JP5058381B1 - Current collector and electrode, and power storage device using the same - Google Patents
Current collector and electrode, and power storage device using the same Download PDFInfo
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Abstract
【課題】二次電池、電気二重層キャパシタ、ハイブリッドキャパシタ等の蓄電素子の出力密度の向上ならびに急速充放電の実現、寿命特性の改善を図る。
【解決手段】金属箔１上に、金属層２と、金属層２を構成する物質とカーボンとが混在してなる混在層３と、実質的にカーボンからなるカーボン層４と、が形成されてなり、混在層３の成分が、実質的に金属層２を構成する物質のみを含む成分から実質的にカーボンのみを含む成分へと、金属層２からカーボン層４へと向かうにつれて変化するよう構成した集電体５を用いる。
【選択図】図１An object of the present invention is to improve the output density of a power storage device such as a secondary battery, an electric double layer capacitor, or a hybrid capacitor, to realize rapid charge / discharge, and to improve life characteristics.
On a metal foil, a metal layer 2, a mixed layer 3 in which a substance constituting the metal layer 2 and carbon are mixed, and a carbon layer 4 substantially made of carbon are formed. The component of the mixed layer 3 is configured to change from the component containing substantially only the substance constituting the metal layer 2 to the component containing substantially only carbon, as it goes from the metal layer 2 to the carbon layer 4. The current collector 5 is used.
[Selection] Figure 1
Description
（関連出願の記載）
本件特許出願は、同一出願人による先の特許出願（特願２０１１−０３４８０３）の関連出願である。
本発明は、集電体及び、電極、ならびに、これを用いた二次電池、電気二重層キャパシタ、ハイブリッドキャパシタなどの蓄電素子に関する。
(Description of related applications)
This patent application is a related application of the previous patent application (Japanese Patent Application No. 2011-034803) by the same applicant.
The present invention relates to a current collector, an electrode, and a storage element such as a secondary battery, an electric double layer capacitor, and a hybrid capacitor using the current collector.
近年、移動体電子機器の多機能化や、自動車及び運輸・建設機械車両の燃費改善、分散型再生可能エネルギーの普及、災害緊急時バックアップ電源の拡充などの観点から、搭載する蓄電素子の需要は増大の一途である。蓄電素子として、電気二重層キャパシタ、ハイブリッドキャパシタ、二次電池などが挙げられるが、その出力密度（Ｗ／ｋｇ、Ｗ／Ｌ）や寿命特性の更なる向上が求められている。 In recent years, the demand for power storage devices to be mounted has been increasing from the viewpoints of multifunctional mobile electronic devices, improvement in fuel efficiency of automobiles and transportation / construction machinery vehicles, widespread use of distributed renewable energy, expansion of backup power supplies for disaster emergency It is increasing. Examples of the power storage element include an electric double layer capacitor, a hybrid capacitor, a secondary battery, and the like, and further improvements in output density (W / kg, W / L) and life characteristics are required.
これらの蓄電素子を構成する電極には、ハンドリング加工強度や電気伝導性等の性能面、生産性、製造コスト等の観点から、多くの場合に、金属箔からなる集電体が用いられている。電極は集電体上に、活物質及び導電助剤、バインダーからなる電極層を形成して構成されるが、集電体と該電極層との密着性及び電気伝導性、化学安定性が不十分な場合には接触抵抗の増加により満足な出力密度が得られないため、急速な充放電が困難である。また更には、蓄電素子の充放電サイクルに伴い、経時的に集電体と電極層との界面が酸化等の化学変化により変質し、もしくは集電体から電極層が剥離するなどして、内部抵抗の増大や寿命の低下をまねくおそれがある。 In many cases, a current collector made of a metal foil is used for the electrodes constituting these power storage elements from the viewpoint of performance such as handling strength and electrical conductivity, productivity, and manufacturing cost. . An electrode is formed by forming an electrode layer composed of an active material, a conductive additive and a binder on a current collector, but the adhesion, electrical conductivity, and chemical stability between the current collector and the electrode layer are poor. If it is sufficient, a satisfactory output density cannot be obtained due to an increase in contact resistance, so that rapid charge / discharge is difficult. Furthermore, with the charge / discharge cycle of the power storage element, the interface between the current collector and the electrode layer changes over time due to chemical changes such as oxidation, or the electrode layer peels off from the current collector. There is a risk of increasing resistance and shortening the service life.
これに関連して、例えば、特許文献１には、集電体と活物質層との間にカーボン被膜層を形成した電池が記されている。 In relation to this, for example, Patent Document 1 describes a battery in which a carbon coating layer is formed between a current collector and an active material layer.
しかしながら、金属箔上に直接カーボン層を形成した場合には、金属箔とカーボン被膜層との密着性及び電気伝導性、化学安定性が充分ではないため、次第に集電体と電極層の接触抵抗が増大し、やがて出力密度の低下や内部抵抗が上昇するといった問題があり、急速な充放電が困難である。 However, when the carbon layer is formed directly on the metal foil, the contact resistance between the current collector and the electrode layer gradually increases because the adhesion, electrical conductivity, and chemical stability between the metal foil and the carbon coating layer are not sufficient. However, there is a problem that the output density is lowered and the internal resistance is increased, and rapid charge / discharge is difficult.
