the total number of the fibrous carbon materials is a branched structure composed of a main trunk and a side branch. Preferably, it is 30% or more, more preferably 50% or more. The ratio of the average fiber diameter of the main trunk and the side branch of the fibrous carbon material (average fiber diameter of the main trunk) / (average fiber diameter of the side branch) is in the range of 2-1000, preferably 5-800, more preferably 10-500. In this case, the main trunk may be an aggregate composed of a plurality of fibrous carbon materials in which a part of the fibrous carbon material is physically fused, contacted or intertwined.
さらに、前記繊維状炭素材料の主幹と側枝の質量比（主幹の質量）/（側枝の質量）は、０．１〜５０の範囲であることが好ましく、かつ主幹の平均繊維長（Ｌ)と平均繊維径（Ｄ)の比｛主幹の平均繊維長（Ｌ)/ 主幹の平均繊維径（Ｄ)｝は、２０から１００００の範囲であることが好ましく、５００から５０００であることがより好ましい。 Furthermore, the mass ratio of the main trunk to the side branch (mass of the main trunk) / (mass of the side branch) of the fibrous carbon material is preferably in the range of 0.1 to 50, and the average fiber length (L) of the main trunk is The ratio of average fiber diameter (D) {average fiber length of main trunk (L) / average fiber diameter of main trunk (D)} is preferably in the range of 20 to 10,000, more preferably 500 to 5,000.
このような構成にすることで、前記繊維状炭素材料を後述する複合導電体に用いた際、繊維状炭素材料１本、１本の隅々まで少ない抵抗で効率的、かつ均一に電流を流すことができるようになる。 With this configuration, when the fibrous carbon material is used in a composite conductor described later, a current is passed efficiently and uniformly with a small resistance to one corner of the fibrous carbon material. Will be able to.
［複合集電体］
本発明の複合集電体とは、上記の繊維状炭素材料の一部が上記の導電性シートの表面に結合しており、主幹または側枝の一部が上記の導電性シートの少なくとも一面に結合されており、主幹端部の少なくとも一方が導電性シートに結合されていることが好ましい。繊維状炭素材料と導電性シート間の結合の形態は、イオン結合や共有結合等の化学結合や分子間力による結合が含まれるが、絶縁性の樹脂結着剤成分を介した圧着、融着、接着等は含まれない。具体的な結合の形態としては、繊維状炭素材料と導電性シートが直接、あるいは還元活性化した触媒粒子を介して結合していることが好ましく、中でも繊維状炭素材料と導電性シートがイオン結合や共有結合等により直接結合していることがより好ましい。
[Composite current collector]
In the composite current collector of the present invention, a part of the fibrous carbon material is bonded to the surface of the conductive sheet, and a part of the main trunk or side branch is bonded to at least one surface of the conductive sheet. It is preferable that at least one of the main trunk ends is bonded to the conductive sheet. The form of the bond between the fibrous carbon material and the conductive sheet includes chemical bonds such as ionic bonds and covalent bonds, and bonds due to intermolecular forces, but crimping and fusing via an insulating resin binder component. Does not include adhesion. As a specific form of bonding, it is preferable that the fibrous carbon material and the conductive sheet are bonded directly or through reduction-activated catalyst particles, and among them, the fibrous carbon material and the conductive sheet are ionic bonded. It is more preferable that they are directly bonded by a covalent bond or the like.
また、上記繊維状炭素材料の主幹の中心間隔（Ｘ）と主幹の平均繊維径（Ｄ)の比｛主幹の中心間隔（Ｘ）/主幹の平均繊維径（Ｄ)｝は、1〜１００であることが好ましく、２〜８０であることがより好ましく、５〜５０であることがさらに好ましい。 Further, the ratio of the center distance (X) of the main trunk of the fibrous carbon material to the average fiber diameter (D) of the main trunk {the center distance of the main trunk (X) / the average fiber diameter (D) of the main trunk} is 1 to 100. Preferably, it is 2-80, more preferably 5-50.
本発明の複合集電体の一例を図１により模式的に説明する。複合集電体１は、導電性シート２の表面に存在する還元活性化した触媒粒子３から生成した、繊維状炭素材料の主幹４と側枝５からなる。主幹の中心間隔（Ｘ）とは、主幹の中心から、隣り合った主幹の中心までの距離のことである。また、主幹の平均繊維径（Ｄ)とは、後述した測定方法により計測した、主幹の直径の平均値である。
An example of the composite current collector of the present invention will be schematically described with reference to FIG. The composite current collector 1 is composed of a
本発明の複合集電体は、前記のような構成にすることで、集電体から繊維状炭素材料全体に効率よく電流を流すことが可能で、かつ強固で均一な導電経路が形成される。そのため、それを用いた電極は、従来の活物質、炭素材料、結着剤および溶媒からなる電極スラリーを、導電性シート上に塗布・乾燥・圧縮して作製された電極と比較して、極めて低い電子抵抗を有し、かつ長期間の充放電サイクルにおいて、電極活物質の膨張・収縮による応力が掛かっても、導電経路を維持することができる電極となり、前記の電極を用いた二次電池は、高い出力特性、高いエネルギー密度、および良好なサイクル特性を有する二次電池となる。 The composite current collector of the present invention is configured as described above, so that a current can efficiently flow from the current collector to the entire fibrous carbon material, and a strong and uniform conductive path is formed. . Therefore, the electrode using it is extremely different from the electrode made by applying, drying and compressing the electrode slurry consisting of the conventional active material, carbon material, binder and solvent on the conductive sheet. A secondary battery using the above-mentioned electrode having a low electronic resistance and capable of maintaining a conductive path even when stress due to expansion / contraction of the electrode active material is applied in a long charge / discharge cycle. Becomes a secondary battery having high output characteristics, high energy density, and good cycle characteristics.
複合集電体の作製方法には特に制限は無いが、例えば以下の方法で作製することもできる。触媒となる遷移金属の酸化物粒子と溶媒を含む分散液を浸漬、塗工、ディスペンサー、インクジェット印刷機、スクリーン印刷機またはスプレー等により、導電性シートの表面に塗布する。次いで、分散液の溶媒を乾燥し、さらに必要に応じて加熱処理することにより、表面に所定の間隔で所望の量の触媒が配置された導電性シートを得ることができる。 また、前記の遷移金属の硝酸塩溶液を導電性シートの表面に塗布し、２００℃ 以上に昇温することによっても、触媒を所定の間隔で所望の量を導電性シート上に配置することができる。上記、触媒の粒子径は、０．０１〜１００μｍであることが好ましく、０．１〜１０μｍであることがより好ましい。触媒は、繊維状炭素材料の成長を促進する遷移金属を含み、遷移金属の具体例としては、Ｃｕ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍn、Ｍｇ、ＡｌおよびＣａ等が挙げられる。 Although there is no restriction | limiting in particular in the production method of a composite electrical power collector, For example, it can also produce with the following method. A dispersion containing oxide particles of transition metal as a catalyst and a solvent is applied to the surface of the conductive sheet by dipping, coating, a dispenser, an ink jet printer, a screen printer, or a spray. Next, the solvent of the dispersion liquid is dried, and further subjected to heat treatment as necessary, whereby a conductive sheet having a desired amount of catalyst arranged on the surface at predetermined intervals can be obtained. Also, a desired amount of catalyst can be arranged on the conductive sheet at predetermined intervals by applying the transition metal nitrate solution to the surface of the conductive sheet and raising the temperature to 200 ° C. or higher. . The particle diameter of the catalyst is preferably 0.01 to 100 μm, and more preferably 0.1 to 10 μm. The catalyst includes a transition metal that promotes the growth of the fibrous carbon material, and specific examples of the transition metal include Cu, Fe, Co, Ni, Mn, Mg, Al, and Ca.
