JP7181400B2 - CURRENT COLLECTOR FOR POWER STORAGE DEVICE ELECTRODE, METHOD FOR MANUFACTURING THE SAME, AND POWER STORAGE DEVICE - Google Patents
CURRENT COLLECTOR FOR POWER STORAGE DEVICE ELECTRODE, METHOD FOR MANUFACTURING THE SAME, AND POWER STORAGE DEVICE Download PDFInfo
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- JP7181400B2 JP7181400B2 JP2021526925A JP2021526925A JP7181400B2 JP 7181400 B2 JP7181400 B2 JP 7181400B2 JP 2021526925 A JP2021526925 A JP 2021526925A JP 2021526925 A JP2021526925 A JP 2021526925A JP 7181400 B2 JP7181400 B2 JP 7181400B2
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Classifications
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/66—Selection of materials
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Description
本発明は、蓄電デバイス電極用集電体、その蓄電デバイス電極用集電体の製造方法、及びその蓄電デバイス電極用集電体を用いた蓄電デバイスに関する。
本願は、２０１９年６月１９日に、日本国に出願された特願２０１９－１１３９００号に基づき優先権を主張し、その内容をここに援用する。The present invention relates to a power storage device electrode current collector, a method for manufacturing the power storage device electrode current collector, and an power storage device using the power storage device electrode current collector.
This application claims priority based on Japanese Patent Application No. 2019-113900 filed in Japan on June 19, 2019, the content of which is incorporated herein.
従来、電気エネルギーを貯蔵する技術として、電気二重層キャパシタ（例えば、特許文献１参照）や二次電池が知られている。電気二重層キャパシタ（ＥＤＬＣ：Ｅｌｅｃｔｒｉｃ ｄｏｕｂｌｅ－ｌａｙｅｒ ｃａｐａｃｉｔｏｒ）は、寿命、安全性、出力密度が二次電池よりも格段に優れている。しかしながら、電気二重層キャパシタは、二次電池に比べてエネルギー密度（体積エネルギー密度）が低いという課題がある。 Conventionally, electric double layer capacitors (see, for example, Patent Document 1) and secondary batteries are known as techniques for storing electrical energy. An electric double-layer capacitor (EDLC) is much superior to a secondary battery in life, safety, and power density. However, the electric double layer capacitor has a problem that its energy density (volumetric energy density) is lower than that of the secondary battery.
ここで、電気二重層キャパシタに蓄積されるエネルギー（Ｅ）は、キャパシタの静電容量（Ｃ）と印加電圧（Ｖ）を用いてＥ＝１／２×Ｃ×Ｖ２と表され、エネルギーは静電容量と印加電圧の二乗とに比例する。従って、電気二重層キャパシタのエネルギー密度を改善するために、電気二重層キャパシタの静電容量や印加電圧を向上する技術が提案されている。Here, the energy (E) stored in the electric double layer capacitor is expressed as E = 1/2 × C × V 2 using the capacitance (C) of the capacitor and the applied voltage (V), and the energy is Proportional to the capacitance and the square of the applied voltage. Therefore, in order to improve the energy density of the electric double layer capacitor, techniques for improving the capacitance and applied voltage of the electric double layer capacitor have been proposed.
電気二重層キャパシタの静電容量を向上する技術としては、電気二重層キャパシタの電極を構成する活性炭の比表面積を増大させる技術が知られている。現在、知られている活性炭は、比表面積が１０００ｍ２／ｇ～２５００ｍ２／ｇである。このような活性炭を電極に用いた電気二重層キャパシタでは、電解液として第四級アンモニウム塩を有機溶媒に溶解させた有機電解液や、硫酸等の水溶液電解液等が用いられている。
有機電解液は使用できる電圧範囲が広いため、印加電圧を高めることができ、エネルギー密度を向上することができる。As a technique for improving the capacitance of an electric double layer capacitor, a technique for increasing the specific surface area of activated carbon constituting the electrodes of the electric double layer capacitor is known. Currently known activated carbon has a specific surface area of 1000 m 2 /g to 2500 m 2 /g. In such an electric double layer capacitor using activated carbon as an electrode, an organic electrolyte obtained by dissolving a quaternary ammonium salt in an organic solvent, an aqueous electrolyte such as sulfuric acid, or the like is used as the electrolyte.
Since the organic electrolytic solution can be used in a wide voltage range, the applied voltage can be increased, and the energy density can be improved.
電気二重層キャパシタの原理を利用して印加電圧を向上させたキャパシタとして、リチウムイオンキャパシタが知られている。負極にリチウムイオンをインターカレート、ディインターカレートできる黒鉛あるいは炭素を用い、正極に電解質イオンを吸脱着できる電気二重層キャパシタの電極材と同等の活性炭を用いるものは、リチウムイオンキャパシタと呼ばれている。また、正極あるいは負極のいずれか一方に電気二重層キャパシタの電極材と同等の活性炭を用い、もう一方の電極にファラデー反応が起こる電極として、金属酸化物、導電性高分子を用いるものについては、ハイブリッドキャパシタと呼ばれている。リチウムイオンキャパシタは、電気二重層キャパシタを構成する電極のうち、負極がリチウムイオン二次電池の負極材料である黒鉛やハードカーボン、ソフトカーボン等で構成され、その黒鉛やハードカーボン、ソフトカーボン内にリチウムイオンが挿入された電極である。リチウムイオンキャパシタは、一般的な電気二重層キャパシタ、すなわち、両極が活性炭で構成されるものよりも印加電圧が大きくなるという特徴がある。 Lithium ion capacitors are known as capacitors in which the applied voltage is improved using the principle of electric double layer capacitors. Graphite or carbon, which can intercalate and deintercalate lithium ions, is used for the negative electrode, and activated carbon, which is equivalent to the electrode material of electric double layer capacitors, for the positive electrode, which can adsorb and desorb electrolyte ions, is called a lithium ion capacitor. ing. In the case where either the positive electrode or the negative electrode uses activated carbon equivalent to the electrode material of the electric double layer capacitor, and the other electrode uses a metal oxide or a conductive polymer as an electrode in which the Faraday reaction occurs, They are called hybrid capacitors. Among the electrodes that make up the electric double layer capacitor, the lithium ion capacitor is composed of graphite, hard carbon, soft carbon, etc., which are the negative electrode materials of lithium ion secondary batteries, and the graphite, hard carbon, soft carbon, etc. It is an electrode into which lithium ions are inserted. Lithium ion capacitors are characterized by a higher applied voltage than common electric double layer capacitors, that is, capacitors whose both electrodes are made of activated carbon.
しかし、電極に黒鉛を用いた場合、電解液の溶媒として知られる、プロピレンカーボネートを用いることができないという課題がある。電極に黒鉛を用いた場合、プロピレンカーボネートが電気分解して、黒鉛の表面にプロピレンカーボネートの分解生成物が付着し、リチウムイオンの可逆性が低下するためである。プロピレンカーボネートは、低温でも動作可能な溶媒である。プロピレンカーボネートを電気二重層キャパシタに適用した場合、その電気二重層キャパシタは－４０℃でも作動することができる。そこで、リチウムイオンキャパシタでは、プロピレンカーボネートが分解し難いハードカーボンやソフトカーボンが電極材料に用いられている。しかし、ハードカーボンやソフトカーボンは、黒鉛に比べて電極の体積当たりの容量が低く、電圧も黒鉛に比べて低くなる（貴な電位になる）。そのため、リチウムイオンキャパシタのエネルギー密度が低くなる等の課題がある。 However, when graphite is used for the electrodes, there is a problem that propylene carbonate, which is known as a solvent for the electrolyte, cannot be used. This is because, when graphite is used for the electrode, propylene carbonate is electrolyzed, and the decomposition product of propylene carbonate adheres to the surface of the graphite, which reduces the reversibility of lithium ions. Propylene carbonate is a solvent that can work even at low temperatures. When propylene carbonate is applied to an electric double layer capacitor, the electric double layer capacitor can operate even at -40°C. Therefore, in lithium ion capacitors, hard carbon or soft carbon, in which propylene carbonate is difficult to decompose, is used as an electrode material. However, hard carbon and soft carbon have a lower capacity per electrode volume than graphite, and a lower voltage (becomes a noble potential) than graphite. Therefore, there are problems such as the energy density of the lithium ion capacitor being low.
新しい概念のキャパシタとして、活性炭の代わりに黒鉛を正極活物質に用いて黒鉛の層間に電解質イオンを挿入脱離する反応を利用したキャパシタが開発された（例えば、特許文献２参照）。特許文献２には、以下のことが記載されている。正極活物質に活性炭を用いる従来の電気二重層キャパシタでは正極に２．５Ｖを超える電圧を印加すると電解液の分解が生じてガスが発生する。これに対して、正極活物質に黒鉛を用いる新しい概念のキャパシタでは３．５Ｖの充電電圧でも電解液の分解を招来せず、正極活物質に活性炭を用いる従来の電気二重層キャパシタよりも高い電圧で動作できる。この技術を用いると、従来の電気二重層キャパシタに比べてエネルギー密度を２～３倍程度高めることができる。サイクル特性や低温特性、出力特性に関しても従来の電気二重層キャパシタと同等以上となる。黒鉛の比表面積は活性炭の比表面積の数百分の１であり、この電解液分解作用の違いはこの大きな比表面積の違いに起因する。 As a new-concept capacitor, a capacitor has been developed in which graphite is used as a positive electrode active material instead of activated carbon, and electrolyte ions are intercalated and deintercalated between graphite layers (see, for example, Patent Document 2). Patent Document 2 describes the following. In a conventional electric double layer capacitor using activated carbon as a positive electrode active material, when a voltage exceeding 2.5 V is applied to the positive electrode, the electrolytic solution is decomposed to generate gas. On the other hand, in the new-concept capacitor using graphite as the positive electrode active material, the electrolytic solution does not decompose even at a charging voltage of 3.5 V, and the voltage is higher than that of the conventional electric double layer capacitor using activated carbon as the positive electrode active material. can work with By using this technique, the energy density can be increased by about two to three times compared to conventional electric double layer capacitors. Cycle characteristics, low-temperature characteristics, and output characteristics are also equal to or better than those of conventional electric double layer capacitors. The specific surface area of graphite is several hundredths of the specific surface area of activated carbon, and the difference in electrolyte decomposition action is due to this large difference in specific surface area.
黒鉛を正極活物質に用いる新しい概念のキャパシタでは、耐久性が十分ではないため、実用化が阻まれていた。しかし、非晶質炭素被膜で被覆されたアルミニウム材を集電体に用いる技術（特許文献３参照）により、高温耐久性能を実用化レベルまで改善できることが分かっている。なお、この新しい概念のキャパシタは、正極に黒鉛の層間に電解質イオンを挿入脱離する反応を用いたキャパシタであり、厳密には電気二重層キャパシタではないが、特許文献３では広義の意味で電気二重層キャパシタと呼んでいる。 A new-concept capacitor that uses graphite as a positive electrode active material has not been put to practical use because of its insufficient durability. However, it is known that high-temperature durability can be improved to a practical level by a technique of using an aluminum material coated with an amorphous carbon film as a current collector (see Patent Document 3). Note that this new-concept capacitor is a capacitor that uses a reaction in which electrolyte ions are inserted and detached between graphite layers in the positive electrode, and is not strictly an electric double layer capacitor. They are called double layer capacitors.
さらに、負極においても活性炭の代わりにチタン酸リチウムやリチウム含有ニオブ酸化物などの金属酸化物を負極活物質に用いてチタン酸リチウムの層間にリチウムイオンを挿入脱離する反応を利用した蓄電デバイスが提案された（例えば、特許文献２と４参照）。充放電において、電解質に含まれている電解質アニオンとリチウムカチオンは、それぞれ反対方向で正極又は負極に向かって移動するので、デュアルイオンバッテリ（ＤＩＢ）と呼ばれている。ＤＩＢは、リチウムイオンのみ移動するリチウムイオン二次電池に比べて出力特性と寿命が優れ、ＳＯＣ（充電状態：ｓｔａｔｅ ｏｆ ｃｈａｒｇｅ）に制約を設ける必要がないものと期待されている。 Furthermore, in the negative electrode, instead of activated carbon, a metal oxide such as lithium titanate or lithium-containing niobium oxide is used as the negative electrode active material, and an electric storage device utilizing the reaction of intercalating and deintercalating lithium ions between the layers of lithium titanate has been developed. have been proposed (see, for example, US Pat. During charging and discharging, the electrolyte anions and lithium cations contained in the electrolyte move in opposite directions toward the positive electrode or the negative electrode, respectively, hence the name dual ion battery (DIB). DIBs are expected to have better output characteristics and lifespan than lithium ion secondary batteries that move only lithium ions, and that there is no need to impose restrictions on SOC (state of charge).
前述の２種類の蓄電デバイスである、ハイブリッドキャパシタ及びデュアルイオンバッテリは従来の電気二重層キャパシタ（ＥＤＬＣ）に比べてエネルギー密度を数倍以上向上できる。一方ＥＤＬＣの大きな特徴である高出力特性に関して、ハイブリッドキャパシタ及びデュアルイオンバッテリもＥＤＬＣ同様に高い出力特性を有する。しかし、さらなる高出力化を目指す課題がある。
本発明は上記事情に鑑みてなされたものであり、ハイブリッドキャパシタやデュアルイオンバッテリなどの蓄電デバイスの電極に用いる集電体（蓄電デバイス電極用集電体）に着目し、蓄電デバイス電極用集電体に含まれている非晶質炭素被膜を高度化することで、さらなる高出力化を図り、高エネルギー密度を維持しつつ、出力特性が優れた蓄電デバイスを提供することを目的とする。また、本発明は、出力特性が優れた蓄電デバイスの電極用集電体、出力特性が優れた蓄電デバイスの電極用集電体の製造方法を提供することを目的とする。The hybrid capacitor and the dual-ion battery, which are the two types of electricity storage devices described above, can improve the energy density by several times or more compared to the conventional electric double layer capacitor (EDLC). On the other hand, with respect to high output characteristics, which is a major feature of EDLCs, hybrid capacitors and dual-ion batteries also have high output characteristics like EDLCs. However, there is a problem in aiming to further increase the output.
The present invention has been made in view of the above circumstances, and focuses on current collectors (current collectors for power storage device electrodes) used for electrodes of power storage devices such as hybrid capacitors and dual ion batteries. An object of the present invention is to provide an electricity storage device with excellent output characteristics while maintaining a high energy density by further increasing the output by improving the amorphous carbon film contained in the body. Another object of the present invention is to provide an electrode current collector for an electric storage device with excellent output characteristics, and a method for manufacturing an electrode current collector for an electric storage device with excellent output characteristics.
上記課題を解決するため、以下の手段を提供する。
［１］ アルミニウム材と、アルミニウム材に形成された非晶質炭素被膜と、を含む蓄電デバイス電極用集電体であって、
非晶質炭素被膜において、ｓｐ２結合炭素及びｓｐ３結合炭素の総量に対するｓｐ２結合炭素の比率（ｓｐ２／（ｓｐ３＋ｓｐ２））は０．３５以上であって、
比率（ｓｐ２／（ｓｐ３＋ｓｐ２））は、Ｘ線吸収微細構造（ＸＡＦＳ）法で測定したものであることを特徴とする蓄電デバイス電極用集電体。
［２］ 蓄電デバイス電極用集電体はハイブリッドキャパシタ正極用集電体又はデュアルイオンバッテリ正極用集電体であって、
ハイブリッドキャパシタ正極又はデュアルイオンバッテリ正極は、正極活物質として黒鉛を含む［１］に記載の蓄電デバイス電極用集電体。
［３］ 蓄電デバイス電極用集電体はハイブリッドキャパシタ負極用集電体又はデュアルイオンバッテリ負極用集電体であって、
ハイブリッドキャパシタ負極又はデュアルイオンバッテリ負極は、負極活物質として活性炭、黒鉛、ハードカーボン、ソフトカーボン、及びチタン酸リチウムからなる群から選択された１種を含む［１］に記載の蓄電デバイス電極用集電体。
［４］ アルミニウム材に非晶質炭素被膜を形成する成膜工程と、
非晶質炭素被膜を４００℃以上の温度で加熱処理する加熱処理工程と
を含むことを特徴とする蓄電デバイス電極用集電体の製造方法。
［５］ 成膜工程の後に、加熱処理工程を行う［４］に記載の蓄電デバイス電極用集電体の製造方法。
［６］ アルミニウム材と、アルミニウム材に形成された非晶質炭素被膜と、を含む蓄電デバイス電極用集電体であって、
非晶質炭素被膜が［４］又は［５］に記載の製造方法で得られたものであることを特徴とする蓄電デバイス電極用集電体。
［７］ 少なくとも正極、負極、及び電解質から構成される蓄電デバイスであって、
正極は正極活物質を含み、かつ、負極は負極活物質を含み、
正極活物質は、黒鉛を含み、
正極側の集電体は［１］又は［６］の何れかに記載の蓄電デバイス電極用集電体であり、
非晶質炭素被膜の厚みが６０ｎｍ以上、３００ｎｍ以下であることを特徴とする蓄電デバイス。
［８］ 黒鉛は菱面体晶を含む［７］に記載の蓄電デバイス。
［９］ 負極活物質は、活性炭、黒鉛、ハードカーボン、及びソフトカーボン、チタン酸リチウムからなる群から選択された１種を含み、
負極側の集電体は［１］及び［７］に記載の蓄電デバイス電極用集電体、エッチドアルミニウム、及び、アルミニウム材からなる群から選択された１種である［７］又は［８］に記載の蓄電デバイス。In order to solve the above problems, the following means are provided.