次に、触媒を担持した導電性シートを、反応炉に入れ、ヘリウムおよび水素ガスを含む混合ガス雰囲気下で加熱処理し、還元活性化した後、ベンゼン等の炭化水素ガスを１１００℃前後で熱分解反応させることにより、導電性シート表面に主幹となる繊維状炭素材料を生成させる（導電性シートＡ）。次いで、前記の導電性シートＡを反応炉から取り出し、導電性シートＡの表面に生成させた繊維状炭素材料の表面に、上記の遷移金属の酸化物粒子と溶媒を含む分散液、あるいは遷移金属の硝酸塩溶液が付着するように浸漬あるいは、スプレー等により塗布する。その後、既述した触媒の活性化工程と繊維状炭素材料の生成工程を、再度繰り返すことで、主幹に対して側枝となる繊維状炭素材料を生成させ、本発明の複合集電体を得る。この際、触媒は繊維状炭素材料の成長に伴って、導電性シートや主幹の表面から離脱してもよく、その場合、繊維状炭素材料の成長末端に触媒元素が担持されていてもよい。また、繊維状炭素材料の繊維径は、触媒の粒子径に依存するので、主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）が２〜１０００となるように、主幹および側枝の生成に用いる触媒の粒子径を適宜調整する。 Next, the conductive sheet carrying the catalyst is placed in a reaction furnace, heat-treated in a mixed gas atmosphere containing helium and hydrogen gas, and reduced and activated, and then a hydrocarbon gas such as benzene is heated at around 1100 ° C. By causing a decomposition reaction, a fibrous carbon material serving as a main trunk is generated on the surface of the conductive sheet (conductive sheet A). Next, the conductive sheet A is taken out from the reaction furnace, and the dispersion containing the transition metal oxide particles and the solvent or the transition metal is formed on the surface of the fibrous carbon material formed on the surface of the conductive sheet A. It is applied by dipping or spraying so that the nitrate solution adheres. Thereafter, the above-described catalyst activation step and fibrous carbon material generation step are repeated again to generate a fibrous carbon material that is a side branch with respect to the main trunk, thereby obtaining the composite current collector of the present invention. At this time, the catalyst may be detached from the surface of the conductive sheet or the main trunk as the fibrous carbon material grows, and in that case, a catalytic element may be supported on the growth terminal of the fibrous carbon material. Further, since the fiber diameter of the fibrous carbon material depends on the particle diameter of the catalyst, the ratio of the average fiber diameter of the main trunk and the side branch (average fiber diameter of the main trunk) / (average fiber diameter of the side branch) is 2 to 1000. Thus, the particle diameter of the catalyst used for the production | generation of a main trunk and a side branch is adjusted suitably.
［正極および負極］
本発明の二次電池におけるカチオンを可逆的に吸蔵放出する正極は、正極活物質、導電助材、結着剤を含む電極合材を本発明の複合集電体に上に製膜してなる二次電池用の電極である。前記の正極活物質としては、例えば、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、層状マンガン酸リチウム（ＬｉＭｎＯ２）あるいは複数の遷移金属を配合した複合酸化物であるＬｉＭｎｘＮｉｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１、０≦ｙ＜１、０≦ｚ＜１、０≦ｘ＜１）などの層状化合物、あるいは１種以上の遷移金属元素を置換したもの、あるいはマンガン酸リチウム（Ｌｉ１＋ｘＭｎ２−ｘＯ４（ただしｘ＝０〜０．３３）、Ｌｉ１＋ｘＭｎ２−ｘ−ｙＭｙＯ４（ただし、ＭはＮｉ、Ｃｏ、Ｃｒ、Ｃｕ、Ｆｅ、Ａｌ、Ｍｇより選ばれた少なくとも１種の金属を含み、ｘ＝０〜０．３３、ｙ＝０〜１．０、２−ｘ−ｙ＞０）、ＬｉＭｎＯ３、ＬｉＭｎ２Ｏ３、ＬｉＭｎＯ２、ＬｉＭｎ２−ｘＭｘＯ２（ただし、ＭはＣｏ、Ｎｉ、Ｆｅ、Ｃｒ、Ｚｎ、Ｔａより選ばれた少なくとも１種の金属を含み、ｘ＝０．０１〜０．１）、Ｌｉ２Ｍｎ３ＭＯ８（ただし、ＭはＣｏ、Ｎｉ、Ｆｅ、Ｃｒ、Ｚｎ）より選ばれた少なくとも１種の金属である）、銅−リチウム酸化物（Ｌｉ２ＣｕＯ２）、鉄−リチウム酸化物（ＬｉＦｅ３Ｏ４）、あるいはであるＬｉＦｅＰＯ４、ＬｉＭｎＰＯ４およびＬｉ２ＭＰＯ４Ｆ（ただし、ＭはＣｏ、Ｎｉ、Ｆｅ、Ｃｒ、Ｚｎより選ばれた少なくとも１種の金属である）などのポリアニオン系化合物、あるいはＬｉＶ３Ｏ８、Ｖ２Ｏ５、Ｃｕ２Ｖ２Ｏ７等のバナジウム酸化物、あるいはジスルフィド化合物、あるいはＬｉ２ＭＳｉＯ４（ただし、ＭはＣｏ、Ｎｉ、Ｆｅ、Ｃｒ、Ｚｎ、Ｔａより選ばれた少なくとも１種の金属である）などのケイ酸塩系化合物、Ｌｉ２ＭＯ３-ＬｉＭＯ２（ただし、ＭはＭｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｒ、Ｚｎより選ばれた少なくとも１種の金属である）あるいは、Ｆｅ２（ＭｏＯ４）３、Ｌｉ２Ｓ、Ｓなどを挙げることができる。前記の導電助材としては、例えば、サーマルブラック、ファーネスブラック、ランプブラック、チャンネルブラック、ロールブラック、ディスクブラック、アセチレンブラック、ケッチェンブラック、黒鉛等の導電性炭素材料を挙げることができる。
[Positive electrode and negative electrode]
The positive electrode reversibly occluding and releasing cations in the secondary battery of the present invention is formed by forming an electrode mixture containing a positive electrode active material, a conductive additive and a binder on the composite current collector of the present invention. This is an electrode for a secondary battery. Examples of the positive electrode active material include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), layered lithium manganate (LiMnO 2 ), or LiMn x Ni that is a composite oxide containing a plurality of transition metals. Layered compound such as y Co z O 2 (x + y + z = 1, 0 ≦ y <1, 0 ≦ z <1, 0 ≦ x <1), or one substituted with one or more transition metal elements, or lithium manganate (Li 1 + xMn 2−x O 4 (where x = 0 to 0.33), Li 1 + x Mn 2−xy M y O 4 (where M is Ni, Co, Cr, Cu, Fe, Al, Mg) comprising at least one metal more selected, x = 0~0.33, y = 0~1.0,2 -x-y> 0), LiMnO 3, LiMn 2 O 3, LiMnO 2, Li n 2-x M x O 2 ( however, M includes Co, Ni, Fe, Cr, Zn, at least one metal selected from Ta, x = 0.01~0.1), Li 2 Mn 3 MO 8 (wherein M is at least one metal selected from Co, Ni, Fe, Cr, Zn), copper-lithium oxide (Li 2 CuO 2 ), iron-lithium oxide (LiFe 3 O 4 ), or polyanionic compounds such as LiFePO 4 , LiMnPO 4 and Li 2 MPO 4 F (wherein M is at least one metal selected from Co, Ni, Fe, Cr, Zn) Or vanadium oxide such as LiV 3 O 8 , V 2 O 5 , Cu 2 V 2 O 7 , or disulfide compound, or Li 2 MSiO 4 (where M is Co, Ni, Fe, Silicate compounds such as Li 2 MO 3 -LiMO 2 (wherein M is selected from Mn, Co, Ni, Fe, Cr, Zn), which is at least one metal selected from Cr, Zn, Ta Or at least one kind of metal) or Fe 2 (MoO 4 ) 3 , Li 2 S, S, and the like. Examples of the conductive aid include conductive carbon materials such as thermal black, furnace black, lamp black, channel black, roll black, disk black, acetylene black, ketjen black, and graphite.
上記の結着剤用の樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリ−１，１−ジメチルエチレン等のアルカン系ポリマー、ポリブタジエン、ポリイソプレン等の不飽和ポリマー、ポリスチレン、ポリメチルスチレン、ポリビニルピリジン、ポリ−N−ビニルピロリドン等の環を有するポリマー、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ブチル、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸、ポリメタクリル酸、ポリアクリルアミド等のアクリル系ポリマー、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリテトラフルオロエチレン等のフッ素系樹脂、ポリアクリルニトリル、ポリビニリデンシアニド等のシアノ基含有ポリマー、ポリ酢酸ビニル、ポリビニルアルコール等のポリビニルアルコール系ポリマー、ポリ塩化ビニル、ポリ塩化ビニリデン等のハロゲン含有ポリマー、ポリアニリン等の導電性ポリマー等が挙げられる。また、上記のポリマーの混合物、変成体、誘導体、ランダム共重合体、交互共重合体、グラフト共重合体、ブロック共重合体などであっても使用できる。また、電池の安定性や寿命を高めるため、トリフルオロプロピレンカーボネート、ビニレンカーボネート、カテコールカーボネート、１，６−ジオキサスピロ[４，４]ノナン−２，７−ジオン、１２−クラウン−４−エーテル等を含んでいても良い。更に、補強材として、各種の無機および有機の球状、板状、棒状、繊維状などのフィラーが使用できる。 Examples of the resin for the binder include alkane polymers such as polyethylene, polypropylene, poly-1,1-dimethylethylene, unsaturated polymers such as polybutadiene and polyisoprene, polystyrene, polymethylstyrene, polyvinylpyridine, Polymers having a ring such as poly-N-vinylpyrrolidone, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, etc. Fluorine resins such as acrylic polymers, polyvinyl fluoride, polyvinylidene fluoride and polytetrafluoroethylene, cyano group-containing polymers such as polyacrylonitrile and polyvinylidene cyanide, polyvinyl resins such as polyvinyl acetate and polyvinyl alcohol Examples thereof include halogen-containing polymers such as nyl alcohol polymers, polyvinyl chloride and polyvinylidene chloride, and conductive polymers such as polyaniline. Further, a mixture, modified product, derivative, random copolymer, alternating copolymer, graft copolymer, block copolymer, or the like of the above-described polymer can be used. In order to increase the stability and life of the battery, trifluoropropylene carbonate, vinylene carbonate, catechol carbonate, 1,6-dioxaspiro [4,4] nonane-2,7-dione, 12-crown-4-ether, etc. It may be included. Furthermore, various inorganic and organic spherical, plate-like, rod-like, and fibrous fillers can be used as the reinforcing material.
本発明におけるリチウムを可逆的に吸蔵放出する負極としては、負極活物質と結着剤を含む負極合材を、本発明の複合集電体に上に製膜してなる二次電池用の電極である。負極活物質としては、例えば、天然黒鉛、石油コークスや石炭ピッチコークス等から得られる易黒鉛化材料を２５００℃以上の高温で熱処理したもの、メソフェースカーボン、あるいは非晶質炭素、炭素繊維等の炭素系材料、リチウム−チタン酸化物（Ｌｉ４Ｔｉ５Ｏ１２等）、リチウムと合金化する金属、あるいは炭素粒子表面に金属を担持させた材料等が用いられる。このような金属としては、例えば、リチウム、アルミニウム、スズ、ケイ素、インジウム、ガリウム、マグネシウムとそれらの合金が挙げられる。また、該金属または金属の酸化物も負極活物質として利用できる。前記の結着剤としては、例えば、前記の正極と同じ結着剤を用いることができる。このような負極活物質の中で、得られる電池のサイクル特性と安全性の観点から、炭素系材料とリチウム−チタン酸化物が好ましい。 As a negative electrode for reversibly occluding and releasing lithium in the present invention, an electrode for a secondary battery formed by forming a negative electrode mixture containing a negative electrode active material and a binder on the composite current collector of the present invention. It is. Examples of the negative electrode active material include those obtained by heat-treating graphitizable materials obtained from natural graphite, petroleum coke, coal pitch coke, and the like at a high temperature of 2500 ° C. or higher, mesophase carbon, amorphous carbon, carbon fiber, and the like. A carbon-based material, lithium-titanium oxide (Li 4 Ti 5 O 12 or the like), a metal alloyed with lithium, or a material in which a metal is supported on the surface of carbon particles is used. Examples of such metals include lithium, aluminum, tin, silicon, indium, gallium, magnesium, and alloys thereof. The metal or metal oxide can also be used as the negative electrode active material. As the binder, for example, the same binder as that of the positive electrode can be used. Among such negative electrode active materials, carbon-based materials and lithium-titanium oxides are preferable from the viewpoint of cycle characteristics and safety of the obtained battery.
正極と負極の作製方法には特に制限は無く、従来公知の二次電池用電極の作製方法を用いて行えば良いが、例えば以下の方法で作製することもできる。活物質とアセチレンブラック等の導電材料を含む混合物を、結着剤の溶媒溶液（分散液）とボールミル、サンドミル、二軸混練機、自転公転式攪拌機、プラネタリーミキサー、ディスパーミキサー等により混合することでスラリーを得る。次いで、このスラリーを本発明の複合集電体上に塗布した後、加熱によりスラリーに含まれる溶剤を除去し、活物質とアセチレンブラック等の導電材料がバインターを介して複合集電体表面の繊維状炭素材料と相互に結着された多孔質体である電極合材層を形成する。さらに複合集電体と電極合材層をロールプレス等により加圧して密着させることにより目的とする電極を得ることができる。
スラリーに用いる溶媒は活物質に対して不活性であり、且つ結着剤を溶解・分散し得る限り特に制限されず、無機または有機の何れの溶剤であってもよい。好適な溶媒の一例としては、Ｎ−メチル−２−ピロリドンが挙げられる。
The method for producing the positive electrode and the negative electrode is not particularly limited, and may be performed using a conventionally known method for producing an electrode for a secondary battery. For example, it can be produced by the following method. Mixing a mixture containing an active material and a conductive material such as acetylene black and a solvent solution (dispersion) of a binder with a ball mill, a sand mill, a twin-screw kneader, a rotating and rotating stirrer, a planetary mixer, a disper mixer, etc. A slurry is obtained. Next, after applying this slurry onto the composite current collector of the present invention, the solvent contained in the slurry is removed by heating, and the conductive material such as the active material and acetylene black passes through the binder to form fibers on the surface of the composite current collector. An electrode mixture layer which is a porous body bound to the carbonaceous material is formed. Furthermore, the target electrode can be obtained by pressurizing and adhering the composite current collector and the electrode mixture layer with a roll press or the like.