[1] A current collector for a power storage device electrode comprising an aluminum material and an amorphous carbon film formed on the aluminum material,
In the amorphous carbon film, the ratio of sp2 - bonded carbon to the total amount of sp2-bonded carbon and sp3- bonded carbon ( sp2 /( sp3 + sp2 )) is 0.35 or more,
A current collector for an electric storage device electrode, wherein the ratio (sp 2 /(sp 3 +sp 2 )) is measured by an X-ray absorption fine structure (XAFS) method.
[2] The electrical storage device electrode current collector is a hybrid capacitor positive electrode current collector or a dual ion battery positive electrode current collector,
The current collector for an electricity storage device electrode according to [1], wherein the hybrid capacitor positive electrode or the dual ion battery positive electrode contains graphite as a positive electrode active material.
[3] The electrical storage device electrode current collector is a hybrid capacitor negative electrode current collector or a dual ion battery negative electrode current collector,
The electricity storage device electrode collection according to [1], wherein the hybrid capacitor negative electrode or dual ion battery negative electrode contains, as a negative electrode active material, one selected from the group consisting of activated carbon, graphite, hard carbon, soft carbon, and lithium titanate. electric body.
[4] A film forming step of forming an amorphous carbon coating on an aluminum material;
and a heat treatment step of heat-treating the amorphous carbon film at a temperature of 400° C. or higher.
[5] The method for producing a current collector for an electricity storage device electrode according to [4], wherein the heat treatment step is performed after the film formation step.
[6] A current collector for a power storage device electrode, comprising an aluminum material and an amorphous carbon film formed on the aluminum material,
A current collector for a power storage device electrode, wherein the amorphous carbon film is obtained by the production method according to [4] or [5].
[7] An electricity storage device comprising at least a positive electrode, a negative electrode, and an electrolyte,
the positive electrode comprises a positive electrode active material, and the negative electrode comprises a negative electrode active material,
The positive electrode active material contains graphite,
The current collector on the positive electrode side is the current collector for an electricity storage device electrode according to either [1] or [6],
An electricity storage device, wherein the amorphous carbon film has a thickness of 60 nm or more and 300 nm or less.
[8] The electricity storage device according to [7], wherein the graphite contains rhombohedral crystals.
[9] the negative electrode active material includes one selected from the group consisting of activated carbon, graphite, hard carbon, soft carbon, and lithium titanate;
The current collector on the negative electrode side is one selected from the group consisting of the current collector for the electricity storage device electrode described in [1] and [7], etched aluminum, and an aluminum material [7] or [8 ] The electrical storage device as described in .
本発明によれば、蓄電デバイス電極用集電体に含まれている非晶質炭素被膜を高度化することにより、さらなる高出力化を図り、高エネルギー密度を維持しつつ、出力特性が優れた蓄電デバイスを提供することができる。また、本発明によれば、出力特性が優れた蓄電デバイスの電極用集電体、出力特性が優れた蓄電デバイスの電極用集電体の製造方法を提供することができる。 According to the present invention, by improving the amorphous carbon film contained in the current collector for the electricity storage device electrode, it is possible to further increase the output, and while maintaining the high energy density, the output characteristics are excellent. A power storage device can be provided. Further, according to the present invention, it is possible to provide a current collector for an electrode of an electricity storage device with excellent output characteristics, and a method for manufacturing an electrode current collector for an electricity storage device with excellent output characteristics.
以下の説明において例示される材料、寸法等は一例であって、本発明はそれらに限定されるものではなく、その要旨を変更しない範囲で適宜変更して実施することが可能である。 The materials, dimensions, and the like exemplified in the following description are examples, and the present invention is not limited to them, and can be implemented with appropriate modifications without changing the gist of the invention.
（蓄電デバイス電極用集電体）
本発明の蓄電デバイス電極用集電体は、アルミニウム材と前記アルミニウム材に形成された非晶質炭素被膜とを含む。前記非晶質炭素被膜において、ｓｐ２結合炭素及びｓｐ３結合炭素の総量に対するｓｐ２結合炭素の比率（「ｓｐ２／（ｓｐ３＋ｓｐ２）比率」をいう）が０．３５以上であることを特徴とする。なお、前記ｓｐ２／（ｓｐ３＋ｓｐ２）比率は、Ｘ線吸収微細構造（ＸＡＦＳ：Ｘ－ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ）法で測定したものである。ＸＡＦＳ法については後で詳細に説明する。また、非晶質炭素被膜と正極活物質との間、もしくは非晶質炭素被膜と負極活物質との間に導電性炭素層が形成されていてもよい。
本発明の蓄電デバイス電極用集電体は、特に効果を発揮できるため、正極活物質として黒鉛を含むハイブリッドキャパシタ正極に用いられること、あるいは、正極活物質として黒鉛を含むデュアルイオンバッテリ正極用集電体に用いられることが好ましい。また、本発明の蓄電デバイス電極用集電体は、ハイブリッドキャパシタ負極用集電体に用いられること、あるいはデュアルイオンバッテリ負極用集電体に用いられることができる。(Current collector for electricity storage device electrode)
A current collector for a power storage device electrode of the present invention includes an aluminum material and an amorphous carbon film formed on the aluminum material. In the amorphous carbon film, the ratio of sp 2- bonded carbon to the total amount of sp 2-bonded carbon and sp 3- bonded carbon (referring to “sp 2 /(sp 3 +sp 2 ) ratio”) is 0.35 or more. characterized by The sp 2 /(sp 3 +sp 2 ) ratio is measured by an X-ray absorption fine structure (XAFS) method. The XAFS method will be described in detail later. A conductive carbon layer may be formed between the amorphous carbon film and the positive electrode active material, or between the amorphous carbon film and the negative electrode active material.
Since the current collector for an electricity storage device electrode of the present invention can exhibit a particular effect, it can be used for a hybrid capacitor positive electrode containing graphite as a positive electrode active material, or a current collector for a dual ion battery positive electrode containing graphite as a positive electrode active material. It is preferably used on the body. Further, the current collector for an electricity storage device electrode of the present invention can be used as a current collector for a hybrid capacitor negative electrode, or can be used as a current collector for a dual ion battery negative electrode.
ここで、本発明の「ハイブリッドキャパシタ」とは、負極には電解質のカチオンの吸脱着という電気二重層の原理を用い、正極には黒鉛への電解質アニオンの挿入脱離（インターカレーション－ディインターカレーション）の原理を用いた蓄電デバイスである。例えば、負極に活性炭、正極に黒鉛を用いたものが挙げられる。 Here, the "hybrid capacitor" of the present invention uses the principle of an electric double layer of adsorption and desorption of cations in the electrolyte for the negative electrode, and the insertion and desorption (intercalation-deintercalation) of electrolyte anions into graphite for the positive electrode. It is an electricity storage device that uses the principle of calration. For example, one using activated carbon for the negative electrode and graphite for the positive electrode can be used.
ここで、本発明の「デュアルイオンバッテリ」とは、負極にリチウムイオンを挿入脱離（インターカレーション－ディインターカレーション）させる原理を用い、正極も黒鉛への電解質アニオンの挿入脱離（インターカレーション－ディインターカレーション）させる原理を用いた蓄電デバイスである。「ハイブリッドキャパシタ」も「デュアルイオンバッテリ」も、電解質のアニオンとカチオンが、充電時には正極及び負極へ挿入あるいは吸着し、放電時には脱離あるいは放出される蓄電デバイスである。これは、リチウムイオン電池のように正極中にリチウムイオンが充放電中に移動する原理とは異なるものである。より具体的には、リチウムイオン電池は充電時に正極中のリチウムイオンが負極へ移動（リチウムイオン挿入反応）され、放電（リチウムイオン脱離反応）されるものである。 Here, the “dual-ion battery” of the present invention uses the principle of intercalation-deintercalation of lithium ions in the negative electrode, and the intercalation and deintercalation of electrolyte anions in the positive electrode and graphite. It is an electricity storage device that uses the principle of calation-deintercalation. Both the "hybrid capacitor" and the "dual ion battery" are electricity storage devices in which the anions and cations of the electrolyte are inserted or adsorbed to the positive electrode and the negative electrode during charging, and desorbed or released during discharging. This is different from the principle in which lithium ions migrate into the positive electrode during charging and discharging as in lithium ion batteries. More specifically, in a lithium ion battery, lithium ions in the positive electrode move to the negative electrode (lithium ion insertion reaction) during charging and are discharged (lithium ion desorption reaction).
本発明の蓄電デバイス電極用集電体は、後述の製造方法で得られたものであることが好ましい。 The current collector for an electricity storage device electrode of the present invention is preferably obtained by the production method described below.
＜アルミニウム材＞
基材であるアルミニウム材としては、一般的に集電体用途で使用されるアルミニウム材を用いることができる。
アルミニウム材の形状としては、箔、シート、フィルム、メッシュなどの形態をとることができる。集電体としては、アルミニウム箔を好適に用いることができる。
また、アルミニウム材としてプレーンなものの他、後述するエッチドアルミニウムを用いてもよい。<Aluminum material>
As the aluminum material that is the base material, an aluminum material that is generally used as a current collector can be used.
The aluminum material may be in the form of foil, sheet, film, mesh, or the like. Aluminum foil can be preferably used as the current collector.
In addition to plain aluminum material, etched aluminum, which will be described later, may be used.
アルミニウム材が箔、シートまたはフィルムである場合の厚みについては、特に限定されないが、セル自体のサイズが同じ場合、薄いほどセルケースに入れる活物質を多く封入できるというメリットはあるが、強度が低下するため、適正な厚みを選択する。実際の厚みとしては、１０μｍ～４０μｍが好ましく、１５μｍ～３０μｍがより好ましい。厚みが１０μｍ未満の場合、アルミニウム材の表面を粗面化する工程、または、他の製造工程中において、アルミニウム材の破断または亀裂を生じるおそれがある。 When the aluminum material is a foil, sheet or film, there are no particular restrictions on its thickness. However, if the size of the cell itself is the same, the thinner the material, the more active material can be enclosed in the cell case, but the strength is reduced. Therefore, select an appropriate thickness. The actual thickness is preferably 10 μm to 40 μm, more preferably 15 μm to 30 μm. If the thickness is less than 10 μm, the aluminum material may break or crack during the step of roughening the surface of the aluminum material or during other manufacturing processes.
アルミニウム材として、エッチドアルミニウムを用いてもよい。
エッチドアルミニウムは、エッチングによって粗面化処理されたものである。エッチングは一般的に塩酸等の酸溶液に浸漬（化学エッチング）したり、塩酸等の酸溶液中でアルミニウムを陽極として電解（電気化学エッチング）する方法等が用いられる。電気化学エッチングでは、電解の際の電流波形、溶液の組成、温度等によりエッチング形状が異なるので、蓄電デバイス性能の観点で選択できる。Etched aluminum may be used as the aluminum material.
Etched aluminum is roughened by etching. Etching is generally performed by immersion in an acid solution such as hydrochloric acid (chemical etching), or by electrolysis (electrochemical etching) using aluminum as an anode in an acid solution such as hydrochloric acid. In electrochemical etching, the etching shape differs depending on the current waveform, composition of the solution, temperature, etc. during electrolysis, so the method can be selected from the viewpoint of the performance of the electricity storage device.
アルミニウム材は、表面に不動態層を備えているもの、備えていないもののいずれも用いることができる。アルミニウム材は、その表面に自然酸化膜である不動態膜が形成されている場合、非晶質炭素被膜層をこの自然酸化膜の上に設けてもよいし、自然酸化膜を例えば、アルゴンスパッタリングにより除去した後に設けてもよい。
アルミニウム材上の自然酸化膜は不動態膜であり、それ自体、電解液に浸食されにくいという利点がある一方、集電体の抵抗の増大につながるため、集電体の抵抗の低減の観点では、自然酸化膜がない方が好ましい。The aluminum material may or may not have a passivation layer on its surface. When the aluminum material has a passive film, which is a natural oxide film, formed on its surface, an amorphous carbon coating layer may be provided on the natural oxide film, or the natural oxide film may be formed by, for example, argon sputtering. may be provided after removal by
The natural oxide film on the aluminum material is a passive film, and while it has the advantage of being resistant to erosion by the electrolytic solution, it leads to an increase in the resistance of the current collector, so from the viewpoint of reducing the resistance of the current collector , it is preferable that there is no natural oxide film.
＜非晶質炭素被膜＞
本明細書において、用語としての「非晶質炭素被膜」とは、非晶質（アモルファス構造）の炭素膜または水素化炭素膜である。通常、ｓｐ２結合炭素及びｓｐ３結合炭素を一定の比率で含む。本発明の蓄電デバイス電極用集電体に用いる非晶質炭素被膜（今後、「本発明の非晶質炭素被膜」をいう）は、ｓｐ２結合炭素及びｓｐ３結合炭素の総量に対するｓｐ２結合炭素の比率（ｓｐ２／（ｓｐ３＋ｓｐ２）比率とも呼ぶ）が０．３５以上であることを特徴とする。なお、（ｓｐ２／（ｓｐ３＋ｓｐ２））比率は、Ｘ線吸収微細構造（ＸＡＦＳ）法で測定したものである。ｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．４０以上であることが好ましい。
また、高い耐薬品性を維持しつつ、より高い導電性を得ることができ、さらにｓｐ２比率が高い方が柔らかくなり活物質層との密着性が高まる等の観点から、ｓｐ２／（ｓｐ３＋ｓｐ２）比率は、０．６以下であることが好ましく、０．５以下であることがより好ましい。
本発明の非晶質炭素被膜を有する蓄電デバイス電極用集電体（今後、「本発明の蓄電デバイス電極用集電体」をいう）を用いる蓄電デバイスは、高エネルギー密度を維持しつつ、出力特性を向上させることができる。特に、黒鉛活物質からなる正極の集電体として、本発明の蓄電デバイス電極用集電体を用いる蓄電デバイスは、高エネルギー密度を維持しつつ、出力特性をさらに向上させることができるため、好適である。<Amorphous carbon coating>
As used herein, the term "amorphous carbon coating" refers to an amorphous (amorphous structure) carbon film or hydrogenated carbon film. It usually contains a proportion of sp2 - bonded carbons and sp3 - bonded carbons. The amorphous carbon film used for the current collector for an electricity storage device electrode of the present invention (hereinafter referred to as the “amorphous carbon film of the present invention”) has sp 2 bonds with respect to the total amount of sp 2 -bonded carbon and sp 3- bonded carbon It is characterized by having a carbon ratio (also referred to as sp 2 /(sp 3 +sp 2 ) ratio) of 0.35 or more. The (sp 2 /(sp 3 +sp 2 )) ratio is measured by the X-ray absorption fine structure (XAFS) method. The sp 2 /(sp 3 +sp 2 ) ratio is preferably 0.40 or more.
In addition, sp 2 / (sp 3 +sp 2 ) ratio is preferably 0.6 or less, more preferably 0.5 or less.
An electricity storage device using the current collector for an electricity storage device electrode having an amorphous carbon film of the present invention (hereinafter referred to as "the current collector for an electricity storage device electrode of the present invention") maintains a high energy density while outputting characteristics can be improved. In particular, an electricity storage device that uses the current collector for an electricity storage device electrode of the present invention as a current collector for a positive electrode made of a graphite active material can maintain a high energy density and further improve output characteristics, and is therefore suitable. is.
ここで、ＸＡＦＳ法について説明する。
一般的に、各元素は、内殻電子の結合エネルギーに相当するエネルギーのＸ線を強く吸収するという性質を持っている。ここで、物質においてＸ線の吸収係数が大きく上昇する部分を吸収端といい、この吸収端に相当するＸ線のエネルギーをＸ線吸収端エネルギーという。各元素は異なる内殻電子の結合エネルギーを持ち、それより大きいエネルギーを持つＸ線が照射されると、内殻電子の放出にともないＸ線の吸収係数が上昇する。そのため、ある元素についてＸ線吸収スペクトルを測定し、吸収端を観測することで、その元素の周囲の環境・構造を反映したＸ線吸収微細構造（ＸＡＦＳ振動）の情報が得られる。このＸＡＦＳ振動を解析することにより着目する元素の周囲の局所構造を知ることができる。さらに、元素の電子状態の変化により吸収端の位置がシフトすることが知られており、吸収端を比較することで着目する元素の価数を知ることができる。ＸＡＦＳ法を用いて、上記で説明したような試料中の平均的なＸ線吸収スペクトルを得るための測定方法は、透過法と蛍光収量法とがある。透過法は、試料にＸ線を照射した際に、試料の前後のＸ線強度を計測して直接Ｘ線吸収量を測定する方法である。蛍光収量法は、試料にＸ線を照射した際に、Ｘ線を吸収して励起した原子から放出される蛍光Ｘ線を測定する方法である。どちらの方法を用いても、対象元素の局所構造や価数を解析して同様の結果を得ることができる。Here, the XAFS method will be explained.
In general, each element has the property of strongly absorbing X-rays of energy corresponding to the binding energy of inner-shell electrons. Here, a portion of a substance where the absorption coefficient of X-rays greatly increases is called an absorption edge, and the energy of X-rays corresponding to this absorption edge is called X-ray absorption edge energy. Each element has a different binding energy of inner-shell electrons, and when irradiated with X-rays having higher energy than that, the absorption coefficient of X-rays increases as the inner-shell electrons are emitted. Therefore, by measuring the X-ray absorption spectrum of a certain element and observing the absorption edge, information on the X-ray absorption fine structure (XAFS oscillation) that reflects the surrounding environment and structure of the element can be obtained. By analyzing this XAFS oscillation, it is possible to know the local structure around the element of interest. Furthermore, it is known that the position of the absorption edge shifts due to a change in the electronic state of the element, and the valence of the element of interest can be known by comparing the absorption edges. Measurement methods for obtaining an average X-ray absorption spectrum in a sample as described above using the XAFS method include a transmission method and a fluorescence yield method. The transmission method is a method of directly measuring the X-ray absorption amount by measuring the X-ray intensity before and after the sample is irradiated with X-rays. The fluorescence yield method is a method of measuring fluorescent X-rays emitted from atoms excited by absorbing X-rays when a sample is irradiated with X-rays. By using either method, the local structure and valence of the target element can be analyzed and similar results can be obtained.
ＸＡＦＳは、吸収端から５０ｅＶ程度の領域に現れる吸収端近傍Ｘ線吸収微細構造（ＮＥＸＡＦＳ：Ｎｅａｒ Ｅｄｇｅ Ｘ－ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ、またはＸＡＮＥＳ：Ｘ－ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｎｅａｒ Ｅｄｇｅ Ｓｔｒｕｃｔｕｒｅ）と、それ以上のエネルギーで現れる広域Ｘ線吸収微細構造（ＥＸＡＦＳ： Ｅｘｔｅｎｄｅｄ Ｘ－ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ）に分けられる。一方、吸収端から５０ｅＶくらいの範囲にある領域で現れるＮＥＸＡＦＳのピークは内殻電子が空軌道非占有軌道に遷移するエネルギーに対応し、着目元素の価数や配位構造等に依存したスペクトル構造を取る。このように空軌道への励起を観測できるのがＮＥＸＡＦＳの特徴である。本出願のＸＡＦＳ測定法は、後述するように高い精度でダイヤモンドライクカーボン（ＤＬＣ）膜のｓｐ2／（ｓｐ２＋ｓｐ３）比率を決定できるため、ＮＥＸＡＦＳを用いる。XAFS has a near-absorption edge X-ray absorption fine structure (NEXAFS: Near Edge X-ray Absorption Fine Structure, or XANES: X-ray Absorption Near Edge Structure) that appears in a region of about 50 eV from the absorption edge, and at higher energies It is divided into the appearing extended X-ray absorption fine structures (EXAFS). On the other hand, the peak of NEXAFS that appears in the range of about 50 eV from the absorption edge corresponds to the energy at which the core electron transitions to the unoccupied orbital, and the spectral structure depends on the valence and coordination structure of the element of interest. I take the. It is a feature of NEXAFS that it can observe the excitation to empty orbits in this way. The XAFS measurement method of the present application uses NEXAFS because it can determine the sp 2 /(sp 2 +sp 3 ) ratio of diamond-like carbon (DLC) films with high accuracy as described later.
図１に一般的なＤＬＣ膜の炭素原子Ｋ端ＮＥＸＡＦＳスペクトルを示す。炭素のイオン化エネルギーは２９５ｅＶであるので、このエネルギーより高いエネルギーでは直接光イオン化で生じた光電子が含まれる。図１のＤｉｒｅｃｔ ｉｏｎｉｚａｔｉｏｎと示した部分には光電子とその後続反応である正常オージェ電子、及びそれらに起因して放出される２次電子が含まれる。２９０～３１０ｅＶに存在するブロードなピークはＣ１ｓ->σ＊共鳴オージェ電子放出過程に由来するオージェ電子及びそれに起因して放出される２次電子を反映している。２８５．４ｅＶ付近に観測されるピークは１ｓ→π*共鳴オージェ電子放出過程に由来するオージェ電子及びそれに起因して放出される２次電子を反映している。ＮＥＸＡＦＳ測定法において、１ｓ→π＊離して観測することで、ｓｐ２／（ｓｐ２＋ｓｐ３）比率を高い精度で決定できる。実際には定めた領域の吸収強度の積分値（Ｉａｌｌ）と１ｓ→π＊のピーク面積（Ｉπ＊）の比（Ｉπ＊／Ｉａｌｌを算出し、ｓｐ２組成が１００％であるＨＯＰＧのＩπ＊／Ｉａｌｌと比較してｓｐ２／（ｓｐ２＋ｓｐ３）比率を決定する。詳細な測定方法及び解析方法については実施例に記載する。FIG. 1 shows a carbon atom K-edge NEXAFS spectrum of a typical DLC film. Since the ionization energy of carbon is 295 eV, photoelectrons produced by direct photoionization are included at energies higher than this energy. A portion indicated by Directionization in FIG. 1 includes photoelectrons, normal Auger electrons which are subsequent reactions thereof, and secondary electrons emitted as a result thereof. The broad peak present at 290-310 eV reflects Auger electrons derived from the C1s->σ * resonance Auger electron emission process and secondary electrons emitted thereby. The peak observed near 285.4 eV reflects Auger electrons derived from the 1s→π* resonance Auger electron emission process and secondary electrons emitted thereby. In the NEXAFS measurement method, the sp 2 /(sp 2 +sp 3 ) ratio can be determined with high accuracy by observing at a distance of 1 s→π*. In practice, the ratio (I π * /I all ) of the integrated value (I all ) of the absorption intensity in the defined region and the peak area (I π * ) of 1s → π* is calculated, and the sp 2 composition is 100%. The sp 2 /(sp 2 +sp 3 ) ratio is determined by comparison with I π* /I all of HOPG, and detailed measurement and analysis methods are described in the Examples.
ｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．３５以上の本発明の非晶質炭素被膜は、例えば、ダイヤモンドライクカーボン（ＤＬＣ）膜、カーボン硬質膜、アモルファスカーボン（ａ－Ｃ）膜、水素化アモルファスカーボン（ａ－Ｃ：Ｈ）膜等を含む。The amorphous carbon film of the present invention having an sp 2 /(sp 3 +sp 2 ) ratio of 0.35 or more includes, for example, a diamond-like carbon (DLC) film, a carbon hard film, an amorphous carbon (aC) film, a hydrogen including amorphous carbon (aC:H) film and the like.
例示した非晶質炭素被膜の材料のうち、ダイヤモンドライクカーボン（ＤＬＣ）膜であることが好ましい。ダイヤモンドライクカーボンは、ダイヤモンド結合（ｓｐ３）とグラファイト結合（ｓｐ２）の両方が混在したアモルファス構造を有する材料であり、高い耐薬品性を有する。ＸＡＦＳ法で測定したｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．３５以上である本発明の非晶質炭素被膜は、黒鉛構造が発達したＤＬＣ膜であることが好ましい。
また、集電体の被膜に用いるには導電性を高めるため、ホウ素や窒素をドーピングすることができる。Among the exemplified materials for the amorphous carbon film, a diamond-like carbon (DLC) film is preferred. Diamond-like carbon is a material having an amorphous structure in which both diamond bonds (sp 3 ) and graphite bonds (sp 2 ) are mixed, and has high chemical resistance. The amorphous carbon film of the present invention having an sp 2 /(sp 3 +sp 2 ) ratio of 0.35 or more as measured by the XAFS method is preferably a DLC film with a developed graphite structure.
In addition, it can be doped with boron or nitrogen in order to increase conductivity when used as a coating of a current collector.
非晶質炭素被膜の厚みは６０ｎｍ以上、３００ｎｍ以下であることが好ましい。非晶質炭素被膜の厚みは、６０ｎｍ未満であると薄すぎて非晶質炭素被膜の被覆効果が小さくなり、定電流定電圧連続充電試験での集電体の腐食を十分抑制できない。また、非晶質炭素被膜の厚みは、３００ｎｍを超えて厚すぎると非晶質炭素被膜が抵抗体となって活物質層との間の抵抗が高くなるので、適正な厚みを適宜選択する。非晶質炭素被膜の厚みは８０ｎｍ以上、３００ｎｍ以下であればより好ましく、１２０ｎｍ以上、３００ｎｍ以下であればさらに好ましい。 The thickness of the amorphous carbon coating is preferably 60 nm or more and 300 nm or less. If the thickness of the amorphous carbon coating is less than 60 nm, it is too thin and the coating effect of the amorphous carbon coating is reduced, and corrosion of the current collector in the constant current constant voltage continuous charging test cannot be sufficiently suppressed. If the thickness of the amorphous carbon film exceeds 300 nm and is too thick, the amorphous carbon film becomes a resistor and the resistance between it and the active material layer increases. The thickness of the amorphous carbon coating is more preferably 80 nm or more and 300 nm or less, and more preferably 120 nm or more and 300 nm or less.
本発明の一実施形態の蓄電デバイスの集電体はアルミニウム材の表面に非晶質炭素被膜を有するので、アルミニウム材が電解液に接することを阻止して、電解液による集電体の腐食を防止することができる。また、Ｘ線吸収微細構造（ＸＡＦＳ）法で測定したｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．３５以上である本発明の非晶質炭素被膜であるため、一定の導電性を有し、高エネルギー密度を維持しつつ、出力特性が向上される。Since the current collector of the electricity storage device of one embodiment of the present invention has an amorphous carbon film on the surface of the aluminum material, the aluminum material is prevented from coming into contact with the electrolyte, and corrosion of the current collector due to the electrolyte is prevented. can be prevented. In addition, since the amorphous carbon film of the present invention has a sp 2 /(sp 3 +sp 2 ) ratio of 0.35 or more as measured by an X-ray absorption fine structure (XAFS) method, it has a certain degree of conductivity. , the output characteristics are improved while maintaining a high energy density.
本発明の非晶質炭素被膜は、後述の製造方法で得られたものが好ましい。例えば、加熱処理温度が４００℃以上、好ましく５００℃以上である後述の製造方法で得られたものが好ましい。また、本発明の非晶質炭素被膜を含む蓄電デバイス電極用集電体、例えば、ＤＬＣ膜を有するアルミニウム箔（今後、「ＤＬＣコートＡｌ箔」をいう）の量産化の観点より、非晶質炭素被膜（ＤＬＣ膜）をロールツーロール法で行う場合、成膜しながら温度を高くする加熱処理工程を行うと、皺が生じやすくなる課題がある。そこで、鋭意検討した結果、例えば、室温などで成膜工程の後に、成膜工程で得られた非晶質炭素被膜（未加熱処理のＤＬＣ膜）に対して、４００℃以上、好ましく５００℃以上で加熱処理を行う製造方法がより好ましい。この製造方法で得られた本発明の非晶質炭素被膜（加熱処理後のＤＬＣ膜）は、ｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．３５以上となるためである。The amorphous carbon film of the present invention is preferably obtained by the manufacturing method described below. For example, it is preferably obtained by a production method described later in which the heat treatment temperature is 400° C. or higher, preferably 500° C. or higher. In addition, from the viewpoint of mass production of current collectors for electricity storage device electrodes containing the amorphous carbon coating of the present invention, for example, aluminum foil having a DLC film (hereinafter referred to as "DLC-coated Al foil"), amorphous When a carbon film (DLC film) is formed by a roll-to-roll method, there is a problem that wrinkles are likely to occur if a heat treatment step is performed in which the temperature is raised while forming the film. Therefore, as a result of extensive studies, for example, after the film formation process at room temperature, etc., the amorphous carbon film (unheated DLC film) obtained in the film formation process is heated to 400 ° C. or higher, preferably 500 ° C. or higher. A manufacturing method in which the heat treatment is performed at is more preferable. This is because the amorphous carbon film (DLC film after heat treatment) of the present invention obtained by this production method has an sp 2 /(sp 3 +sp 2 ) ratio of 0.35 or more.
＜導電性炭素層＞
本発明の一実施形態の蓄電デバイス電極用集電体は、非晶質炭素被膜と正極活物質との間、もしくは非晶質炭素被膜と負極活物質との間に、さらに、導電性炭素層が形成されていることが好ましい。例えば従来の蓄電デバイスで用いられる活性炭負極に比べて、より卑な電極電位に長くさらされるので、導電性炭素層の厚みは５μｍ以下であれば好ましく、３μｍ以下であればより好ましい。厚みが５μｍを超えると、セルや電極になったとき、エネルギー密度が小さくなるからである。導電性炭素層の材料としては、導電性が高い炭素ならば種類を問わないが、導電性が高い炭素として黒鉛が含まれていることが好ましく、黒鉛のみであればより好ましい。<Conductive carbon layer>
In one embodiment of the current collector for an electricity storage device electrode of the present invention, between the amorphous carbon film and the positive electrode active material, or between the amorphous carbon film and the negative electrode active material, a conductive carbon layer is preferably formed. For example, compared to activated carbon negative electrodes used in conventional electricity storage devices, the conductive carbon layer is exposed to a more base electrode potential for a longer period of time. This is because if the thickness exceeds 5 μm, the energy density becomes small when it becomes a cell or an electrode. As the material of the conductive carbon layer, any type of carbon can be used as long as it has high conductivity, but graphite is preferably included as carbon with high conductivity, and graphite alone is more preferable.
導電性炭素層の材料の粒径は、活物質である黒鉛等の大きさに比べて１／１０以下であることが好ましい。これは、粒径がこの範囲にあれば、導電性炭素層と活物質層が接する界面での接触性が高くなり、界面（接触）抵抗を低減できるからである。具体的には導電性炭素層の炭素材料の粒径が、１μｍ以下であれば好ましく、０．５μｍ以下であればより好ましい。
導電性炭素層を備えることにより、非晶質炭素被膜にピンホールがある場合でも、そのピンホールを封孔して、アルミニウム材が電解液に接することを阻止して、電解液による集電体の腐食を防止することができる。
また、導電性炭素層を備えることにより、集電体を被覆する非晶質炭素被膜と正極活物質、又は非晶質炭素被膜と負極活物質との接触抵抗を低減し、放電率を高め、出力特性を高めるとともに高温耐久性を高めることができる。The particle size of the material of the conductive carbon layer is preferably 1/10 or less of the size of the active material such as graphite. This is because if the particle size is within this range, the contact at the interface between the conductive carbon layer and the active material layer is enhanced, and the interfacial (contact) resistance can be reduced. Specifically, the particle size of the carbon material of the conductive carbon layer is preferably 1 μm or less, more preferably 0.5 μm or less.
By providing the conductive carbon layer, even if there is a pinhole in the amorphous carbon film, the pinhole is sealed to prevent the aluminum material from contacting the electrolyte, and the current collector by the electrolyte corrosion can be prevented.
In addition, by providing the conductive carbon layer, the contact resistance between the amorphous carbon film covering the current collector and the positive electrode active material or between the amorphous carbon film and the negative electrode active material is reduced, the discharge rate is increased, It is possible to improve output characteristics and high temperature durability.
また、導電性炭素層を形成する際、溶媒と共にバインダーを加えて塗料化し、ＤＬＣコーティングしたアルミニウム箔上に塗布する。塗布方法としては、スクリーン印刷、グラビア印刷、コンマコーター（登録商標）、スピンコーター等を用いることができる。バインダーとしては、セルロース、アクリル、ポリビニルアルコール、熱可塑性樹脂、ゴム、有機樹脂を用いることができる。熱可塑性樹脂としてはポリエチレンやポリプロピレン、ゴムとしてはＳＢＲ（スチレンーブタジエンラバー）やＥＰＤＭ、有機樹脂としてはフェノール樹脂やポリイミド樹脂等を用いることができる。 Also, when forming the conductive carbon layer, a solvent and a binder are added to form a paint, which is applied onto a DLC-coated aluminum foil. Screen printing, gravure printing, comma coater (registered trademark), spin coater, etc. can be used as the coating method. Cellulose, acryl, polyvinyl alcohol, thermoplastic resin, rubber, and organic resin can be used as the binder. Polyethylene and polypropylene can be used as thermoplastic resins, SBR (styrene-butadiene rubber) and EPDM can be used as rubbers, and phenol resins and polyimide resins can be used as organic resins.
導電性炭素層は、粒子間の隙間が少なく、接触抵抗が低い方が好ましい。また、上記の導電性炭素層を形成するためのバインダーを溶かすための溶剤としては、水溶液と有機溶剤の２種類がある。電極活物質層を形成するためのバインダーが有機溶剤に溶解するものであれば、導電性炭素層には水溶液に溶解するバインダーを用いるのが好ましい。逆に電極活物質層を形成するためのバインダーが水溶液の場合は導電性炭素層には有機溶剤に溶解するバインダーを用いるのが好ましい。これは同種の溶剤を電極活物質層と導電性炭素層に用いると、電極活物質層を塗布する際に導電性炭素層のバインダーが溶けやすく、不均一になりやすいからである。 The conductive carbon layer preferably has few gaps between particles and low contact resistance. Moreover, as a solvent for dissolving the binder for forming the above conductive carbon layer, there are two kinds of solvents: an aqueous solution and an organic solvent. If the binder for forming the electrode active material layer is soluble in an organic solvent, it is preferable to use a binder soluble in an aqueous solution for the conductive carbon layer. Conversely, when the binder for forming the electrode active material layer is an aqueous solution, it is preferable to use a binder that dissolves in an organic solvent for the conductive carbon layer. This is because if the same kind of solvent is used for the electrode active material layer and the conductive carbon layer, the binder of the conductive carbon layer tends to dissolve when the electrode active material layer is applied, resulting in unevenness.