The solvent used for the slurry is not particularly limited as long as it is inactive with respect to the active material and can dissolve and disperse the binder, and may be any inorganic or organic solvent. An example of a suitable solvent is N-methyl-2-pyrrolidone.
［二次電池］
本発明の二次電池の作製方法には、特に制限は無く、従来公知の二次電池の作製方法を用いて行えば良いが、例えば、図２に模式的に示した構成で、以下の方法により作製することもできる。すなわち、前記の電極６とリチウム箔電極７との間に絶縁層となるポリオレフィン製微多孔膜１０を配し、電極６およびポリオレフィン製微多孔膜１０の空隙部分に非水電解液が十分に染込むまで注液することで作製することができる。
[Secondary battery]
The method for producing the secondary battery of the present invention is not particularly limited and may be performed using a conventionally known method for producing a secondary battery. For example, the following method is used in the configuration schematically shown in FIG. Can also be produced. That is, a
本発明の二次電池の用途は、特に限定されないが、例えば、デジタルカメラ、ビデオカメラ、ポータブルオーディオプレイヤー、携帯液晶テレビ等の携帯ＡＶ機器、ノート型パソコン、携帯電話、通信機能付き電子手帳等の携帯情報端末、その他、携帯ゲーム機器、電動工具、電動式自転車、ハイブリット自動車、電気自動車、電力貯蔵システム等の幅広い分野において使用することができる。 The application of the secondary battery of the present invention is not particularly limited, but for example, digital AV cameras, video cameras, portable audio players, portable liquid crystal televisions and other portable AV devices, notebook computers, mobile phones, electronic notebooks with communication functions, etc. It can be used in a wide range of fields such as portable information terminals, portable game devices, electric tools, electric bicycles, hybrid cars, electric cars, power storage systems, and the like.
以下、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明は、その趣旨を損なわない限り、以下に示す実施例に限定されるものではない。また実施例および比較例とも使用した部材は、適切な予備乾燥を行った。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the Example shown below, unless the meaning is impaired. Moreover, the member used with the Example and the comparative example performed appropriate preliminary drying.
（電池の作製例）
アルゴン置換し、露点が−７０℃以下に制御したグローブボックス内で、正極または負極の電極合材塗工面がリチウム金属負極と中央で対向するようにし、さらに電極間にポリオレフィン製微多孔膜を配置した。次に７０×１４０ｍｍ角に切断・加工したアルミラミネートシートを、長辺の中央部で二つ折りにし、電極の集電用タブがラミネートシートの外部に露出するように配置して挟み込んだ。次にヒートシーラーを用いて、アルミラミネートシートの集電用タブが露出した辺を含む２辺を加熱融着した後、シールしていない一辺から、２gの電解液[キシダ化学製、エチレンカーボネート/ジエチルカーボネート＝３／７（ｖｏｌ）＋１Ｍ ＬｉＰＦ６溶液、電解液と表記]を注液し、正極およびポリオレフィン製微多孔膜に十分に染み込ませてから、真空ヒートシーラーにより、電池の内部を減圧しながら、アルミラネートシートの残り１辺を加熱融着して電池を得た。
(Example of battery production)
In a glove box that is purged with argon and controlled to a dew point of −70 ° C. or lower, the electrode composite coating surface of the positive electrode or the negative electrode is opposed to the lithium metal negative electrode in the center, and a polyolefin microporous film is disposed between the electrodes. did. Next, the aluminum laminate sheet cut and processed into a 70 × 140 mm square was folded in half at the center of the long side, and placed and sandwiched so that the current collecting tab of the electrode was exposed to the outside of the laminate sheet. Next, after heat-sealing the two sides including the side where the current collecting tab of the aluminum laminate sheet is exposed using a heat sealer, 2 g of electrolytic solution [made by Kishida Chemical, ethylene carbonate / After injecting diethyl carbonate = 3/7 (vol) + 1M LiPF 6 solution, expressed as electrolyte solution] and sufficiently infiltrating the positive electrode and the microporous membrane made of polyolefin, the inside of the battery was decompressed with a vacuum heat sealer. However, the remaining one side of the aluminum laninate sheet was heat-sealed to obtain a battery.
（実施例１）
平均粒子径０．１５μｍのＣｏ３Ｏ４とＭｇＯの混合粒子１（混合質量比：Ｃｏ３Ｏ４／ＭｇＯ＝６０／４０）を触媒として準備した。この混合粒子１を、０．０５質量％のポリオキシエチレンドデシルエーテルリン酸エステルを溶解させたエタノールと混合して、混合粒子１を０．１質量％含有する触媒分散液を作製した。次いで、導電性シートであるのＡｌ箔（日本製箔株式会社製、サイズ１０×１０ｃｍ、厚さ２０μｍ）の片面に、スプレーにより触媒分散液０．５ｇを均一に塗布した後、１００℃で１時間乾燥して、Ａｌ箔上に触媒が配置された導電性シートを得た。次いで、触媒が配置された導電性シートをヘリウムガスおよび水素ガスを含む混合ガス雰囲気下で加熱し、活性化させた後、ヘリウムガス雰囲気下で６５０℃に加熱し、一酸化炭素ガスと水素ガスを含む混合ガス（混合容積比：一酸化炭素ガス／水素ガス＝８０／２０）を原料ガスとして、この原料ガスを供給しながら約１０時間保持して、Ａｌ箔表面に主幹となる繊維状炭素材料が生成した導電性シートを得た。この時、主幹となる繊維状炭素材料の質量は、２８．１ｍｇであった。
次いで、前記の導電性シートを反応炉から取り出し、繊維状炭素材料生成させた面に、平均粒子径０．０１μｍのＣｏ３Ｏ４とＭｇＯの混合粒子２（混合質量比：Ｃｏ３Ｏ４／ＭｇＯ＝６０／４０）を触媒とし、この混合粒子２を、０．０５質量％のポリオキシエチレンドデシルエーテルリン酸エステルを溶解させたエタノールと混合して、混合粒子２を０．１質量％含有する触媒分散液を作製した。この触媒分散液１５ｇを主幹となる繊維状炭素材料を生成させた面に対して、均一にスプレーした後、上記の触媒を活性化させる工程と繊維状炭素材料を生成させる工程を再度繰り返し、主幹に対して側枝となる繊維状炭素材料を生成させて、本発明の複合集電体Ａを得た。この複合集電体Ａの主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）は１５であり、側枝となる繊維状炭素材料の質量は、２４．２ｍｇであった。また、ＳＥＭ観察により、生成した繊維状炭素材料が中空構造を有していることが確認された。結果を表１に示した。
Example 1
Co 3 O 4 and MgO mixed particles 1 having an average particle size of 0.15 μm (mixing mass ratio: Co 3 O 4 / MgO = 60/40) were prepared as catalysts. The mixed particles 1 were mixed with ethanol in which 0.05% by mass of polyoxyethylene dodecyl ether phosphate was dissolved to prepare a catalyst dispersion containing 0.1% by mass of the mixed particles 1. Next, 0.5 g of the catalyst dispersion was uniformly applied by spraying to one side of an Al foil (made by Nippon Foil Co., Ltd.,