（蓄電デバイス電極用集電体の製造方法）
本発明の蓄電デバイス電極用集電体の製造方法は、アルミニウム材に非晶質炭素被膜を形成する成膜工程と、非晶質炭素被膜を４００℃以上の温度で加熱処理する加熱処理工程とを含むことを特徴とする。成膜工程及び加熱処理工程の順序は任意であってもよい。例えば、成膜工程と加熱処理工程とが同時に進行する製造方法（直接成膜法ともいうことがある。）、あるいは、成膜工程の後に、加熱処理工程を行う製造方法（後加熱処理成膜法ともいうことがある。）のいずれも可能である。加熱処理工程の処理温度は、３００℃以上が好ましく、また、６００℃以下であることが好ましく、５００℃以下であることがより好ましい。加熱温度を高くする方がｓｐ２／（ｓｐ３＋ｓｐ２）比率が高くなり、抵抗が小さくなるので好ましい。一方、基材のアルミニウムの融点は６６０℃である。融点に近づくほどアルミニウム材が軟化し易くなり、アルミニウム材に皺が入り、基材の平坦性がなくなるので、皺が入りにくい温度が上限値となる。なお、他の金属やアルミニウム合金を基材として用いた場合の上限温度は異なり、各々の融点以下で基材の皺が発生しない温度が上限温度となる。(Manufacturing method of current collector for electricity storage device electrode)
A method for producing a current collector for an electric storage device electrode of the present invention comprises a film forming step of forming an amorphous carbon film on an aluminum material, and a heat treatment step of heat-treating the amorphous carbon film at a temperature of 400° C. or higher. characterized by comprising The order of the film formation process and the heat treatment process may be arbitrary. For example, a manufacturing method in which a film formation process and a heat treatment process proceed simultaneously (sometimes referred to as a direct film formation method), or a manufacturing method in which a heat treatment process is performed after the film formation process (post heat treatment film formation It may also be called law.) is possible. The treatment temperature in the heat treatment step is preferably 300° C. or higher, preferably 600° C. or lower, and more preferably 500° C. or lower. A higher heating temperature is preferable because the sp 2 /(sp 3 +sp 2 ) ratio becomes higher and the resistance becomes smaller. On the other hand, the melting point of aluminum as the base material is 660°C. As the temperature approaches the melting point, the aluminum material softens more easily, wrinkles appear in the aluminum material, and the flatness of the substrate is lost. Note that the upper limit temperature differs when other metals or aluminum alloys are used as the base material, and the upper limit temperature is the temperature below the melting point of each material at which wrinkles do not occur in the base material.
成膜工程と加熱処理工程とが同時に進行する製造方法（直接成膜法）とは、アルミニウム材に非晶質炭素被膜を形成しながら、同じ雰囲気において、例えば、アルミニウム材などを４００℃以上に加熱処理する方法である。 A manufacturing method (direct film forming method) in which a film forming step and a heat treatment step proceed at the same time is, for example, an aluminum material that is heated to 400 ° C. or higher in the same atmosphere while forming an amorphous carbon film on the aluminum material. It is a method of heat treatment.
成膜工程の後に、加熱処理工程を行う製造方法（後加熱処理成膜法）とは、アルミニウム材に非晶質炭素被膜を形成してから、非晶質炭素被膜が形成されているアルミニウム材などを４００℃以上に加熱処理する方法である。加熱処理の雰囲気は、例えば、原料ガスを供給しない雰囲気、好ましくアルゴン雰囲気であってもよい。成膜工程で得られた非晶質炭素被膜を有するアルミニウム材を、成膜工程と異なる別の容器において、例えば、窒素、アルゴンなどの雰囲気で４００℃以上に加熱処理する方法である。その際、成膜工程の処理温度は、２００℃未満であることが好ましく、１００℃以下であることがより好ましく、５０℃以下であることがさらに好ましい。室温であることがもっとも好ましい。 A manufacturing method in which a heat treatment step is performed after a film formation step (post heat treatment film formation method) is an aluminum material in which an amorphous carbon film is formed after forming an amorphous carbon film on an aluminum material. etc. is a method of heat-treating at 400° C. or higher. The atmosphere of the heat treatment may be, for example, an atmosphere in which no source gas is supplied, preferably an argon atmosphere. In this method, the aluminum material having the amorphous carbon film obtained in the film forming process is heat-treated at 400° C. or higher in an atmosphere of, for example, nitrogen or argon, in a container different from that used in the film forming process. At that time, the processing temperature in the film formation step is preferably less than 200° C., more preferably 100° C. or less, and even more preferably 50° C. or less. Room temperature is most preferred.
本発明の蓄電デバイス電極用集電体の製造方法としては、量産化の観点から、上記後加熱処理成膜法が好ましい。例えば、ＤＬＣコートＡｌ箔などの本発明の蓄電デバイス電極用集電体をロールツーロール法で行う場合、上記直接成膜法を用いると、皺が生じやすくなる問題があるからである。 From the viewpoint of mass production, the post-heating film formation method is preferable as the method for producing the current collector for an electricity storage device electrode of the present invention. For example, when the current collector for an electricity storage device electrode of the present invention, such as a DLC-coated Al foil, is produced by the roll-to-roll method, the use of the direct film-forming method causes the problem that wrinkles are likely to occur.
非晶質炭素被膜の成膜方法としては、炭化水素系ガスを用いたプラズマＣＶＤ法、スパッタ蒸着法、イオンプレーティング法、真空アーク蒸着法等の公知の方法を用いることができる。炭化水素系ガスを用いたプラズマＣＶＤ法が好ましい。なお、非晶質炭素被膜は、集電体として機能する程度の導電性を有することが好ましい。
炭化水素系ガスを用いたプラズマＣＶＤ法によって非晶質炭素被膜を成膜した場合、非晶質炭素被膜の厚みはアルミニウム材へ注入するエネルギー、具体的には印加電圧、印加時間、温度で制御することができる。As a method for forming the amorphous carbon coating, known methods such as plasma CVD using a hydrocarbon gas, sputtering vapor deposition, ion plating, and vacuum arc vapor deposition can be used. A plasma CVD method using a hydrocarbon-based gas is preferred. In addition, the amorphous carbon film preferably has conductivity to the extent that it functions as a current collector.
When an amorphous carbon film is formed by plasma CVD using a hydrocarbon gas, the thickness of the amorphous carbon film is controlled by the energy injected into the aluminum material, specifically the applied voltage, applied time, and temperature. can do.
より具体的には、本発明の蓄電デバイス電極用集電体において、４００℃以上の温度で成膜した本発明の非晶質炭素被膜（例えば、ＤＬＣコートＡｌ箔）を用いると、ＸＡＦＳ法で測定したｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．３５以上になる。黒鉛構造が発達した非晶質炭素被膜（ＤＬＣ膜）が得られる。また、非晶質炭素被膜（ＤＬＣコートＡｌ箔）の量産化の観点より、非晶質炭素被膜（ＤＬＣコートＡｌ箔）をロールツーロール法で行う場合、成膜温度を高くすると皺が生じやすくなる課題がある。一方、室温成膜の場合は皺の発生を抑制できるが黒鉛構造が発達しにくい課題があった。その未加熱処理の非晶質炭素被膜（ＤＬＣコートＡｌ箔）は、ｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．２９以下であり、ハイブリッドキャパシタ及びデュアルイオンバッテリ用の電極へ適用した場合、集電体と活物質層の界面抵抗が高くなり、出力特性が低下する恐れがある。そこで、鋭意検討した結果、前述の後加熱処理成膜法において、室温成膜した後、非晶質炭素被膜（ＤＬＣコートＡｌ箔）に対して、不活性雰囲気下で４００℃以上の加熱処理を行うことで、ｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．３５以上にできることを見出した。これは４００℃以上で成膜を直接行った直接成膜法の場合と同等以上のｓｐ２／（ｓｐ３＋ｓｐ２）であった。得られる非晶質炭素被膜（ＤＬＣコートＡｌ箔）を黒鉛からなる正極の集電体として用いることで、出力特性をさらに向上させることができる。More specifically, in the current collector for an electricity storage device electrode of the present invention, when the amorphous carbon coating of the present invention (for example, DLC-coated Al foil) formed at a temperature of 400 ° C. or higher is used, the XAFS method The measured sp 2 /(sp 3 +sp 2 ) ratio is 0.35 or more. An amorphous carbon film (DLC film) with a developed graphite structure is obtained. In addition, from the viewpoint of mass production of the amorphous carbon coating (DLC-coated Al foil), when the amorphous carbon coating (DLC-coated Al foil) is formed by the roll-to-roll method, wrinkles are likely to occur if the film formation temperature is increased. There is another issue. On the other hand, in the case of room temperature film formation, the occurrence of wrinkles can be suppressed, but there is a problem that the graphite structure is difficult to develop. The unheated amorphous carbon coating (DLC-coated Al foil) has a sp 2 /(sp 3 +sp 2 ) ratio of 0.29 or less, and when applied to electrodes for hybrid capacitors and dual ion batteries, The interfacial resistance between the current collector and the active material layer increases, and the output characteristics may deteriorate. Therefore, as a result of intensive studies, in the post-heat treatment film formation method described above, after film formation at room temperature, the amorphous carbon coating (DLC-coated Al foil) is subjected to heat treatment at 400°C or higher in an inert atmosphere. By doing so, the sp 2 /(sp 3 +sp 2 ) ratio can be made 0.35 or more. This was sp 2 /(sp 3 +sp 2 ) equal to or higher than that of the direct film formation method in which film formation was performed directly at 400° C. or higher. Output characteristics can be further improved by using the obtained amorphous carbon coating (DLC-coated Al foil) as a current collector of a positive electrode made of graphite.
ロールツーロール法で直接成膜の際に課題であった箔の皺に関しても、本発明の後加熱処理によって防止することができる。これは、ロールツーロール法で直接成膜では成膜温度（成膜時の雰囲気温度）に加えて、プラズマによるエネルギーによってＡｌ箔の温度が高くなることで雰囲気温度以上になることによる影響があった。しかし、本発明の後加熱処理成膜法では、成膜した箔に対して雰囲気温度だけしかかからないので皺の発生を抑制できる。 The post-heat treatment of the present invention can also prevent wrinkling of the foil, which has been a problem in direct film formation by the roll-to-roll method. This is because in direct film formation by the roll-to-roll method, in addition to the film formation temperature (ambient temperature during film formation), the temperature of the Al foil increases due to the energy of the plasma, which causes the temperature to exceed the atmospheric temperature. rice field. However, in the post-heat treatment film formation method of the present invention, only the ambient temperature is applied to the film-formed foil, so that the occurrence of wrinkles can be suppressed.
（蓄電デバイス）
本発明の一実施形態に係る蓄電デバイスは、正極と負極とセパレータと電解質とを有する。
本発明の蓄電デバイスはハイブリッドキャパシタ又はデュアルイオンバッテリであることが好ましい。(storage device)
A power storage device according to one embodiment of the present invention has a positive electrode, a negative electrode, a separator, and an electrolyte.
The electric storage device of the present invention is preferably a hybrid capacitor or dual ion battery.
（ハイブリッドキャパシタ）
以下、本発明の蓄電デバイスの一実施形態であるハイブリッドキャパシタを詳細に説明する。(hybrid capacitor)
A hybrid capacitor, which is one embodiment of the electricity storage device of the present invention, will be described in detail below.
本実施形態のハイブリッドキャパシタの負極側の集電体、正極側の集電体の少なくとも１つは、前述の本発明の蓄電デバイス電極用集電体を用いることが好ましい。正極が黒鉛を含む場合、少なくとも正極側の集電体は、前述の本発明の蓄電デバイス電極用集電体を用いるが好ましい。負極側の集電体及び正極側の集電体のいずれも、前述の本発明の蓄電デバイス電極用集電体を用いることがより好ましい。 At least one of the current collector on the negative electrode side and the current collector on the positive electrode side of the hybrid capacitor of the present embodiment preferably uses the current collector for the electricity storage device electrode of the present invention described above. When the positive electrode contains graphite, at least the current collector on the positive electrode side is preferably the above-described current collector for an electricity storage device electrode of the present invention. It is more preferable to use the current collector for an electricity storage device electrode of the present invention as described above for both the current collector on the negative electrode side and the current collector on the positive electrode side.
＜正極＞
本実施形態のハイブリッドキャパシタで用いる正極は、集電体（正極側の集電体）とその上に形成されている正極活物質層を含む。正極活物質層は、正極活物質とバインダーと導電材とを含む。
正極活物質層は主に、正極活物質、バインダー、及び、必要に応じた量の導電材を含むペースト状の正極材料を、正極側の集電体上に塗布し、乾燥して、形成することができる。<Positive electrode>
The positive electrode used in the hybrid capacitor of this embodiment includes a current collector (positive electrode-side current collector) and a positive electrode active material layer formed thereon. The positive electrode active material layer includes a positive electrode active material, a binder, and a conductive material.
The positive electrode active material layer is formed by applying a paste-like positive electrode material containing a positive electrode active material, a binder, and an appropriate amount of conductive material onto the current collector on the positive electrode side and drying it. be able to.
［正極活物質］
本実施形態のハイブリッドキャパシタで用いる正極活物質は、黒鉛を含むものである。黒鉛としては、人造黒鉛、天然黒鉛のいずれも用いることができる。また、天然黒鉛としては鱗片状のものと土状のものが知られている。天然黒鉛は、採掘した原鉱石を粉砕し、浮遊選鉱と呼ばれる選鉱を繰り返すことによって得られる。また、人造黒鉛は例えば、高温度によって炭素材料を焼成する黒鉛化工程を経て製造されるものである。より具体的には例えば、原料のコークスにピッチなどの結合剤を加えて成形し、１３００℃付近まで加熱することで一次焼成し、次に一次焼成品をピッチ樹脂に含浸させ、さらに３０００℃に近い高温で二次焼成することで得られる。また、黒鉛粒子表面を炭素でコーティングしているものも用いることができる。[Positive electrode active material]
The positive electrode active material used in the hybrid capacitor of this embodiment contains graphite. As graphite, both artificial graphite and natural graphite can be used. As natural graphite, scale-like and soil-like ones are known. Natural graphite is obtained by pulverizing mined raw ore and repeating beneficiation called flotation. Also, artificial graphite is manufactured through a graphitization process of firing a carbon material at a high temperature, for example. More specifically, for example, a binder such as pitch is added to coke as a raw material and molded, heated to about 1300 ° C. for primary firing, then the primary fired product is impregnated with pitch resin, and further heated to 3000 ° C. Obtained by secondary firing at a near high temperature. Graphite particles whose surfaces are coated with carbon can also be used.
黒鉛の結晶構造は大きく分けて、ＡＢＡＢからなる層構造の六方晶と、ＡＢＣＡＢＣからなる層構造の菱面体晶がある。これらは条件によってそれらの構造単独、あるいは混合状態になるが、いずれの結晶構造のものも混合状態のものも用いることができる。例えば、後述する実施例で用いたイメリス・ジーシー・ジャパン株式会社製ＫＳ－６（商品名）の黒鉛は菱面体晶の比率が２６％であり、大阪ガスケミカル株式会社製の人造黒鉛であるメソカーボンマイクロビーズ（ＭＣＭＢ）は菱面体晶の比率０％である。 The crystal structure of graphite is roughly divided into a hexagonal crystal with a layered structure of ABAB and a rhombohedral crystal with a layered structure of ABCABC. Depending on the conditions, these may be in a single structure or in a mixed state, and any crystal structure or mixed state may be used. For example, the graphite KS-6 (trade name) manufactured by Imerys GC Japan Co., Ltd. used in the examples described later has a ratio of rhombohedral crystals of 26%, and is an artificial graphite manufactured by Osaka Gas Chemicals Co., Ltd. Carbon microbeads (MCMB) have a rhombohedral ratio of 0%.
本発明の他の実施形態で用いている黒鉛は、従来のＥＤＬＣで用いられている活性炭とは静電容量の発現メカニズムが異なる。活性炭の場合には、比表面積が大きいことを活かし、その表面に電解質イオンが吸脱着することにより、静電容量を発現するものである。これに対して黒鉛の場合は、その層間において、電解質イオンであるアニオンが挿入脱離（インターカレーション－ディインターカレーション）することにより、静電容量を発現するものである。このような違いから、本実施形態に係る黒鉛を用いる蓄電デバイスは、特許文献３においては広義の意味で電気二重層キャパシタと呼んでいたが、ハイブリッドキャパシタと呼ぶことができ、電気二重層を有する活性炭を用いるＥＤＬＣと区別されるものである。 Graphite used in another embodiment of the present invention has a different capacitance development mechanism from activated carbon used in conventional EDLCs. In the case of activated carbon, by taking advantage of its large specific surface area, electrolyte ions are adsorbed and desorbed on its surface, thereby developing a capacitance. In the case of graphite, on the other hand, anions, which are electrolyte ions, are intercalated and deintercalated between the layers to develop a capacitance. Due to such a difference, the electricity storage device using graphite according to the present embodiment was called an electric double layer capacitor in a broad sense in Patent Document 3, but can be called a hybrid capacitor and has an electric double layer. It is distinguished from EDLC using activated carbon.
［正極側の集電体］
本実施形態のハイブリッドキャパシタで用いる正極側の集電体は、耐食性を向上させたアルミニウム材である非晶質炭素被膜で被覆されたアルミニウム材を用いることが好ましく、本発明の蓄電デバイス電極用集電体を用いることがより好ましい。
正極側の集電体はさらに、非晶質炭素被膜と正極活物質との間に導電性炭素層が形成されていることが好ましい。[Current collector on the positive electrode side]
The current collector on the positive electrode side used in the hybrid capacitor of the present embodiment preferably uses an aluminum material coated with an amorphous carbon film, which is an aluminum material with improved corrosion resistance. It is more preferable to use an electric body.
It is preferable that the current collector on the positive electrode side further has a conductive carbon layer formed between the amorphous carbon film and the positive electrode active material.
＜負極＞
本実施形態のハイブリッドキャパシタで用いる負極は、集電体（負極側の集電体）とその上に形成されている負極活物質層を含む。負極活物質層は、負極活物質とバインダーと導電材とを含む。
負極活物質層は主に、負極活物質、バインダー、及び、必要に応じた量の導電材を含むペースト状の負極材料を、負極側の集電体上に塗布し、乾燥して、形成することができる。<Negative Electrode>
The negative electrode used in the hybrid capacitor of this embodiment includes a current collector (a current collector on the negative electrode side) and a negative electrode active material layer formed thereon. The negative electrode active material layer includes a negative electrode active material, a binder, and a conductive material.
The negative electrode active material layer is formed by applying a paste-like negative electrode material containing a negative electrode active material, a binder, and an appropriate amount of conductive material onto the current collector on the negative electrode side and drying it. be able to.
［負極活物質］
本実施形態のハイブリッドキャパシタで用いる負極活物質は、耐電圧が高い蓄電デバイスを得るため、電解質イオンであるカチオンを吸脱着できる炭素質材料である。
負極活物質としては、電解質イオンであるカチオンを吸脱着できる材料を用いることができ、例えば、活性炭、黒鉛、ハードカーボン、及び、ソフトカーボンからなる群から選択された炭素質材料を用いることができる。[Negative electrode active material]
The negative electrode active material used in the hybrid capacitor of the present embodiment is a carbonaceous material capable of adsorbing and desorbing cations, which are electrolyte ions, in order to obtain an electricity storage device with a high withstand voltage.
As the negative electrode active material, a material that can adsorb and desorb cations, which are electrolyte ions, can be used. For example, a carbonaceous material selected from the group consisting of activated carbon, graphite, hard carbon, and soft carbon can be used. .
［負極側の集電体］
本実施形態のハイブリッドキャパシタで用いる負極側の集電体としては、公知のものを用いることができるが、非晶質炭素被膜と負極活物質との間に導電性炭素層が形成されているアルミニウム材、非晶質炭素被膜で被覆されたアルミニウム材、エッチドアルミニウム、及び、アルミニウム材からなる群から選択されたものを用いることができる。非晶質炭素被膜と負極活物質との間に導電性炭素層が形成されているアルミニウム材や非晶質炭素被膜で被覆されたアルミニウム材が好ましい。これらのアルミニウム材は耐食性を向上させたアルミニウム材である。これらのアルミニウム材を用いる場合、本発明の蓄電デバイス電極用集電体を用いることができ、ハイブリッドキャパシタを高電圧で作動させたときに、高温耐久性能を向上できる。
本実施形態のハイブリッドキャパシタは、非晶質炭素被膜と負極活物質との間に導電性炭素層が形成されているアルミニウム材や非晶質炭素被膜で被覆されたアルミニウム材を用いる場合、前述の本発明の蓄電デバイス電極用集電体を用いることが好ましい。[Current collector on the negative electrode side]
As the current collector on the negative electrode side used in the hybrid capacitor of the present embodiment, a known one can be used. material, aluminum material coated with an amorphous carbon coating, etched aluminum, and aluminum material. An aluminum material in which a conductive carbon layer is formed between the amorphous carbon coating and the negative electrode active material or an aluminum material coated with an amorphous carbon coating is preferable. These aluminum materials are aluminum materials with improved corrosion resistance. When these aluminum materials are used, the current collector for an electricity storage device electrode of the present invention can be used, and the high temperature durability performance can be improved when the hybrid capacitor is operated at a high voltage.
In the hybrid capacitor of the present embodiment, when using an aluminum material in which a conductive carbon layer is formed between an amorphous carbon film and a negative electrode active material or an aluminum material coated with an amorphous carbon film, the above-mentioned It is preferable to use the current collector for an electricity storage device electrode of the present invention.
＜バインダー＞
本実施形態のハイブリッドキャパシタで用いる電極は、さらにバインダーを含むことが好ましい。
バインダーとしては、例えば、フッ素樹脂、ゴム、アクリル系樹脂、オレフイン系樹脂、カルボキシメチルセルロース（ＣＭＣ）系樹脂、天然高分子を用いることができる。フッ素樹脂の例としては、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）が挙げられる。ゴムの例としては、フッ素ゴム、エチレンプロピレンジエンゴム、スチレンブタジエンゴムが挙げられる。天然高分子の例としては、ゼラチン、キトサン、アルギン酸が挙げられる。これらのバインダーは、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。<Binder>
It is preferable that the electrodes used in the hybrid capacitor of the present embodiment further contain a binder.
Examples of binders that can be used include fluororesins, rubbers, acrylic resins, olefin resins, carboxymethylcellulose (CMC) resins, and natural polymers. Examples of fluororesins include polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). Examples of rubber include fluororubber, ethylene propylene diene rubber, and styrene butadiene rubber. Examples of natural polymers include gelatin, chitosan and alginic acid. These binders may be used individually by 1 type, and may be used in combination of 2 or more type.
＜導電材＞
本実施形態のハイブリッドキャパシタで用いる導電材は、負極活物質層又は正極活物質層の導電性を良好にするものであれば特に限定されず、公知の導電材を用いることができる。例えば、カーボンブラック、炭素繊維を用いることができる。炭素繊維の例としては、カーボンナノチューブ（ＣＮＴ）、ＶＧＣＦ（登録商標）が挙げられる。カーボンナノチューブは、単層カーボンナノチューブであってもよいし、多層カーボンナノチューブであってもよい。これらの導電材は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。<Conductive material>
The conductive material used in the hybrid capacitor of the present embodiment is not particularly limited as long as it improves the conductivity of the negative electrode active material layer or the positive electrode active material layer, and known conductive materials can be used. For example, carbon black and carbon fiber can be used. Examples of carbon fibers include carbon nanotubes (CNT), VGCF®. The carbon nanotubes may be single-walled carbon nanotubes or multi-walled carbon nanotubes. One of these conductive materials may be used alone, or two or more thereof may be used in combination.
＜電解液＞
本実施形態のハイブリッドキャパシタで用いる電解質としては、例えば有機溶媒を用いた有機電解液を用いることができる。電解質イオンを含んでいれば、有機電解液に限らない。また、例えばゲルでもよい。電解液は、電極に吸脱着可能な電解質イオンを含む。電解質イオンは、そのイオン径ができるだけ小さいものの方が好ましい。具体的には、アンモニウム塩やホスホニウム塩、あるいはイオン液体、リチウム塩等を用いることができる。<Electrolyte>
As the electrolyte used in the hybrid capacitor of the present embodiment, for example, an organic electrolytic solution using an organic solvent can be used. As long as it contains electrolyte ions, it is not limited to the organic electrolyte. It may also be, for example, a gel. The electrolytic solution contains electrolyte ions that can be adsorbed and desorbed by the electrodes. It is preferable that the electrolyte ions have the smallest possible ion diameter. Specifically, an ammonium salt, a phosphonium salt, an ionic liquid, a lithium salt, or the like can be used.
アンモニウム塩としては、テトラエチルアンモニウム（ＴＥＡ）塩、トリエチルアンモニウム（ＴＥＭＡ）塩等を用いることができる。また、ホスホニウム塩としては、二つの五員環を持つスピロ化合物等を用いることができる。 Tetraethylammonium (TEA) salt, triethylammonium (TEMA) salt, or the like can be used as the ammonium salt. Moreover, as a phosphonium salt, a spiro compound having two five-membered rings, or the like can be used.
イオン液体としては、その種類は特に問わないが、電解質イオンを移動し易くする観点から、粘度ができる限り低く、また、導電性（導電率）が高い材料が好ましい。イオン液体を構成するカチオンとしては、例えばイミダゾリウムイオン、ピリジニウムイオン等が挙げられる。イミダゾリウムイオンとしては、例えば、１－エチル－３－メチルイミダゾリウム（１－ｅｔｈｙｌ－３－ｍｅｔｈｙｌｉｍｉｄａｚｏｌｉｕｍ）（ＥＭＩｍ）イオン、１－メチル－１－プロピルピロリジニウム（１－ｍｅｔｈｙｌ－１－ｐｒｏｐｙｌｐｙｒｒｏｌｉｄｉｎｉｕｍ）（ＭＰＰｙ）イオン、１－メチル－１－プロピルピペリジニウム（１－ｍｅｔｈｙｌ－１－ｐｒｏｐｙｌｐｉｐｅｒｉｄｉｎｉｕｍ）（ＭＰＰｉ）イオン等が挙げられる。また、リチウム塩としては四フッ化ホウ酸リチウムＬｉＢＦ４、六フッ化リン酸リチウムＬｉＰＦ６等を用いることができる。The type of ionic liquid is not particularly limited, but from the viewpoint of facilitating movement of electrolyte ions, a material having the lowest possible viscosity and high electrical conductivity (conductivity) is preferable. Examples of cations constituting the ionic liquid include imidazolium ions and pyridinium ions. Examples of imidazolium ions include, for example, 1-ethyl-3-methylimidazolium (EMIm) ion, 1-methyl-1-propylpyrrolidinium (1-methyl-1-propylpyrrolidinium) (MPPy) ion, 1-methyl-1-propylpiperidinium (MPPi) ion and the like. As the lithium salt, lithium tetrafluoroborate LiBF 4 , lithium hexafluorophosphate LiPF 6 or the like can be used.
ピリジニウムイオンとしては、例えば、１－エチルピリジニウム（１－ｅｔｈｙｌｐｙｒｉｄｉｎｉｕｍ）イオン、１－ブチルピリジニウム（１－ｂｕｔｈｙｌｐｙｒｉｄｉｎｉｕｍ）イオン等が挙げられる。 Examples of pyridinium ions include 1-ethylpyridinium ion, 1-butylpyridinium ion, and the like.
イオン液体を構成するアニオンとしては、ＢＦ４イオン、ＰＦ６イオン、［（ＣＦ３ＳＯ２）２Ｎ］イオン、ＦＳＩ（ビス（フルオロスルホニル）イミド、ｂｉｓ（ｆｌｕｏｒｏｓｕｌｆｏｎｙｌ）ｉｍｉｄｅ）イオン、ＴＦＳＩ（ビス（トリフルオロメチルスルホニル）イミド、ｂｉｓ（ｔｒｉｆｌｕｏｒｏｍｅｔｈｙｌｓｕｌｆｏｎｙｌ）ｉｍｉｄｅ）イオン等が挙げられる。Anions constituting the ionic liquid include BF 4 ion, PF 6 ion, [(CF 3 SO 2 ) 2 N] ion, FSI (bis(fluorosulfonyl)imide, bis(fluorosulfonyl)imide) ion, TFSI (bis( trifluoromethylsulfonyl)imide, bis(trifluoromethylsulfonyl)imide) ion, and the like.
溶媒としてはアセトニトリルやプロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、ジメチルスルホン、エチルイソプロピルスルホン、エチルカーボネート、フルオロエチレンカーボネート、γブチロラクトン、スルホラン、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド等を用いることができる。これらの溶媒は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Acetonitrile, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl sulfone, ethyl isopropyl sulfone, ethyl carbonate, fluoroethylene carbonate, γ-butyrolactone, sulfolane, N,N-dimethylformamide, dimethyl sulfoxide, etc. can be used as the solvent. can be done. These solvents may be used singly or in combination of two or more.
＜セパレータ＞
本実施形態のハイブリッドキャパシタで用いるセパレータとしては、正極と負極の短絡防止や電解液保液性の確保等の理由から、セルロース系の紙状セパレータや、ガラス繊維セパレータ、ポリエチレンやポリプロピレンの微多孔膜等が好適である。<Separator>
As the separator used in the hybrid capacitor of the present embodiment, for reasons such as prevention of short circuit between the positive electrode and the negative electrode and securing of electrolyte solution holding property, cellulose paper separator, glass fiber separator, polyethylene or polypropylene microporous film etc. are preferred.
以上のように、本実施形態のハイブリッドキャパシタは、本発明の非晶質炭素被膜で被覆されたアルミニウム材（本発明の蓄電デバイス電極用集電体）を、黒鉛を含む正極の側の集電体として用いる。このことにより、本実施形態のハイブリッドキャパシタは、高出力化を図り、高エネルギー密度を維持しつつ、出力特性向上を図るものである。
また、本実施形態のハイブリッドキャパシタに係るその他の実施形態のハイブリッドキャパシタは、本発明の非晶質炭素被膜で被覆されたアルミニウム材（本発明の蓄電デバイス電極用集電体）を、負極側の集電体として用いる。このことにより、本実施形態のハイブリッドキャパシタに係るその他の実施形態のハイブリッドキャパシタは、さらに高出力化を図り、高エネルギー密度を維持しつつ、出力特性をさらに向上したものである。As described above, in the hybrid capacitor of the present embodiment, the aluminum material coated with the amorphous carbon film of the present invention (the current collector for the electricity storage device electrode of the present invention) is used as a current collector on the side of the positive electrode containing graphite. used as a body. As a result, the hybrid capacitor of the present embodiment achieves higher output and improves output characteristics while maintaining high energy density.
Further, in the hybrid capacitor of another embodiment according to the hybrid capacitor of the present embodiment, the aluminum material coated with the amorphous carbon film of the present invention (the current collector for the electricity storage device electrode of the present invention) is used on the negative electrode side. Used as current collector. As a result, the hybrid capacitors of the other embodiments of the hybrid capacitors of the present embodiment achieve a higher output, maintain high energy density, and further improve the output characteristics.
本発明の非晶質炭素被膜で被覆されたアルミニウム材（本発明の蓄電デバイス電極用集電体）は、黒鉛を含む正極を有するハイブリッドキャパシタの電極用集電体として使用することが好ましい。また、本発明の非晶質炭素被膜で被覆されたアルミニウム材（本発明の蓄電デバイス電極用集電体）は、ＥＤＬＣ等の蓄電デバイスの電極用集電体としても、使用することができる。 The aluminum material coated with the amorphous carbon film of the present invention (electricity storage device electrode current collector of the present invention) is preferably used as an electrode current collector of a hybrid capacitor having a positive electrode containing graphite. In addition, the aluminum material coated with the amorphous carbon film of the present invention (electrical storage device electrode current collector of the present invention) can also be used as an electrode current collector for an electrical storage device such as EDLC.
（デュアルイオンバッテリ）
本発明の蓄電デバイスのその他の実施形態であるデュアルイオンバッテリ（ＤＩＢ）は、正極側の集電体とその上に形成された正極活物質層とを含む正極と、負極側の集電体とその上に形成された負極活物質層とを含む負極と、を有する。正極活物質は黒鉛を含み、負極活物質はカチオンを吸蔵放出し得る金属酸化物を含む。正極側の集電体及び負極側の集電体は、非晶質炭素被膜で被覆されたアルミニウム材からなる。(dual ion battery)
A dual-ion battery (DIB), which is another embodiment of the electricity storage device of the present invention, includes a positive electrode including a positive electrode-side current collector and a positive electrode active material layer formed thereon, and a negative electrode-side current collector. and a negative electrode including a negative electrode active material layer formed thereon. The positive electrode active material contains graphite, and the negative electrode active material contains a metal oxide capable of intercalating and deintercalating cations. The current collector on the positive electrode side and the current collector on the negative electrode side are made of an aluminum material coated with an amorphous carbon film.
以下、本発明の蓄電デバイスのその他の実施形態としてデュアルイオンバッテリを詳細に説明するが、前述のハイブリッドキャパシタと共通する構成については省略する。 Hereinafter, a dual-ion battery will be described in detail as another embodiment of the electricity storage device of the present invention, but the configuration common to the hybrid capacitor described above will be omitted.
本実施形態では、負極を従来の蓄電デバイスの活性炭負極から、本実施形態のデュアルイオンバッテリのリチウムを含有する金属酸化物あるいはリチウムを含有しない金属酸化物（以後、単に「ＭＯＸ」とする）としたことによって負極の充放電容量が大きくなった。リチウムを含有する金属酸化物としては、例えば、チタン酸リチウムが挙げられる。従来の蓄電デバイスにおいて負極の活性炭が律速となってエネルギー密度向上を阻んでいた課題を解決した。正極の黒鉛の容量をより使えるようにしたことによって、理論的にはエネルギー密度を高めることができたが、今度は、サイクル寿命特性が低下するという課題が現れた。この課題の原因は、負極にチタン酸リチウムなどのＭＯＸを用いると、活性炭を用いた場合の電極電位が斜めに直線状に減少変化するのに比べて、チタン酸リチウムなどのＭＯＸの電位曲線が平坦になることである。このため、負極にチタン酸リチウムなどのＭＯＸを用いた場合の電位曲線は、活性炭の電位曲線よりも、より卑な電位でさらされる時間が長くなる。これによって、本実施形態のデュアルイオンバッテリの負極側の集電体は、従来の蓄電デバイスの負極側の集電体より溶解し易くなる。この結果、高温耐久性能が低下したり、充放電サイクル寿命特性が低下したりする。この課題に対して、本実施形態の耐食性を高めた集電体を負極側の集電体に用いることで、集電体の溶解を抑制できることを見出した。すなわち、充放電容量が活性炭よりも大きな負極活物質を用いることで、セルのエネルギー密度を向上できたが、負極側の集電体が溶解する影響が顕在化した。本実施形態の耐食性を高めた集電体を適用することでその課題を解決することができる。In this embodiment, the negative electrode is changed from the activated carbon negative electrode of the conventional power storage device to the lithium-containing metal oxide or lithium-free metal oxide (hereinafter simply referred to as “MO x ”) of the dual-ion battery of this embodiment. As a result, the charge/discharge capacity of the negative electrode was increased. Examples of lithium-containing metal oxides include lithium titanate. This solves the problem of the rate-limiting activated carbon in the negative electrode of conventional electricity storage devices, which hinders improvements in energy density. Theoretically, the energy density could be increased by making more use of the capacity of the graphite in the positive electrode, but this time, the problem of deterioration in cycle life characteristics appeared. The reason for this problem is that when MOX such as lithium titanate is used for the negative electrode, the electrode potential decreases linearly obliquely when activated carbon is used. The curve is flattened. Therefore, the potential curve in the case of using MOX such as lithium titanate for the negative electrode has a longer exposure time at a less noble potential than the potential curve of activated carbon. As a result, the current collector on the negative electrode side of the dual-ion battery of the present embodiment is easier to dissolve than the current collector on the negative electrode side of the conventional power storage device. As a result, the high-temperature endurance performance deteriorates, and the charge-discharge cycle life characteristics deteriorate. In order to solve this problem, the present inventors have found that dissolution of the current collector can be suppressed by using the current collector with improved corrosion resistance according to the present embodiment as the current collector on the negative electrode side. That is, by using a negative electrode active material having a higher charge/discharge capacity than activated carbon, the energy density of the cell could be improved, but the effect of dissolution of the current collector on the negative electrode side became apparent. The problem can be solved by applying the current collector with improved corrosion resistance according to the present embodiment.