Next, the conductive sheet is taken out of the reaction furnace, and on the surface on which the fibrous carbon material is produced, the
（実施例２）
実施例１の混合粒子１の触媒分散液のスプレー量を０．５ｇから１ｇに、混合粒子２のスプレー量を１５ｇから３０ｇにそれぞれ変更した以外は、実施例１と同様にして複合集電体Ｂを得た。この複合集電体Ｂの主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）は１７であり、主幹となる繊維状炭素材料の質量は５２．１ｍｇ、側枝となる繊維状炭素材料の質量は５２．８ｍｇであった。結果を表１に示した。
(Example 2)
The composite current collector was the same as in Example 1 except that the spray amount of the catalyst dispersion of the mixed particles 1 of Example 1 was changed from 0.5 g to 1 g, and the spray amount of the
（実施例３）
実施例１の混合粒子１と混合粒子２の触媒分散液濃度をそれぞれ０．１質量％から０．４質量％に変更した以外は、実施例１と同様にして複合集電体Ｃを得た。この複合集電体Ｃの主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）は１３であり、主幹となる繊維状炭素材料の質量は８０．２ｍｇ、側枝となる繊維状炭素材料の質量は９１．４ｍｇであった。結果を表１に示した。
(Example 3)
A composite current collector C was obtained in the same manner as in Example 1 except that the catalyst dispersion concentrations of the
（実施例４）
実施例１の混合粒子１の平均粒子径を０．１５μｍから１．０μｍに変更し、混合粒子２の平均粒子径を０．０１μｍから０．００１μｍに変更した以外は、実施例１と同様にして複合集電体Ｄを得た。この複合集電体Ｄの主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）は５９０であり、主幹となる繊維状炭素材料の質量は４０．５ｍｇ、側枝となる繊維状炭素材料の質量は８．１ｍｇであった。結果を表１に示した。
Example 4
Similar to Example 1 except that the average particle size of the mixed particles 1 of Example 1 was changed from 0.15 μm to 1.0 μm and the average particle size of the
（実施例５）
実施例１の混合粒子１の触媒分散液濃度を０．１質量％から０．００１質量％に変更し、導電性シートをAl箔からCu箔（古河サーキットフォイル株式会社製、サイズ１０×１０ｃｍ、厚さ１８μｍ）に変更した以外は、実施例１と同様にして複合集電体Ｅを得た。この複合集電体Ｅの主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）は１４であり、主幹となる繊維状炭素材料の質量は０．３ｍｇ、側枝となる繊維状炭素材料の質量は０．２ｍｇであった。結果を表１に示した。
(Example 5)
The catalyst dispersion concentration of the mixed particles 1 of Example 1 was changed from 0.1% by mass to 0.001% by mass, and the conductive sheet was changed from Al foil to Cu foil (Furukawa Circuit Foil Co., Ltd.,
（比較例１）
実施例１の混合粒子２の平均粒子径を０．０１μｍから０．１５μｍに変更し、混合粒子２を０．１質量％含有する触媒分散液のスプレー量を１５ｇから０．５ｇに変更した以外は、実施例１と同様にして複合集電体Ｆを得た。この複合集電体Ｆの主幹と側枝の平均繊維径の比（主幹の平均繊維径）/（側枝の平均繊維径）は１であり、主幹となる繊維状炭素材料の質量は２４．３ｍｇ、側枝となる繊維状炭素材料の質量は２６．１ｍｇであった。結果を表１に示した。
(Comparative Example 1)
The average particle diameter of the
（比較例２）
実施例２において、側枝の生成工程を行わなかったこと以外は、実施例２と同様にして複合集電体Ｇを得た。なお、主幹となる繊維状炭素材料の質量は５１．３ｍｇであった。結果を表１に示した。
(Comparative Example 2)
A composite current collector G was obtained in the same manner as in Example 2 except that the side branch generation step was not performed in Example 2. In addition, the mass of the fibrous carbon material used as a main trunk was 51.3 mg. The results are shown in Table 1.
（評価方法１）
上記にて得られた実施例１〜５、比較例１および２の各複合集電体について、以下の方法により平均繊維径の測定を行った。結果を表１に示した。
(Evaluation method 1)
For each of the composite current collectors of Examples 1 to 5 and Comparative Examples 1 and 2 obtained above, the average fiber diameter was measured by the following method. The results are shown in Table 1.
＜平均繊維径の測定＞
各実施例および比較例で作製した複合集電体を、ＳＥＭ（日本電子株式会社製、商品名ＪＳＭ７４００Ｆ）を用いて、導電性シートに対して水平方向から繊維状炭素材料の微細構造を観察した。得られたＳＥＭ画像から、主幹および側枝となる繊維状炭素材料の繊維径をSEMの画像処理機能を用いて各々５０本計測し、その平均値を平均繊維径とした。
<Measurement of average fiber diameter>
Using the SEM (trade name JSM7400F, manufactured by JEOL Ltd.), the composite current collector produced in each example and comparative example was observed for the fine structure of the fibrous carbon material from the horizontal direction with respect to the conductive sheet. . From the obtained SEM images, 50 fiber diameters of the fibrous carbon material serving as the main trunk and side branches were measured using the image processing function of the SEM, and the average value was taken as the average fiber diameter.
（電極の作製例）
＜Ｍｎ系正極＞
正極活物質であるニッケルマンガン酸リチウム粉末および結着剤となるポリフッ化ビニリデン Ｎ−メチルピロリドン１２質量％溶液（呉羽化学工業株式会社製、商品名L＃１１２０）、さらに必要に応じて導電助材となるアセチレンブラック（電気化学工業株式会社製、商品名ＨＳ−１００、比表面積４０ｍ２／ｇ）または繊維状炭素材料をＮ−メチルピロリドンを除いた固形成分の質量比で、ニッケルマンガン酸リチウム粉末／ポリフッ化ビニリデン／導電助材＝９０／５／５になるよう配合し、適宜、Ｎ−メチルピロリドンを追加して粘度調整をしながら、プラネタリーミキサーで混練し、スラリー状の分散溶液を得た。
得られた分散溶液をドクターブレードにより厚さ２００μｍおよび４００μｍで複合集電体（導電性シートとして厚さ２０μｍのアルミニウム箔を使用）上に塗布した後、真空下１００℃で５時間乾燥した。乾燥終了後、卓上プレス機を用いてアルミ箔を除いた正極の密度が２．５ｇ／ｃｍ３になるように室温で圧縮してから、正極合材の塗布面が４０×４０ｍｍの大きさになるように切り出し、集電用タブとして４×４０×０．１ｍｍのアルミタブを超音波溶接により接合しＭｎ系正極を得た。
(Example of electrode production)
<Mn-based positive electrode>
Lithium nickel manganate powder as a positive electrode active material and polyvinylidene fluoride N-methylpyrrolidone 12% by mass solution (trade name L # 1120, manufactured by Kureha Chemical Industry Co., Ltd.) as a binder, and if necessary, a conductive aid Acetylene black (trade name HS-100 manufactured by Denki Kagaku Kogyo Co., Ltd., specific surface area 40 m 2 / g) or a fibrous carbon material in a mass ratio of solid components excluding N-methylpyrrolidone, lithium nickel manganate powder / Polyvinylidene fluoride / conducting aid = 90/5/5, kneaded with a planetary mixer while adjusting viscosity by adding N-methylpyrrolidone as appropriate, to obtain a slurry dispersion solution It was.