本実施形態のデュアルイオンバッテリの負極側の集電体、正極側の集電体の少なくとも１つは、前述の本発明の蓄電デバイス電極用集電体を用いることが好ましい。正極が黒鉛を含む場合、少なくとも正極側の集電体は、前述の本発明の蓄電デバイス電極用集電体を用いることが好ましい。負極側の集電体及び正極側の集電体のいずれも、前述の本発明の蓄電デバイス電極用集電体を用いることがより好ましい。 At least one of the current collector on the negative electrode side and the current collector on the positive electrode side of the dual-ion battery of the present embodiment preferably uses the current collector for an electricity storage device electrode of the present invention described above. When the positive electrode contains graphite, at least the current collector on the positive electrode side is preferably the above-described current collector for an electricity storage device electrode of the present invention. It is more preferable to use the current collector for an electricity storage device electrode of the present invention as described above for both the current collector on the negative electrode side and the current collector on the positive electrode side.
＜負極＞
本実施形態のデュアルイオンバッテリで用いる負極は、集電体（負極側の集電体）とその上に形成されている負極活物質層を含む。負極活物質層は、負極活物質とバインダーと導電材とを含む。
負極活物質層は主に、負極活物質、バインダー、及び、必要に応じた量の導電材を含むペースト状の負極材料を、負極側の集電体上に塗布し、乾燥して、形成することができる。<Negative Electrode>
The negative electrode used in the dual-ion battery of this embodiment includes a current collector (a current collector on the negative electrode side) and a negative electrode active material layer formed thereon. The negative electrode active material layer includes a negative electrode active material, a binder, and a conductive material.
The negative electrode active material layer is formed by applying a paste-like negative electrode material containing a negative electrode active material, a binder, and an appropriate amount of conductive material onto the current collector on the negative electrode side and drying it. be able to.
［負極活物質］
本実施形態のデュアルイオンバッテリの負極活物質としては、後述する電解液に含まれる電解質イオンであるカチオンを吸蔵放出し得る金属酸化物を含むものである。すなわち、カチオンを可逆的に挿入脱離できる材料であれば用いることができる。カチオンとしては、例えば、Ｌｉ、Ｎａ、Ｋ等のアルカリ金属イオン、Ｍｇ、Ｃａ等のアルカリ土類金属イオン等を用いることができる。
ここで、リチウムを用いた例を例示する。例えば、リチウムを挿入脱離できる金属酸化物を用いることができる。より具体的には、リチウムを含有する金属酸化物あるいはリチウムを含有しない金属酸化物を用いることができる。リチウムを挿入脱離できる金属酸化物の金属としては、周期律表の４、５、６周期の４、５、６族を用いることができる。具体的には、チタン（Ｔｉ）、バナジウム（Ｖ）、クロム（Ｃｒ）、ジルコニウム（Ｚｒ）、ニオブ（Ｎｂ）、モリブデン（Ｍｏ）等の遷移金属を用いることが好ましい。リチウムを含有する金属酸化物としては、例えばリチウム含有チタン酸化物であるＬｉ４Ｔｉ５Ｏ１２やリチウム含有ニオブ酸化物であるＬｉＮｂＯ２、リチウム含有バナジウム酸化物であるＬｉ１．１Ｖ０．９Ｏ２等を用いることができる。また、リチウムを含有しない金属酸化物としては、例えばＴｉＯ２、ＮｂＯ２、Ｖ２Ｏ５等を用いることができる。[Negative electrode active material]
The negative electrode active material of the dual-ion battery of the present embodiment contains a metal oxide capable of intercalating and deintercalating cations, which are electrolyte ions contained in an electrolytic solution to be described later. That is, any material can be used as long as it can reversibly insert and deintercalate cations. Examples of cations that can be used include alkali metal ions such as Li, Na and K, alkaline earth metal ions such as Mg and Ca, and the like.
Here, an example using lithium is illustrated. For example, a metal oxide that can intercalate and deintercalate lithium can be used. More specifically, a metal oxide containing lithium or a metal oxide not containing lithium can be used. As the metal of the metal oxide capable of intercalating and deintercalating lithium, metals in groups 4, 5 and 6 of periods 4, 5 and 6 of the periodic table can be used. Specifically, transition metals such as titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), and molybdenum (Mo) are preferably used. Examples of metal oxides containing lithium include Li 4 Ti 5 O 12 which is a lithium-containing titanium oxide, LiNbO 2 which is a lithium-containing niobium oxide, and Li 1.1 V 0.9 which is a lithium-containing vanadium oxide. O 2 and the like can be used. Moreover , TiO2 , NbO2 , V2O5 etc. can be used as a metal oxide which does not contain lithium, for example.
高温耐久性をより向上させる観点から、負極活物質の単位重量当たりの容量は、後述する正極活物質（黒鉛）の単位重量当たりの容量よりも高いことが好ましい。正極に用いる黒鉛の理論容量は、３７２ｍＡｈ／ｇである。しかし、リチウムイオンに比べて大きなアニオンを挿入脱離する本発明の黒鉛正極の容量は、サイクル寿命や黒鉛正極の膨張度合の観点から５０ｍＡｈ／ｇ～１００ｍＡｈ／ｇが好ましい。一方、負極に用いる活物質の理論容量は各々次のとおりである。Ｌｉ４Ｔｉ５Ｏ１２は１７５ｍＡｈ／ｇ、ＬｉＮｂＯ２は２０３ｍＡｈ／ｇ、Ｌｉ１．１Ｖ０．９Ｏ２は３１３ｍＡｈ／ｇ、ＴｉＯ２は３３５ｍＡｈ／ｇ、ＮｂＯ２は２１４ｍＡｈ／ｇ、Ｖ２Ｏ５は１４７ｍＡｈ／ｇである。これらの負極活物質を用いた負極は上記黒鉛正極とは異なり、理論容量近くまで充放電することができる。したがって、上記負極活物質の実用容量は、上記黒鉛正極の実用容量（５０ｍＡｈ／ｇ～１００ｍＡｈ／ｇ）よりも大きい。すなわち、本発明の正極活物質は、実用容量が５０ｍＡｈ／ｇ～１００ｍＡｈ／ｇである黒鉛であり、本発明の負極活物質は、その黒鉛正極の実用容量より高いことが好ましい。本発明の正極活物質は、実用容量が５０ｍＡｈ／ｇ～１００ｍＡｈ／ｇである黒鉛であることがより好ましい。本発明の負極活物質は、Ｌｉ４Ｔｉ５Ｏ１２、ＬｉＮｂＯ２、Ｌｉ１．１Ｖ０．９Ｏ２、ＴｉＯ２、ＮｂＯ２、及びＶ２Ｏ５からなる群から選択される少なくとも１種であることがより好ましい。本発明の正極活物質は、実用容量が５０ｍＡｈ／ｇ～１００ｍＡｈ／ｇである黒鉛であり、本発明の負極活物質は、Ｌｉ４Ｔｉ５Ｏ１２であることがさらに好ましい。From the viewpoint of further improving high-temperature durability, the capacity per unit weight of the negative electrode active material is preferably higher than the capacity per unit weight of the positive electrode active material (graphite) described later. The theoretical capacity of graphite used for the positive electrode is 372 mAh/g. However, the capacity of the graphite positive electrode of the present invention, which inserts and desorbs anions larger than lithium ions, is preferably 50 mAh/g to 100 mAh/g from the viewpoint of cycle life and degree of expansion of the graphite positive electrode. On the other hand, the theoretical capacities of active materials used for negative electrodes are as follows. Li4Ti5O12 is 175mAh/g, LiNbO2 is 203mAh / g , Li1.1V0.9O2 is 313mAh/g, TiO2 is 335mAh/g , NbO2 is 214mAh/g , V2O 5 is 147 mAh/g. A negative electrode using these negative electrode active materials can be charged and discharged to near the theoretical capacity, unlike the above graphite positive electrode. Therefore, the practical capacity of the negative electrode active material is larger than the practical capacity (50 mAh/g to 100 mAh/g) of the graphite positive electrode. That is, the positive electrode active material of the present invention is graphite having a practical capacity of 50 mAh/g to 100 mAh/g, and the negative electrode active material of the present invention preferably has a higher practical capacity than the graphite positive electrode. More preferably, the positive electrode active material of the present invention is graphite having a practical capacity of 50 mAh/g to 100 mAh/g. The negative electrode active material of the present invention is at least one selected from the group consisting of Li4Ti5O12 , LiNbO2 , Li1.1V0.9O2 , TiO2 , NbO2 , and V2O5 . is more preferable. More preferably, the positive electrode active material of the present invention is graphite having a practical capacity of 50 mAh/g to 100 mAh/g, and the negative electrode active material of the present invention is Li 4 Ti 5 O 12 .
［負極側の集電体］
本実施形態のデュアルイオンバッテリで用いる負極側の集電体は、非晶質炭素被膜で被覆されたアルミニウム材を用いることが好ましい。この非晶質炭素被膜で被覆されたアルミニウム材は、耐食性を向上させたアルミニウム材である。また、本実施形態のデュアルイオンバッテリで用いる負極側の集電体は、本発明の蓄電デバイス電極用集電体を用いることがより好ましい。[Current collector on the negative electrode side]
An aluminum material coated with an amorphous carbon film is preferably used for the current collector on the negative electrode side used in the dual-ion battery of the present embodiment. The aluminum material coated with this amorphous carbon film is an aluminum material with improved corrosion resistance. Further, it is more preferable to use the current collector for an electricity storage device electrode of the present invention as the current collector on the negative electrode side used in the dual-ion battery of the present embodiment.
負極側の集電体はさらに、非晶質炭素被膜と負極活物質との間に導電性炭素層が形成されていることが好ましい。 It is preferable that the current collector on the negative electrode side further has a conductive carbon layer formed between the amorphous carbon film and the negative electrode active material.
＜正極＞
本実施形態のデュアルイオンバッテリで用いる正極は、集電体（正極側の集電体）とその上に形成されている正極活物質層を含む。正極活物質層は、正極活物質とバインダーと導電材とを含む。
正極活物質層は主に、正極活物質、バインダー、及び、必要に応じた量の導電材を含むペースト状の正極材料を、正極側の集電体上に塗布し、乾燥して、形成することができる。<Positive electrode>
The positive electrode used in the dual-ion battery of this embodiment includes a current collector (positive electrode-side current collector) and a positive electrode active material layer formed thereon. The positive electrode active material layer includes a positive electrode active material, a binder, and a conductive material.
The positive electrode active material layer is formed by applying a paste-like positive electrode material containing a positive electrode active material, a binder, and an appropriate amount of conductive material onto the current collector on the positive electrode side and drying it. be able to.
［正極活物質］
本実施形態のデュアルイオンバッテリで用いる正極活物質は、耐電圧が高いデュアルイオンバッテリを得るため、電解質イオンであるアニオンを挿入脱離できる炭素質材料である黒鉛を含むものである。
黒鉛の詳細については、前述の本発明の一実施形態の蓄電デバイスであるハイブリッドキャパシタの［正極活物質］での記載のとおりである。[Positive electrode active material]
The positive electrode active material used in the dual-ion battery of the present embodiment contains graphite, which is a carbonaceous material capable of intercalating and deintercalating anions, which are electrolyte ions, in order to obtain a dual-ion battery with a high withstand voltage.
The details of graphite are as described in [Positive electrode active material] of the hybrid capacitor, which is the electricity storage device of one embodiment of the present invention.
［正極側の集電体］
本実施形態のデュアルイオンバッテリで用いる正極側の集電体は、上記負極側の集電体と同様に、非晶質炭素被膜で被覆されたアルミニウム材を用いることが好ましい。この非晶質炭素被膜で被覆されたアルミニウム材は、耐食性を向上させたアルミニウム材である。また、本実施形態のデュアルイオンバッテリで用いる正極側の集電体は、本発明の蓄電デバイス電極用集電体を用いることがより好ましい。
正極側の集電体はさらに、上記負極側の集電体と同様に、非晶質炭素被膜と正極活物質との間に導電性炭素膜が形成されていることが好ましい。[Current collector on the positive electrode side]
As for the current collector on the positive electrode side used in the dual-ion battery of the present embodiment, it is preferable to use an aluminum material coated with an amorphous carbon film, like the current collector on the negative electrode side. The aluminum material coated with this amorphous carbon film is an aluminum material with improved corrosion resistance. Further, it is more preferable to use the current collector for an electricity storage device electrode of the present invention as the current collector on the positive electrode side used in the dual-ion battery of the present embodiment.
It is preferable that the current collector on the positive electrode side further has a conductive carbon film formed between the amorphous carbon coating and the positive electrode active material, similarly to the current collector on the negative electrode side.
＜バインダー＞
本実施形態のデュアルイオンバッテリで用いる負極又は正極は、さらにバインダーを含むことが好ましい。
バインダーは、前述の本発明の一実施形態の蓄電デバイス（ハイブリッドキャパシタ）と同様な類型のものを用いることができる。<Binder>
The negative electrode or positive electrode used in the dual-ion battery of this embodiment preferably further contains a binder.
The binder can be of the same type as the electricity storage device (hybrid capacitor) of one embodiment of the present invention described above.
＜導電材＞
本実施形態のデュアルイオンバッテリで用いる導電材は、負極活物質層又は正極活物質層の導電性を良好にするものであれば特に限定されず、公知の導電材を用いることができる。例えば、前述の本発明の一実施形態の蓄電デバイス（ハイブリッドキャパシタ）と同様な類型のものを用いることができる。<Conductive material>
The conductive material used in the dual-ion battery of the present embodiment is not particularly limited as long as it improves the conductivity of the negative electrode active material layer or the positive electrode active material layer, and known conductive materials can be used. For example, the same type of storage device (hybrid capacitor) as that of one embodiment of the present invention described above can be used.
＜電解液＞
本実施形態のデュアルイオンバッテリで用いる電解液としては、例えば、有機溶媒に電解質を溶解した有機電解液を用いることができる。電解液としては、電極に挿入脱離可能な電解質イオンを含む。具体的には、リチウム塩等を用いることができる。
有機溶媒としては、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、トリフルオロプロピレンカーボネート等の環状カーボネート；ジエチルカーボネート、ジメチルカーボネート、エチルメチルカーボネート、ジプロピルカーボネート等の鎖状カーボネート等が挙げられる。これらの有機溶媒は、１種を単独で用いてもよいし、２種以上を混合して用いてもよい。
リチウム塩としては、例えば、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＮ（ＣＦ３ＳＯ２）２等が挙げられる。
また、高温耐久性能や充放電サイクル特性、入出力特性等を高めるために、電解液に添加剤を用いてもよい。<Electrolyte>
As the electrolytic solution used in the dual-ion battery of the present embodiment, for example, an organic electrolytic solution in which an electrolyte is dissolved in an organic solvent can be used. The electrolytic solution contains electrolytic ions that can be inserted into and removed from the electrodes. Specifically, a lithium salt or the like can be used.
Examples of organic solvents include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate and trifluoropropylene carbonate; chain carbonates such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate and dipropyl carbonate. These organic solvents may be used singly or in combination of two or more.
Lithium salts include, for example, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiN(CF 3 SO 2 ) 2 and the like.
Additives may also be used in the electrolytic solution in order to improve high-temperature durability, charge/discharge cycle characteristics, input/output characteristics, and the like.
＜セパレータ＞
本実施形態のデュアルイオンバッテリで用いるセパレータとしては、前述の本発明の一実施形態の蓄電デバイス（ハイブリッドキャパシタ）と同様な類型のものを用いることができる。<Separator>
As the separator used in the dual-ion battery of this embodiment, the same type of separator as that of the electricity storage device (hybrid capacitor) of one embodiment of the present invention described above can be used.
（製造例１）集電体の製造
ＤＬＣコーティングしたアルミニウム箔からなる集電体の作製
ＤＬＣコーティングしたアルミニウム箔（「ＤＬＣコートアルミニウム箔」、「ＤＬＣコートＡｌ箔」ということがある）は正極側の集電体及び負極側の集電体であり、非晶質炭素被膜で被覆されたアルミニウム材に相当する。ＤＬＣコートアルミニウム箔の製造法は以下のとおりである。純度９９．９９％のアルミニウム箔（株式会社ＵＡＣＪ製箔製、厚さ２０μｍ）に対して、アルゴンスパッタリングでアルミニウム箔表面の自然酸化膜を除去した。その後、そのアルミニウム箔表面近傍にメタン、アセチレン及び窒素の混合ガス中で放電プラズマを発生させ、アルミニウム材に負のバイアス電圧を印加することによりＤＬＣ膜を生成させた。
成膜時の雰囲気温度を２５℃にて成膜したＤＬＣコートＡｌ箔を、アルゴン雰囲気炉に移し、アルゴンフロー（５００ｍＬ／分）下で加熱処理温度である５００℃まで昇温した。その後、この温度で１時間保持した後、室温まで自然冷却させ、ＤＬＣコートＡｌ箔（Ａ）を製造した。ここで、ＤＬＣをコーティング（被覆）したアルミニウム箔上のＤＬＣ膜の厚みを、ブルカー（ＢＲＵＫＥＲ）社製触針式表面形状測定器ＤｅｋｔａｋＸＴを用いて計測したところ、１５０ｎｍであった。ＤＬＣコートＡｌ箔（Ａ）を後述のＸＡＦＳ法で測定した結果、ｓｐ２／（ｓｐ３＋ｓｐ２）比率は０．４３であった。結果を表１に示す。(Production Example 1) Production of current collector Production of current collector made of DLC-coated aluminum foil It is a current collector and a current collector on the negative electrode side, and corresponds to an aluminum material coated with an amorphous carbon film. The method for producing the DLC-coated aluminum foil is as follows. A natural oxide film on the aluminum foil surface was removed by argon sputtering on an aluminum foil with a purity of 99.99% (manufactured by UACJ Foil Corporation, thickness 20 μm). After that, discharge plasma was generated in the vicinity of the surface of the aluminum foil in a mixed gas of methane, acetylene and nitrogen, and a negative bias voltage was applied to the aluminum material to form a DLC film.
The DLC-coated Al foil formed at an atmosphere temperature of 25° C. during film formation was transferred to an argon atmosphere furnace and heated to 500° C., which is the heat treatment temperature, under an argon flow (500 mL/min). Then, after holding at this temperature for 1 hour, it was naturally cooled to room temperature to produce a DLC-coated Al foil (A). Here, the thickness of the DLC film on the DLC-coated (coated) aluminum foil was measured using a stylus surface profiler DektakXT manufactured by BRUKER, and found to be 150 nm. The sp 2 /(sp 3 +sp 2 ) ratio was 0.43 as a result of measuring the DLC-coated Al foil (A) by the XAFS method described later. Table 1 shows the results.
＜評価方法：ＸＡＦＳ法＞
ＮＥＸＡＦＳ分析は立命館大ＳＲセンターＢＬ－２超軟Ｘ線分光ラインにて実施し、スペクトルは試料電流測定による全電子収量法（ＴＥＹ：Ｔｏｔａｌ Ｅｌｅｃｔｒｏｎ Ｙｉｅｌｄ）により取得した。測定したＮＥＸＡＦＳスペクトルはＣ Ｋ－ｅｄｇｅ（２６０～３４５ｅＶ）である。スリットサイズは２５×２５μｍ、試料に対するＸ線の入射角は９０°であり、スペクトルの積算時間を各３０分とした。
エネルギー軸校正は、標準試料である高配向熱分解グラファイト（ＨＯＰＧ：Ｈｉｇｈｌｙ ｏｒｉｅｎｔｅｄ ｐｙｒｏｌｙｔｉｃ ｇｒａｐｈｉｔｅ）の文献値で行った。また、同日に測定したＨＯＰＧのスペクトルを基準にｓｐ２／（ｓｐ３＋ｓｐ２）比率を算出した。<Evaluation method: XAFS method>
The NEXAFS analysis was performed at the BL-2 ultra-soft X-ray spectroscopy line at the Ritsumeikan University SR Center, and the spectra were obtained by the Total Electron Yield (TEY) method by sample current measurement. The measured NEXAFS spectrum is C K-edge (260-345 eV). The slit size was 25×25 μm, the incident angle of X-rays to the sample was 90°, and the spectrum integration time was 30 minutes.
Energy axis calibration was performed using literature values of highly oriented pyrolytic graphite (HOPG), which is a standard sample. Also, the sp 2 /(sp 3 +sp 2 ) ratio was calculated based on the spectrum of HOPG measured on the same day.
（製造例２～５）
加熱処理温度がそれぞれ１００℃、２００℃、３００℃、４００℃であること以外は、製造例１と同様の後加熱処理方法で、ＤＬＣコートＡｌ箔（Ｂ）、ＤＬＣコートＡｌ箔（Ｃ）、ＤＬＣコートＡｌ箔（Ｄ）、ＤＬＣコートＡｌ箔（Ｅ）をそれぞれ製造した。得られたＤＬＣコートＡｌ箔に関して、製造例１と同様の方法で、ｓｐ２／（ｓｐ３＋ｓｐ２）比率を測定した。結果を表１に示す。(Production Examples 2-5)
DLC-coated Al foil (B), DLC-coated Al foil (C), A DLC-coated Al foil (D) and a DLC-coated Al foil (E) were produced. The sp 2 /(sp 3 +sp 2 ) ratio of the obtained DLC-coated Al foil was measured in the same manner as in Production Example 1. Table 1 shows the results.
（製造例６）
成膜時の雰囲気温度を２５℃にて成膜したＤＬＣコートＡｌ箔を加熱処理せず、室温まで自然冷却させた以外は製造例１と同様の方法でＤＬＣコートＡｌ箔（Ｆ）を製造した。得られたＤＬＣコートＡｌ箔に関して、製造例１と同様の方法で、ｓｐ２／（ｓｐ３＋ｓｐ２）の比率を測定した。結果を表１に示す。(Production example 6)
A DLC-coated Al foil (F) was produced in the same manner as in Production Example 1, except that the DLC-coated Al foil formed at an atmospheric temperature of 25° C. during film formation was not heat-treated and was naturally cooled to room temperature. . The ratio of sp 2 /(sp 3 +sp 2 ) was measured in the same manner as in Production Example 1 for the obtained DLC-coated Al foil. Table 1 shows the results.
（合成例１）負極活物質の合成
チタン酸リチウムの合成
平均粒径が３μｍのアナターゼ型酸化チタンと水酸化リチウムをチタンとリチウムの化学量論比が５：４モルになるように秤量した。それらをるつぼに入れ、電気式雰囲気炉に投入した。大気中８００℃で５時間焼成して、チタン酸リチウム（Ｌｉ４Ｔｉ５Ｏ１２、ＬＴＯ）が得られた。(Synthesis Example 1) Synthesis of Negative Electrode Active Material Synthesis of Lithium Titanate Anatase-type titanium oxide having an average particle size of 3 μm and lithium hydroxide were weighed so that the stoichiometric ratio of titanium to lithium was 5:4 mol. They were placed in a crucible and put into an electric atmosphere furnace. Lithium titanate (Li 4 Ti 5 O 12 , LTO) was obtained by firing at 800° C. in air for 5 hours.
「ハイブリッドキャパシタの作製」
（実施例１）
（１）蓄電デバイス電極用ペーストの調製
正極活物質としてイメリス・ジーシー・ジャパン株式会社製黒鉛（商品名：ＫＳ－６、平均粒径６μｍ）、アセチレンブラック（導電材）、ポリフッ化ビニリデン（有機溶剤系バインダー）を、重量パーセント濃度（ｗｔ％）の比率が８０：１０：１０となるように秤量した。それらをＮ－メチルピロリドン（有機溶剤）で溶解混合し、本実施例の正極用ペーストを調整した。
負極活物質として株式会社クラレ製活性炭ＹＰ－５０Ｆと、アセチレンブラック（導電材）と、カルボキシメチルセルロース（水溶液系バインダー１）と、ポリアクリル酸（水溶液系バインダー２）と、が８５ｗｔ％：５ｗｔ％：５ｗｔ％：５ｗｔ％の比率になるように秤量した。その後、それらを純水で溶解混合し、本実施例の負極用ペーストを調整した。"Fabrication of hybrid capacitors"
(Example 1)
(1) Preparation of electricity storage device electrode paste As a positive electrode active material, graphite manufactured by Imerys GC Japan Co., Ltd. (trade name: KS-6, average particle size 6 μm), acetylene black (conductive material), polyvinylidene fluoride (organic solvent) system binder) were weighed out in a weight percent concentration (wt%) ratio of 80:10:10. These were dissolved and mixed in N-methylpyrrolidone (organic solvent) to prepare the positive electrode paste of this example.
Active carbon YP-50F manufactured by Kuraray Co., Ltd. as a negative electrode active material, acetylene black (conductive material), carboxymethyl cellulose (aqueous solution binder 1), and polyacrylic acid (aqueous solution binder 2) are 85 wt%: 5 wt%: It was weighed so as to have a ratio of 5 wt%:5 wt%. After that, they were dissolved and mixed with pure water to prepare the negative electrode paste of this example.
（２）蓄電デバイス電極の作製
前記製造例１で得られたＤＬＣコートＡｌ箔（Ａ）を正極側の集電体として用い、卓上コーターを用いて、調製した正極用ペーストをその上に塗布した後、１００℃で１時間乾燥し、本実施例の正極を作製した。
マイクロメーターを用いて正極の厚みを計測したところ、６８μｍであった。
日本蓄電器工業株式会社製エッチドアルミニウム箔（厚さ２０μｍ）を負極側の集電体として用い、卓上コーターを用いて、調製した負極用ペーストをその上に塗布した後、１００℃で１時間乾燥し、本実施例の負極を作製した。
マイクロメーターを用いて負極の厚みを計測したところ、８８μｍであった。(2) Preparation of electricity storage device electrode The DLC-coated Al foil (A) obtained in Production Example 1 was used as a current collector on the positive electrode side, and the prepared positive electrode paste was applied thereon using a desktop coater. After that, it was dried at 100° C. for 1 hour to prepare the positive electrode of this example.
It was 68 micrometers when the thickness of the positive electrode was measured using the micrometer.
Using an etched aluminum foil (thickness 20 μm) manufactured by Nippon Capacitor Industry Co., Ltd. as a current collector on the negative electrode side, using a tabletop coater, apply the prepared negative electrode paste on it, and then dry at 100 ° C. for 1 hour. Then, the negative electrode of this example was produced.
When the thickness of the negative electrode was measured using a micrometer, it was 88 μm.
＜コインセル型ハイブリッドキャパシタの作製＞
次に、得られた正極を直径１６ｍｍ、得られた負極を直径１４ｍｍの円板状に打ち抜いたものを１５０℃で２４時間真空乾燥した。その後、アルゴングローブボックスへ移動した。乾燥後の正極と負極を、ニッポン高度紙工業株式会社製紙セパレータ（商品名：ＴＦ４５４０）を介して積層した。電解質に１ＭのＳＢＰ－ＢＦ４（四フッ化ホウ酸５－アゾニアスピロ［４．４］ノナン）、溶媒にＰＣ（プロピレンカーボネート）を用いた電解液０．１ｍＬを加えて、アルゴングローブボックス中で本実施例のハイブリッドキャパシタである２０３２型コインセルを作製した。
得られたハイブリッドキャパシタは、後述の評価方法で放電率特性及び放電容量改善率を評価した。結果を表２に示す。<Production of coin cell type hybrid capacitor>
Next, the obtained positive electrode was punched into a disk shape of 16 mm in diameter, and the obtained negative electrode was punched into a disk shape of 14 mm in diameter, which were vacuum-dried at 150° C. for 24 hours. After that, I moved to the argon glove box. The dried positive electrode and negative electrode were laminated via a paper separator (trade name: TF4540) manufactured by Nippon Kodoshi Kogyo Co., Ltd. 1 M SBP-BF 4 (5-azoniaspiro[4.4]nonane tetrafluoroborate) was added as the electrolyte, and 0.1 mL of the electrolyte using PC (propylene carbonate) as the solvent was added. A 2032-type coin cell, which is a hybrid capacitor of the example, was produced.
The obtained hybrid capacitor was evaluated for discharge rate characteristics and discharge capacity improvement rate by the evaluation methods described later. Table 2 shows the results.
（実施例２）
前記製造例５で得られたＤＬＣコートＡｌ箔（Ｅ）を用いたこと以外は、実施例１と同様の方法で、実施例２の正極を作製した。また、実施例２の正極を用いたこと以外は、実施例１と同様の方法でハイブリッドキャパシタを作製した。得られたハイブリッドキャパシタは、後述の評価方法で放電率特性及び放電容量改善率を評価した。結果を表２に示す。(Example 2)
A positive electrode of Example 2 was produced in the same manner as in Example 1, except that the DLC-coated Al foil (E) obtained in Production Example 5 was used. A hybrid capacitor was produced in the same manner as in Example 1, except that the positive electrode of Example 2 was used. The obtained hybrid capacitor was evaluated for discharge rate characteristics and discharge capacity improvement rate by the evaluation methods described later. Table 2 shows the results.
（比較例１）
前記製造例６で得られたＤＬＣコートＡｌ箔（Ｆ）を用いたこと以外は、実施例１と同様の方法で、比較例１の正極を作製した。また、この正極を用いたこと以外は、実施例１と同様の方法でハイブリッドキャパシタを作製した。得られたハイブリッドキャパシタは、後述の評価方法で放電率特性及び放電容量改善率を評価した。結果を表２に示す。(Comparative example 1)
A positive electrode of Comparative Example 1 was produced in the same manner as in Example 1, except that the DLC-coated Al foil (F) obtained in Production Example 6 was used. A hybrid capacitor was produced in the same manner as in Example 1, except that this positive electrode was used. The obtained hybrid capacitor was evaluated for discharge rate characteristics and discharge capacity improvement rate by the evaluation methods described later. Table 2 shows the results.
（比較例２～４）
前記製造例２～４で得られたＤＬＣコートＡｌ箔（Ｂ）、ＤＬＣコートＡｌ箔（Ｃ）、ＤＬＣコートＡｌ箔（Ｄ）をそれぞれ用いたこと以外は、実施例１と同様の方法で、比較例２～４の正極を作製した。また、この正極を用いたこと以外は、実施例１と同様の方法でハイブリッドキャパシタを作製した。得られたハイブリッドキャパシタは、後述の評価方法で放電率特性及び放電容量改善率を評価した。結果を表２に示す。(Comparative Examples 2-4)
In the same manner as in Example 1 except that the DLC-coated Al foil (B), the DLC-coated Al foil (C), and the DLC-coated Al foil (D) obtained in Production Examples 2 to 4 were used, Positive electrodes of Comparative Examples 2 to 4 were produced. A hybrid capacitor was produced in the same manner as in Example 1, except that this positive electrode was used. The obtained hybrid capacitor was evaluated for discharge rate characteristics and discharge capacity improvement rate by the evaluation methods described later. Table 2 shows the results.
「デュアルイオンバッテリの作製」
（実施例３）
＜負極の作製＞
負極活物質として合成１で得られたチタン酸リチウム（Ｌｉ４Ｔｉ５Ｏ１２、ＬＴＯ）、アセチレンブラック（導電材）、ポリフッ化ビニリデン（有機溶剤系バインダー）を、重量パーセント濃度（ｗｔ％）の比率が８０：１０：１０となるように秤量した。これらをＮ－メチルピロリドン（有機溶剤）で溶解混合することで得た負極用ペーストを、プレーンＡｌ（株式会社ＵＡＣＪ製箔製、厚さ２０μｍ）上に、ドクターブレードを用いて塗布した。その後、乾燥させ、本実施例の負極が得られた。マイクロメーターを用いて負極の厚みを計測したところ、４８μｍであった。"Fabrication of Dual Ion Battery"
(Example 3)
<Production of negative electrode>
Lithium titanate (Li 4 Ti 5 O 12 , LTO) obtained in Synthesis 1 as a negative electrode active material, acetylene black (conductive material), and polyvinylidene fluoride (organic solvent-based binder) were added at a weight percent concentration (wt%). Weighed so that the ratio was 80:10:10. A negative electrode paste obtained by dissolving and mixing these in N-methylpyrrolidone (organic solvent) was applied onto plain Al (manufactured by UACJ Foil Corporation, thickness 20 μm) using a doctor blade. After that, it was dried to obtain the negative electrode of this example. When the thickness of the negative electrode was measured using a micrometer, it was 48 μm.
＜コインセル型デュアルイオンバッテリの作製＞
作製した本実施例の負極を用い、電解液として３－ＬｉＰＦ６／ＥＭＣを用いたこと以外は、実施例１と同様の方法で、本実施例のデュアルイオンバッテリである２０３２型コインセルを作製した。得られたデュアルイオンバッテリは、後述の評価方法で放電率特性及び放電容量改善率を評価した。結果を表３に示す。<Fabrication of coin cell type dual ion battery>
A 2032-type coin cell, which is a dual-ion battery of this example, was produced in the same manner as in Example 1, except that the produced negative electrode of this example was used and 3-LiPF 6 /EMC was used as the electrolyte. . The obtained dual-ion battery was evaluated for discharge rate characteristics and discharge capacity improvement rate by the evaluation methods described later. Table 3 shows the results.
（実施例４）
負極側の集電体として製造例１で得られたＤＬＣコートＡｌ箔（Ａ）を用いたこと以外は、実施例３と同様の方法でコインセルを作製した。得られたデュアルイオンバッテリは、後述の評価方法で放電率特性及び放電容量改善率を評価した。結果を表３に示す。(Example 4)
A coin cell was produced in the same manner as in Example 3, except that the DLC-coated Al foil (A) obtained in Production Example 1 was used as the current collector on the negative electrode side. The obtained dual-ion battery was evaluated for discharge rate characteristics and discharge capacity improvement rate by the evaluation methods described later. Table 3 shows the results.
（比較例５）
比較例１と同様な正極を用いたこと以外は、実施例３と同様の方法でコインセルを作製した。得られたデュアルイオンバッテリは、後述の評価方法で放電率特性及び放電容量改善率を評価した。結果を表３に示す。(Comparative Example 5)
A coin cell was produced in the same manner as in Example 3, except that the same positive electrode as in Comparative Example 1 was used. The obtained dual-ion battery was evaluated for discharge rate characteristics and discharge capacity improvement rate by the evaluation methods described later. Table 3 shows the results.