The obtained dispersion solution was applied onto a composite current collector (using an aluminum foil having a thickness of 20 μm as a conductive sheet) with a doctor blade at a thickness of 200 μm and 400 μm, and then dried under vacuum at 100 ° C. for 5 hours. After completion of drying, after compression at room temperature so that the density of the positive electrode, excluding the aluminum foil, becomes 2.5 g / cm 3 using a desktop press, the coated surface of the positive electrode mixture has a size of 40 × 40 mm. Then, a 4 × 40 × 0.1 mm aluminum tab as a current collecting tab was joined by ultrasonic welding to obtain a Mn-based positive electrode.
＜ＬＦＰ系正極＞
正極活物質であるリン酸鉄リチウム粉末（ＳＴＬ社製、商品名ＳＬＦＰ-ＰＤ６０）および結着剤となるポリフッ化ビニリデン Ｎ−メチルピロリドン１２質量％溶液（呉羽化学工業株式会社製、商品名L＃１１２０）、さらに必要に応じて導電助材となるアセチレンブラック（電気化学工業株式会社製、商品名ＨＳ−１００、比表面積４０ｍ２／ｇ）または繊維状炭素材料をＮ−メチルピロリドンを除いた固形成分の質量比で、リン酸鉄リチウム粉末／ポリフッ化ビニリデン／導電助材＝８０／１０／１０になるよう配合し、適宜、Ｎ−メチルピロリドンを追加して粘度調整をしながら、プラネタリーミキサーで混練し、スラリー状の分散溶液を得た。得られた分散溶液をドクターブレードにより厚さ２００μｍおよび４００μｍで複合集電体（導電性シートとして厚さ２０μｍのアルミニウム箔を使用）上に塗布した後、真空下１００℃で５時間乾燥した。乾燥終了後、卓上ロールプレス機を用いてアルミ箔を除いた正極の密度が２．０ｇ／ｃｍ３になるように室温で圧縮してから、正極合剤の塗布面が４０×４０ｍｍの大きさになるように切り出し、集電用タブとして４×４０×０．１ｍｍのアルミタブを超音波溶接により接合し、ＬＦＰ系正極を得た。
<LFP positive electrode>
Lithium iron phosphate powder (product name: SLFP-PD60), which is a positive electrode active material, and a 12% by weight polyvinylidene fluoride N-methylpyrrolidone solution (product name: L #, Kureha Chemical Industry Co., Ltd.) as a binder 1120), acetylene black (trade name HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd., specific surface area 40 m 2 / g) or a fibrous carbon material, which is a conductive auxiliary material, if necessary, or a solid obtained by removing N-methylpyrrolidone Planetary mixer while adjusting the viscosity by adding N-methylpyrrolidone as appropriate, blending so that the mass ratio of the components is lithium iron phosphate powder / polyvinylidene fluoride / conductive aid = 80/10/10 Kneaded to obtain a slurry dispersion solution. The obtained dispersion solution was applied onto a composite current collector (using an aluminum foil having a thickness of 20 μm as a conductive sheet) with a doctor blade at a thickness of 200 μm and 400 μm, and then dried under vacuum at 100 ° C. for 5 hours. After completion of drying, the surface of the positive electrode mixture is compressed to 40 × 40 mm after being compressed at room temperature using a desktop roll press so that the density of the positive electrode excluding the aluminum foil is 2.0 g / cm 3. The aluminum tab of 4x40x0.1mm was joined by ultrasonic welding as a current collection tab, and the LFP type positive electrode was obtained.
＜人造黒鉛負極＞
負極活物質である人造黒鉛粉末（日立化成株式会社製、商品名ＭＡＧ-Ｄ）および結着剤となるポリフッ化ビニリデンとＮ−メチルピロリドンの１２質量％溶液（呉羽化学工業株式会社製、商品名L＃１１２０）、さらに必要に応じて導電助材となるアセチレンブラック（電気化学工業株式会社製、商品名ＨＳ−１００、比表面積４０ｍ２／ｇ）または繊維状炭素材料をＮ−メチルピロリドンを除いた固形成分の質量比で、人造黒鉛粉末／ポリフッ化ビニリデン／導電助材＝９２／５／３になるよう配合し、適宜、Ｎ−メチルピロリドンを追加して粘度調整をしながら、プラネタリーミキサーで混練し、スラリー状の分散溶液を得た。得られた分散溶液をドクターブレードにより厚さ６０μｍで複合集電体（導電性シートとして厚さ１５μｍの銅箔を使用）上に塗布した後、真空下１００℃で５時間乾燥した。
乾燥終了後、卓上ロールプレス機を用いてアルミ箔を除いた正極の密度が１．５ｇ／ｃｍ３になるように室温で圧縮してから、負極合材の塗布面が４２×４２ｍｍの大きさになるように切り出し、集電用タブとして４×４０×０．１ｍｍのニッケルタブを超音波溶接により接合し、人造黒鉛負極を得た。
<Artificial graphite negative electrode>
Artificial graphite powder (trade name MAG-D, manufactured by Hitachi Chemical Co., Ltd.) as a negative electrode active material, and a 12% by mass solution of polyvinylidene fluoride and N-methylpyrrolidone as a binder (trade name, manufactured by Kureha Chemical Industry Co., Ltd.) L # 1120), and acetylene black (trade name HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd., specific surface area 40 m 2 / g) or a fibrous carbon material, which is a conductive additive, if necessary, except for N-methylpyrrolidone Planetary mixer while adjusting the viscosity by adding N-methylpyrrolidone as appropriate, blending so that the mass ratio of the solid component is artificial graphite powder / polyvinylidene fluoride / conductive aid = 92/5/3 Kneaded to obtain a slurry dispersion solution. The obtained dispersion solution was applied onto a composite current collector (using a copper foil having a thickness of 15 μm as a conductive sheet) with a doctor blade at a thickness of 60 μm, and then dried at 100 ° C. for 5 hours under vacuum.
After drying, after compressing at room temperature using a desktop roll press so that the density of the positive electrode excluding the aluminum foil is 1.5 g / cm 3 , the coated surface of the negative electrode mixture has a size of 42 × 42 mm. Then, a nickel tab of 4 × 40 × 0.1 mm was joined as a current collecting tab by ultrasonic welding to obtain an artificial graphite negative electrode.
＜リチウム箔電極＞
厚さ０．５ｍｍのリチウム金属箔（本城金属株式会社製）を、４２×４２ｍｍの大きさになるように切り出し、集電用タブとして４×４０×０．１ｍｍのニッケルタブを圧着し、リチウム箔電極を得た。
<Lithium foil electrode>
Cut out a 0.5 mm thick lithium metal foil (Honjo Metal Co., Ltd.) to a size of 42 × 42 mm, and crimp a 4 × 40 × 0.1 mm nickel tab as a current collecting tab. A lithium foil electrode was obtained.
（評価方法２）
上記にて得られた実施例１〜５、比較例１および２の各複合集電体を用いて、電極および二次電池を作製し、以下の方法に従って各種特性の測定を行った。結果を表２に示した。
(Evaluation method 2)
An electrode and a secondary battery were prepared using each of the composite current collectors of Examples 1 to 5 and Comparative Examples 1 and 2 obtained above, and various characteristics were measured according to the following methods. The results are shown in Table 2.
＜電極抵抗値の測定＞
各実施例および比較例の複合集電体を用いて電極を作製し、φ10mmの円盤状に切断・加工した。得られた円盤状の電極をφ１３ｍｍ、長さ５ｍｍの円柱状ＳＵＳ製電極に挟み込み、ＳＵＳ製２極セル内に固定した。次いで、２５℃に設定した恒温槽内にＳＵＳ製２極セルを設置し、ソーラトロン１２６０８Ｗ型電気化学測定システムを用いて、印加電流値 ０．２、０．４、０．６、０．８および１．０ｍＡで各１０秒間、定電流分極試験を行った。試験結果からＩ−Ｖプロットを行い、得られた近似直線の傾きから、数式（１）より電極抵抗値を算出した。
電極抵抗値＝（Ｉ−Ｖプロットの傾き×電極の面積） ・・・数式（１）
<Measurement of electrode resistance value>
Electrodes were produced using the composite current collectors of the examples and comparative examples, and cut and processed into a disk shape of φ10 mm. The obtained disc-shaped electrode was sandwiched between cylindrical SUS electrodes having a diameter of 13 mm and a length of 5 mm, and was fixed in a SUS bipolar cell. Next, a SUS bipolar cell was installed in a thermostat set at 25 ° C., and an applied current value of 0.2, 0.4, 0.6, 0.8 and a Solartron 12608W electrochemical measurement system was used. A constant current polarization test was performed at 1.0 mA for 10 seconds each. An IV plot was performed from the test results, and an electrode resistance value was calculated from Equation (1) from the slope of the obtained approximate line.
Electrode resistance value = (slope of IV plot × electrode area) Expression (1)
＜電池特性の測定＞
各実施例および比較例の複合集電体を用いて作製した、アルミタブを接合したＭｎ系正極、LFP系正極またはニッケルタブを接合した人造黒鉛系負極とニッケル端子を圧着したリチウム箔電極で、４５×４５ｍｍに加工したポリオレフィン多孔質膜を挟み込み、電解液を正極、ポリオレフィン多孔質膜に充分に染み込むように滴下した後、アルゴン雰囲気下でアルミラミネートフィルムに封入することにより電池を得た。（実施例６〜１２および比較例３〜６）次いで、２５℃に設定した恒温槽内に電池を設置し、充放電試験機（北斗電工株式会社製、商品名ＳＤ８）を用いて、充放電試験を行った。各電極の充放電試験は、後述した条件に従って行った。
<Measurement of battery characteristics>
A lithium foil electrode in which an aluminum tab-bonded Mn-based positive electrode, an LFP-based positive electrode, or an artificial graphite-based negative electrode bonded to a nickel tab and a nickel terminal are pressure-bonded and produced using the composite current collector of each example and comparative example, 45 A polyolefin porous membrane processed to × 45 mm was sandwiched and the electrolyte was dropped so as to sufficiently penetrate the positive electrode and the polyolefin porous membrane, and then sealed in an aluminum laminate film in an argon atmosphere to obtain a battery. (Examples 6-12 and Comparative Examples 3-6) Next, a battery was installed in a thermostat set to 25 ° C., and charge / discharge was performed using a charge / discharge tester (trade name SD8, manufactured by Hokuto Denko Co., Ltd.). A test was conducted. The charge / discharge test of each electrode was performed according to the conditions described later.
＜Ｍｎ系正極の充放電条件＞
５．０Ｖまで１ＣＡのレートで定電流充電を行い、電圧が５．０Ｖに達してから５時間定電圧充電を行った。次いで、開回路状態で１０分間保持した後、３．０Ｖになるまで１ＣＡのレートで定電流放電を行い、開回路状態で１０分間保持した。前記の条件での放電・充電を１サイクルとして、充放電を５サイクル繰り返した。次いで、１ＣＡで定電流および定電圧放電を行った後、１ＣＡと１０ＣＡで定電流充電を行い、１ＣＡの充電容量と１０ＣＡの充電容量を、それぞれ１ＣＡ充電容量と１０ＣＡ充電容量とした。次に、１ＣＡのレートでの充放電を５０サイクル繰り返し、１サイクル目と５０サイクル目の充電で得られた負極活物質１ｇ当りの充電容量を、それぞれ初回充電容量と最終充電容量とした。
また、数式（２）〜（４）より、ＣＡ、レート特性および放電容量維持率をそれぞれ算出した。
ＣＡ＝（放電電流値／電極の設計容量） ・・・数式（２）
レート特性＝（１０ＣＡ放電容量／１ＣＡ放電容量）×１００ ・・・数式（３）
放電容量維持率＝（最終放電容量／初回放電容量）×１００ ・・・数式（４）
<Charging / discharging conditions of Mn-based positive electrode>
Constant current charging was performed at a rate of 1 CA up to 5.0 V, and constant voltage charging was performed for 5 hours after the voltage reached 5.0 V. Next, after maintaining for 10 minutes in the open circuit state, constant current discharge was performed at a rate of 1 CA until 3.0 V was reached, and the state was maintained for 10 minutes in the open circuit state. Charging / discharging was repeated 5 cycles, with discharging / charging under the above conditions as one cycle. Subsequently, after performing constant current and constant voltage discharge at 1CA, constant current charging was performed at 1CA and 10CA, and the 1CA charge capacity and 10CA charge capacity were set to 1CA charge capacity and 10CA charge capacity, respectively. Next, charging / discharging at a rate of 1CA was repeated 50 cycles, and the charge capacities per gram of the negative electrode active material obtained by charging in the first and 50th cycles were defined as the initial charge capacity and the final charge capacity, respectively.
In addition, CA, rate characteristics, and discharge capacity retention ratio were calculated from Equations (2) to (4), respectively.
CA = (discharge current value / electrode design capacity) Equation (2)
Rate characteristic = (10 CA discharge capacity / 1 CA discharge capacity) × 100 (3)
Discharge capacity retention ratio = (final discharge capacity / initial discharge capacity) × 100 (4)
＜ＬＦＰ系正極の充放電条件＞
Ｍｎ系正極の充放電条件において、定電流、定電圧充電の電圧を５．０Ｖから４．１Ｖに変更し、定電流放電の電圧を３．０Ｖから２．１Ｖに変更した以外は、Ｍｎ系正極の充放電条件と同様に評価を行った。
<Charging and discharging conditions of LFP positive electrode>
Except for changing the constant current and constant voltage charging voltage from 5.0 V to 4.1 V and changing the constant current discharging voltage from 3.0 V to 2.1 V under the charge and discharge conditions of the Mn positive electrode, Evaluation was performed in the same manner as the charge / discharge conditions of the positive electrode.