（試験１）蓄電デバイスの評価
＜放電率特性＞
得られたセルについて、株式会社ナガノ製充放電試験装置ＢＴＳ２００４を用いて、２５℃の恒温槽中で、０．２ｍＡ／ｃｍ２あるいは１４ｍＡ／ｃｍ２の電流密度、３．５Ｖの電圧で定電流定電圧充電を行なった。その後、電流密度０．２ｍＡ／ｃｍ２の放電電流値で所定の終止電圧まで放電を行なう充放電試験を行なった。ここで、実施例１～４及び比較例１～４のハイブリッドキャパシタの場合の放電の終止電圧は０Ｖで、実施例５、６及び比較例５のデュアルイオンバッテリの場合の放電の終止電圧は２Ｖで行った。その結果として得られた０．２ｍＡ／ｃｍ２の電流密度で充放電試験を行なった場合の放電容量に対する１４ｍＡ／ｃｍ２での放電容量の比率を算出し、放電率を得た。その結果を表２と表３に示す。表２においては、実施例１、２及び比較例２、３の放電率特性の結果は、比較例１の放電率の値を１００として規格化した値を示す。例えば、比較例１の放電率がＸであり、実施例１の放電率がＹである場合、比較例１の放電率特性が１００となり、実施例１の放電率特性が１００Ｙ／Ｘとなる。表３においては、実施例３、４の放電率特性の結果は、比較例５を１００として規格化した値を示す。(Test 1) Evaluation of electricity storage device <discharge rate characteristics>
The resulting cell was subjected to constant current testing at a current density of 0.2 mA/cm 2 or 14 mA/cm 2 and a voltage of 3.5 V in a constant temperature chamber at 25° C. using a charge/discharge tester BTS2004 manufactured by Nagano Co., Ltd. Constant voltage charging was performed. After that, a charging/discharging test was conducted in which the battery was discharged to a predetermined final voltage at a discharge current value of a current density of 0.2 mA/cm 2 . Here, the final discharge voltage of the hybrid capacitors of Examples 1 to 4 and Comparative Examples 1 to 4 is 0V, and the final discharge voltage of the dual-ion batteries of Examples 5 and 6 and Comparative Example 5 is 2V. I went with As a result, the ratio of the discharge capacity at 14 mA/cm 2 to the discharge capacity when a charge/discharge test was performed at a current density of 0.2 mA/cm 2 was calculated to obtain the discharge rate. The results are shown in Tables 2 and 3. In Table 2, the results of the discharge rate characteristics of Examples 1 and 2 and Comparative Examples 2 and 3 are normalized with the value of the discharge rate of Comparative Example 1 set to 100. For example, when the discharge rate of Comparative Example 1 is X and the discharge rate of Example 1 is Y, the discharge rate characteristic of Comparative Example 1 is 100, and the discharge rate characteristic of Example 1 is 100Y/X. In Table 3, the results of the discharge rate characteristics of Examples 3 and 4 are normalized values with the value of Comparative Example 5 set to 100.
（試験２）蓄電デバイスの評価
＜放電容量改善率＞
得られたセルについて、株式会社ナガノ製充放電試験装置ＢＴＳ２００４を用いて、２５℃の恒温槽中で、０．２ｍＡ／ｃｍ２の電流密度、３．５Ｖの電圧で定電流定電圧充電を行なった。その後、電流密度０．２ｍＡ／ｃｍ２の放電電流値で所定の終止電圧まで放電を行なう充放電試験を行った。また、定電流定電圧連続充電試験前の放電容量を計測した。ここで、ハイブリッドキャパシタの場合の放電の終止電圧は０Ｖで、デュアルイオンバッテリの場合の放電の終止電圧は２Ｖで行った。
次に充放電試験装置ＢＴＳ２００４を用いて、６０℃の恒温槽中で、電流密度０．２ｍＡ／ｃｍ２、電圧３．５Ｖで連続充電試験（定電流定電圧連続充電試験）を行った。具体的には、充電の途中、所定の時間で充電を止め、セルを２５℃の恒温槽に移した後、上記と同様に０．２ｍＡ／ｃｍ２の電流密度、３．５Ｖの電圧で定電流定電圧充電を行なった。その後、電流密度０．２ｍＡ／ｃｍ２の放電電流値で所定の終止電圧まで放電を行なった。この充放電試験を５回行うことで放電容量を得た。ここで、ハイブリッドキャパシタの場合の放電の終止電圧は０Ｖで、デュアルイオンバッテリの場合の放電の終止電圧は２Ｖで行った。その後、６０℃の恒温槽に戻して連続充電試験を再開し、連続充電試験時間の総計が２０００時間になるまで試験を実施した。その際の放電容量を計測した。
放電容量改善率とは、定電流定電圧連続充電試験開始前の放電容量に対して、定電流定電圧連続充電試験後の放電容量維持率が８０％以下になった充電時間を寿命とし、比較対象の比較例での寿命になった時間を１００として規格化した値である。(Test 2) Evaluation of electricity storage device <discharge capacity improvement rate>
The resulting cell was subjected to constant-current and constant-voltage charging at a current density of 0.2 mA/cm 2 and a voltage of 3.5 V in a constant temperature bath at 25° C. using a charge/discharge tester BTS2004 manufactured by Nagano Co., Ltd. rice field. After that, a charging/discharging test was performed in which the battery was discharged to a predetermined final voltage at a discharge current value of a current density of 0.2 mA/cm 2 . Also, the discharge capacity before the constant current constant voltage continuous charge test was measured. Here, the final discharge voltage of the hybrid capacitor was 0V, and the final discharge voltage of the dual-ion battery was 2V.
Next, a continuous charge test (constant-current constant-voltage continuous charge test) was performed at a current density of 0.2 mA/cm 2 and a voltage of 3.5 V in a 60° C. constant temperature bath using a charge/discharge test apparatus BTS2004. Specifically, charging was stopped at a predetermined time during charging, the cell was transferred to a constant temperature bath at 25° C., and then the current density was 0.2 mA/cm 2 and the voltage was 3.5 V in the same manner as above. Current constant voltage charging was performed. After that, discharge was performed at a discharge current value of a current density of 0.2 mA/cm 2 to a predetermined final voltage. The discharge capacity was obtained by performing this charge/discharge test five times. Here, the final discharge voltage of the hybrid capacitor was 0V, and the final discharge voltage of the dual-ion battery was 2V. Thereafter, the battery was returned to the constant temperature bath at 60° C. and the continuous charging test was restarted until the total continuous charging test time reached 2000 hours. The discharge capacity at that time was measured.
The discharge capacity improvement rate is the charging time when the discharge capacity retention rate after the constant current and constant voltage continuous charging test is 80% or less with respect to the discharge capacity before the constant current and constant voltage continuous charging test. It is a value normalized with 100 as the time at which the life of the target comparative example is reached.
表２においては、実施例１、２及び比較例２、３の放電容量改善率の結果は、比較例１の放電容量改善率の値を１００として規格化した値を示す。表３においては、実施例３、４の放電容量改善率の結果は、比較例５の放電容量改善率を１００として規格化した値を示す。 In Table 2, the results of the discharge capacity improvement rate of Examples 1 and 2 and Comparative Examples 2 and 3 are normalized with the value of the discharge capacity improvement rate of Comparative Example 1 set to 100. In Table 3, the results of the discharge capacity improvement rate of Examples 3 and 4 show values normalized by setting the discharge capacity improvement rate of Comparative Example 5 to 100.
表２に示したとおり、本発明の蓄電デバイス電極用集電体を用いた実施例１、２は、比較例１～４に比べ、優れた放電率特性及び放電容量改善率が得られた。同様に、表３に示したとおり、本発明の蓄電デバイス電極用集電体を用いる実施例３、４は、比較例５に比べ、優れた放電率特性及び放電容量改善率が得られた。４００℃以上の温度で成膜したＤＬＣコートＡｌ箔（Ａ）、ＤＬＣコートＡｌ箔（Ｅ）、ＤＬＣコートＡｌ箔（Ｆ）、ＤＬＣコートＡｌ箔（Ｇ）は、ＸＡＦＳ法で測定したｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．３５以上を示した。そのため、黒鉛構造が発達したＤＬＣ膜であった。そのＤＬＣ膜を含む蓄電デバイス電極用集電体を、実施例１～４のハイブリッドキャパシタ及び実施例５、６のデュアルイオンバッテリ用の正極へ適用した場合、集電体と活物質層の界面抵抗が低くなり、出力特性を向上させることができたと考えられる。As shown in Table 2, in Examples 1 and 2 using the current collector for an electricity storage device electrode of the present invention, excellent discharge rate characteristics and discharge capacity improvement rate were obtained as compared with Comparative Examples 1 to 4. Similarly, as shown in Table 3, in Examples 3 and 4 using the current collector for an electricity storage device electrode of the present invention, compared to Comparative Example 5, excellent discharge rate characteristics and discharge capacity improvement rate were obtained. DLC-coated Al foil (A), DLC-coated Al foil (E), DLC-coated Al foil (F), and DLC-coated Al foil (G) formed at a temperature of 400° C. or higher have sp 2 / The (sp 3 +sp 2 ) ratio was 0.35 or more. Therefore, it was a DLC film with a developed graphite structure. When the current collector for an electricity storage device electrode containing the DLC film is applied to the positive electrodes for the hybrid capacitors of Examples 1 to 4 and the dual ion batteries of Examples 5 and 6, the interface resistance between the current collector and the active material layer It is considered that the output characteristics were improved.
実施例１の蓄電デバイスは、５００℃以上の処理温度で得られたＤＬＣコートＡｌ箔（Ａ）のｓｐ２／（ｓｐ３＋ｓｐ２）比率が０．４０以上であるため、実施例２の蓄電デバイスに比べさらに優れた特性を示したことが分かった。In the electricity storage device of Example 1, the sp 2 /(sp 3 +sp 2 ) ratio of the DLC-coated Al foil (A) obtained at a treatment temperature of 500 ° C. or higher is 0.40 or more. It was found that the characteristics were even better than those of the device.
実施例４は、負極側の集電体と正極側の集電体のいずれも本発明の蓄電デバイス電極用集電体（ＤＬＣコートＡｌ箔（Ａ）を用いる。実施例３は、正極側の集電体のみ本発明の蓄電デバイス電極用集電体（ＤＬＣコートＡｌ箔（Ａ）を用いる。実施例４は、実施例３と比較し、放電率特性は同程度であったが、放電容量改善率がさらに向上した。本発明の蓄電デバイス電極用集電体は、負極に適用しても、有効であることがわかった。 In Example 4, the current collector for an electricity storage device electrode of the present invention (DLC-coated Al foil (A) is used for both the current collector on the negative electrode side and the current collector on the positive electrode side. Only the current collector used is the current collector for the electricity storage device electrode of the present invention (DLC-coated Al foil (A). In Example 4, compared with Example 3, the discharge rate characteristics were about the same, but the discharge capacity The rate of improvement was further improved, and it was found that the current collector for an electricity storage device electrode of the present invention is effective even when applied to a negative electrode.
Claims (9)
前記アルミニウム材に形成された非晶質炭素被膜と、
を含む蓄電デバイス電極用集電体であって、
前記非晶質炭素被膜において、ｓｐ２結合炭素及びｓｐ３結合炭素の総量に対するｓｐ２結合炭素の比率（ｓｐ２／（ｓｐ３＋ｓｐ２））は０．３５以上かつ０．６以下であって、
前記比率（ｓｐ２／（ｓｐ３＋ｓｐ２））は、Ｘ線吸収微細構造（ＸＡＦＳ）法で測定したものである
ことを特徴とする蓄電デバイス電極用集電体。 an aluminum material;
an amorphous carbon coating formed on the aluminum material;
A current collector for an electrical storage device electrode comprising
In the amorphous carbon film, the ratio of sp2 - bonded carbon to the total amount of sp2-bonded carbon and sp3- bonded carbon ( sp2 /( sp3 + sp2 )) is 0.35 or more and 0.6 or less. ,
A current collector for an electric storage device electrode, wherein the ratio (sp 2 /(sp 3 +sp 2 )) is measured by an X-ray absorption fine structure (XAFS) method.
前記アルミニウム材に形成された非晶質炭素被膜と、
を含む蓄電デバイス電極用集電体であって、
前記非晶質炭素被膜において、ｓｐ２結合炭素及びｓｐ３結合炭素の総量に対するｓｐ２結合炭素の比率（ｓｐ２／（ｓｐ３＋ｓｐ２））は０．３５以上であって、
前記比率（ｓｐ２／（ｓｐ３＋ｓｐ２））は、Ｘ線吸収微細構造（ＸＡＦＳ）法で測定したものであり、
前記蓄電デバイス電極用集電体は、ハイブリッドキャパシタ正極用集電体又はデュアルイオンバッテリ正極用集電体であって、
前記ハイブリッドキャパシタ正極又はデュアルイオンバッテリ正極は、正極活物質として黒鉛を含む
ことを特徴とする蓄電デバイス電極用集電体。 an aluminum material;
an amorphous carbon coating formed on the aluminum material;
A current collector for an electrical storage device electrode comprising
In the amorphous carbon film, the ratio of sp2 - bonded carbon to the total amount of sp2 - bonded carbon and sp3- bonded carbon ( sp2 /( sp3 + sp2 )) is 0.35 or more,
The ratio (sp 2 /(sp 3 +sp 2 )) is measured by an X-ray absorption fine structure (XAFS) method,
The power storage device electrode current collector is a hybrid capacitor positive electrode current collector or a dual ion battery positive electrode current collector,
A current collector for an electricity storage device electrode, wherein the hybrid capacitor positive electrode or the dual ion battery positive electrode contains graphite as a positive electrode active material.
前記アルミニウム材に形成された非晶質炭素被膜と、
を含む蓄電デバイス電極用集電体であって、
前記非晶質炭素被膜において、ｓｐ２結合炭素及びｓｐ３結合炭素の総量に対するｓｐ２結合炭素の比率（ｓｐ２／（ｓｐ３＋ｓｐ２））は０．３５以上であって、
前記比率（ｓｐ２／（ｓｐ３＋ｓｐ２））は、Ｘ線吸収微細構造（ＸＡＦＳ）法で測定したものであり、
前記蓄電デバイス電極用集電体は、ハイブリッドキャパシタ負極用集電体又はデュアルイオンバッテリ負極用集電体であって、
前記ハイブリッドキャパシタ負極又はデュアルイオンバッテリ負極は、負極活物質として活性炭、黒鉛、ハードカーボン、ソフトカーボン、及びチタン酸リチウムからなる群から選択された１種を含む
ことを特徴とする蓄電デバイス電極用集電体。 an aluminum material;
an amorphous carbon coating formed on the aluminum material;
A current collector for an electrical storage device electrode comprising
In the amorphous carbon film, the ratio of sp2 - bonded carbon to the total amount of sp2 - bonded carbon and sp3- bonded carbon ( sp2 /( sp3 + sp2 )) is 0.35 or more,
The ratio (sp 2 /(sp 3 +sp 2 )) is measured by an X-ray absorption fine structure (XAFS) method,
The electrical storage device electrode current collector is a hybrid capacitor negative electrode current collector or a dual ion battery negative electrode current collector,
The hybrid capacitor negative electrode or the dual ion battery negative electrode contains, as a negative electrode active material, one selected from the group consisting of activated carbon, graphite, hard carbon, soft carbon, and lithium titanate. electric body.
アルミニウム材に非晶質炭素被膜を形成する成膜工程と、
前記非晶質炭素被膜を４００℃以上の温度で加熱処理する加熱処理工程と
を含む
ことを特徴とする蓄電デバイス電極用集電体の製造方法。 A method for producing the current collector for an electricity storage device electrode according to any one of claims 1 to 3,
A film forming step of forming an amorphous carbon film on an aluminum material;
and a heat treatment step of heat-treating the amorphous carbon film at a temperature of 400° C. or higher.
請求項４に記載の蓄電デバイス電極用集電体の製造方法。 The method of manufacturing a current collector for an electricity storage device electrode according to claim 4, wherein the heat treatment step is performed after the film formation step.
前記正極は正極活物質を含み、かつ、前記負極は負極活物質を含み、
前記正極活物質は、黒鉛を含み、
正極側の集電体は、請求項１に記載の蓄電デバイス電極用集電体である
ことを特徴とする蓄電デバイス。 An electricity storage device comprising at least a positive electrode, a negative electrode, and an electrolyte,
the positive electrode comprises a positive electrode active material, and the negative electrode comprises a negative electrode active material,
The positive electrode active material contains graphite,
An electricity storage device , wherein the current collector on the positive electrode side is the current collector for an electricity storage device electrode according to claim 1 .
前記正極は正極活物質を含み、かつ、前記負極は負極活物質を含み、
前記正極活物質は、黒鉛を含み、
正極側の集電体は、請求項１に記載の蓄電デバイス電極用集電体であり、
前記負極活物質は、活性炭、黒鉛、ハードカーボン、及びソフトカーボン、チタン酸リチウムからなる群から選択された１種を含み、
負極側の集電体は請求項１に記載の蓄電デバイス電極用集電体、エッチドアルミニウム、及び、アルミニウム材からなる群から選択された１種である
ことを特徴とする蓄電デバイス。 An electricity storage device comprising at least a positive electrode, a negative electrode, and an electrolyte,
the positive electrode comprises a positive electrode active material, and the negative electrode comprises a negative electrode active material,
The positive electrode active material contains graphite,
The current collector on the positive electrode side is the current collector for an electricity storage device electrode according to claim 1,
The negative electrode active material includes one selected from the group consisting of activated carbon, graphite, hard carbon, soft carbon, and lithium titanate,
The current collector on the negative electrode side is one selected from the group consisting of the current collector for an electricity storage device electrode according to claim 1 , etched aluminum, and an aluminum material.
An electricity storage device characterized by:
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