＜人造黒鉛負極の充放電条件＞
０．０１Ｖまで１ＣＡのレートで定電流放電（リチウムイオンの吸蔵）を行い、電圧が０．０１Ｖに達してから５時間定電圧放電を行った。次いで、開回路状態で１０分間保持した後、１．５Ｖになるまで１ＣＡのレートで定電流充電（リチウムイオンの放出）を行い、開回路状態で１０分間保持した。前記の条件での放電・充電を１サイクルとして、充放電を５サイクル繰り返した。次いで、１ＣＡで定電流および定電圧放電を行った後、１ＣＡと１０ＣＡで定電流充電を行い、１ＣＡの充電容量と１０ＣＡの充電容量を、それぞれ１ＣＡ充電容量と１０ＣＡ充電容量とした。次に、１ＣＡのレートでの充放電を５０サイクル繰り返し、１サイクル目と５０サイクル目の充電で得られた負極活物質１ｇ当りの充電容量を、それぞれ初回充電容量と最終充電容量とした。
<Charging and discharging conditions of artificial graphite negative electrode>
A constant current discharge (occlusion of lithium ions) was performed at a rate of 1 CA up to 0.01 V, and a constant voltage discharge was performed for 5 hours after the voltage reached 0.01 V. Next, after holding for 10 minutes in the open circuit state, constant current charging (release of lithium ions) was performed at a rate of 1 CA until 1.5 V was reached, and the state was maintained for 10 minutes in the open circuit state. Charging / discharging was repeated 5 cycles, with discharging / charging under the above conditions as one cycle. Subsequently, after performing constant current and constant voltage discharge at 1CA, constant current charging was performed at 1CA and 10CA, and the 1CA charge capacity and 10CA charge capacity were set to 1CA charge capacity and 10CA charge capacity, respectively. Next, charging / discharging at a rate of 1CA was repeated 50 cycles, and the charge capacities per gram of the negative electrode active material obtained by charging in the first and 50th cycles were defined as the initial charge capacity and the final charge capacity, respectively.
表２に示した結果から以下のことが分かった。 The following was found from the results shown in Table 2.
（１）実施例６〜１２に用いた複合集電体は、本発明の範囲を満たすので、それを用いて作製した電極は極板抵抗が低く、電池特性の評価では、高いレート特性と良好な放電容量維持率を示したことから、高い出力特性と良好なサイクル特性を備えていることが分かった。さらに、実施例７と８においては、塗工厚みが４００μｍの電極であっても、２００μｍの電極と同等の特性を示したことから、高いエネルギー密度を兼ね備えていることが分かった。 (1) Since the composite current collector used in Examples 6 to 12 satisfies the scope of the present invention, an electrode produced using the composite current collector has a low electrode plate resistance, and in the evaluation of battery characteristics, high rate characteristics and good Since it showed a high discharge capacity retention rate, it was found that it had high output characteristics and good cycle characteristics. Furthermore, in Examples 7 and 8, even if the coating thickness was 400 μm, the characteristics equivalent to those of the 200 μm electrode were exhibited.
（２）比較例３に用いた複合集電体は、（主幹の平均繊維径）/（側枝の平均繊維径）が１であるため、本発明の範囲を満たさない。そのため、それを用いて作製した電極は極板抵抗が大きく、電池特性の評価では、レート特性および放電容量維持率が不十分であった。 (2) The composite current collector used in Comparative Example 3 does not satisfy the scope of the present invention because (average fiber diameter of main trunk) / (average fiber diameter of side branch) is 1. Therefore, an electrode produced using the electrode plate has a large electrode plate resistance, and the rate characteristics and the discharge capacity retention rate were insufficient in evaluating the battery characteristics.
（５）比較例４に用いた複合集電体は、主幹のみで構成されているため、本発明の範囲を満たさない。そのため、それを用いて作製した電極は極板抵抗が大きく、電池特性の評価では、レート特性および放電容量維持率が不十分であった。 (5) Since the composite current collector used in Comparative Example 4 is composed only of the main trunk, it does not satisfy the scope of the present invention. Therefore, an electrode produced using the electrode plate has a large electrode plate resistance, and the rate characteristics and the discharge capacity retention rate were insufficient in evaluating the battery characteristics.
（６）比較例５は、複合集電体を用いず、導電助材として、アセチレンブラックを用いたため、本発明の範囲を満たさない。そのため、作製した電極は極板抵抗が大きく、電池特性の評価では、レート特性および放電容量維持率が不十分であった。 (6) Since Comparative Example 5 does not use a composite current collector and uses acetylene black as a conductive additive, the range of the present invention is not satisfied. Therefore, the produced electrode has a large electrode plate resistance, and the rate characteristics and the discharge capacity retention rate were insufficient in evaluating the battery characteristics.
（７）比較例６は、複合集電体を用いず、導電助材として、粉砕した繊維状炭素材料を用いた。用いた繊維状炭素材料の作製方法を以下に記載する。実施例３で作製した複合集電体Ｃから、剃刀によりＡｌ箔と繊維状炭素材料を分離した。次いで、分離した繊維状炭素材料５ｇ、エタノール５０ｇおよび直径１．０ｍｍのジルコニア製ビーズ２００ｇをアルミナ製ポットに投入し、ボールミリング法により、４時間粉砕処理を行った後、１５０℃に設定した真空乾燥機で１晩乾燥した。粉砕した繊維状炭素材料は本発明の範囲を満たさないため、作製した電極は極板抵抗が大きく、電池特性の評価では、レート特性および放電容量維持率が不十分であった。 (7) Comparative Example 6 did not use a composite current collector, and used a pulverized fibrous carbon material as a conductive additive. The method for producing the fibrous carbon material used is described below. The Al foil and the fibrous carbon material were separated from the composite current collector C produced in Example 3 with a razor. Next, 5 g of the separated fibrous carbon material, 50 g of ethanol, and 200 g of zirconia beads having a diameter of 1.0 mm were put into an alumina pot, and pulverized by ball milling for 4 hours, and then a vacuum set at 150 ° C. Dried overnight in a dryer. Since the pulverized fibrous carbon material does not satisfy the scope of the present invention, the produced electrode has a large electrode plate resistance, and the rate characteristics and the discharge capacity retention rate were insufficient in evaluating the battery characteristics.
（８）表２から明らかなように、本発明によれば、強固で均一な導電経路を有する複合集電体が得られる。また、それを用いた電極および電池は、高い出力特性、良好なサイクル特性、および高いエネルギー密度を兼ね備える。 (8) As is apparent from Table 2, according to the present invention, a composite current collector having a strong and uniform conductive path can be obtained. Moreover, the electrode and battery using the same have high output characteristics, good cycle characteristics, and high energy density.
１・・・複合集電体、２・・・導電性シート、３・・・活性化した触媒粒子、４・・・繊維状炭素材料(主幹)、５・・・繊維状炭素材料(側枝)
６・・・電極、７・・・リチウム箔電極、８・・・正極アルミタブまたは負極ニッケルタブ、９・・・リチウム箔電極ニッケルタブ、１０・・・ポリオレフィン製微多孔膜、１１・・・アルミラミネートフィルム。
DESCRIPTION OF SYMBOLS 1 ... Composite current collector, 2 ... Conductive sheet, 3 ... Activated catalyst particle, 4 ... Fibrous carbon material (main trunk), 5 ... Fibrous carbon material (side branch)
6 ... Electrode, 7 ... Lithium foil electrode, 8 ... Positive electrode aluminum tab or negative electrode nickel tab, 9 ... Lithium foil electrode nickel tab, 10 ... Polyolefin microporous membrane, 11 ... Aluminum Laminate film.
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