本発明は、このような従来技術における問題を解決し、長期に亘り内部抵抗の増大が少なく、高い出力密度を維持することで急速な充放電を可能とし、寿命特性にも優れた蓄電素子を実現するために、集電体と電極層との密着性及び電気伝導性を高めると共に、集電体と電極層との界面の化学変化による変質を抑制することを目的とするものである。 The present invention solves such a problem in the prior art, has a small increase in internal resistance over a long period of time, enables rapid charge / discharge by maintaining a high output density, and has an excellent life characteristic. In order to achieve this, the object is to improve the adhesion and electrical conductivity between the current collector and the electrode layer, and to suppress alteration due to chemical changes at the interface between the current collector and the electrode layer.
この目的を達成するために、本発明は、金属を含む基材上に、金属を含む第１の導電層と、金属を含む第１の導電層を構成する物質とグラファイトライクカーボンとが混在してなる混在層と、グラファイトライクカーボンからなる第２の導電層と、が形成されてなり、混在層の成分が、金属を含む第１の導電層を構成する物質のみを含む成分からグラファイトライクカーボンのみを含む成分へと、金属を含む第１の導電層から第２の導電層へと向かうにつれて変化するよう構成されたことを特徴とする、電極用集電体を提供する。 In order to achieve this object, according to the present invention, a first conductive layer containing a metal, a material constituting the first conductive layer containing a metal, and graphite-like carbon are mixed on a base material containing a metal. a mixture layer composed of Te, a second conductive layer made of graphite-like carbon, it is the formation, component mixed layer, graphite-like carbon from components containing only material constituting the first conductive layer including metal An electrode current collector is provided that is configured to change from a first conductive layer containing metal to a second conductive layer, to a component containing only metal.
本発明により提供される集電体においては、金属を含む基材表面とグラファイトライクカーボンからなる第２の導電層との間に、金属を含む第１の導電層、及び、両導電層の構成成分が混在する混在層が形成されているため、基材と第１の導電層との密着性、第１の導電層と第２の導電層との密着性がそれぞれ向上し、これにより、各界面の電気伝導性及び化学安定性が向上する。このような構成によれば、基材とグラファイトライクカーボンとの密着性及び界面の電気伝導性や化学安定性が不十分なために、集電体と電極層の接触抵抗が増大し、繰り返し使用するに従い、集電体の内部抵抗が上昇して電極の出力密度が低下する、といった従来技術の問題が解消される。また、第２の導電層はグラファイトライクカーボンからなるため電気伝導性及び酸化等の化学変化に対する耐性に優れている。さらに、第１の導電層と第２の導電層との境界領域において、混在層内の第１の導電層側の領域には第１の導電層を構成する物質のみが、混在層内の第２の導電層側の領域にはグラファイトライクカーボンのみが、それぞれ含まれるよう構成されているため、それら境界領域において成分が急激に変化することにより大きな界面抵抗が生じるといった問題も起こらない。 In the current collector provided by the present invention, the first conductive layer containing metal between the surface of the substrate containing metal and the second conductive layer made of graphite-like carbon, and the configuration of both conductive layers Since the mixed layer in which the components are mixed is formed, the adhesion between the base material and the first conductive layer and the adhesion between the first conductive layer and the second conductive layer are improved. The electrical conductivity and chemical stability of the interface are improved. According to such a configuration, the contact resistance between the current collector and the electrode layer is increased due to insufficient adhesion between the base material and graphite-like carbon, and electrical conductivity and chemical stability of the interface. As a result, the problems of the prior art such as an increase in the internal resistance of the current collector and a decrease in the output density of the electrode are solved. In addition, since the second conductive layer is made of graphite-like carbon, it is excellent in electrical conductivity and resistance to chemical changes such as oxidation. Further, in the boundary region between the first conductive layer and the second conductive layer, only the substance constituting the first conductive layer is present in the region on the first conductive layer side in the mixed layer. Since the region on the conductive layer side of 2 includes only graphite-like carbon, there is no problem that a large interfacial resistance is caused by abrupt change of components in the boundary region.
なお、上記記載中、「金属を含む第１の導電層を構成する物質のみを含む」とは、当該第１の導電層を構成する物質以外の成分が一切含まれないことを必ずしも意味するものではない。層内の成分純度の制御、不純物の混入に関する製造技術上の限界や、個別の製品において上記集電体に許容される誤差としての密着性や接触抵抗の程度等に応じて、混在層と各導電層との境界領域における実際の成分構成はさまざまに変わりうる。この点は、「グラファイトライクカーボンからなる」、「グラファイトライクカーボンのみを含む」などの記載、及び、後述の実施例における成分に関する全ての記述についても同様である。 In the above description, “including only the substance constituting the first conductive layer containing metal” does not necessarily mean that no components other than the substance constituting the first conductive layer are included. is not. Control of component purity within the layer, manufacturing technology limitations regarding the contamination of impurities, and the mixed layer and each resistance depending on the degree of adhesion and contact resistance as errors allowed for the current collector in individual products The actual component composition in the boundary region with the conductive layer can vary. The same applies to descriptions such as “consisting of graphite-like carbon”, “including only graphite-like carbon” , and all descriptions relating to components in Examples described later .
また、上記記載中、「混在層の成分が、金属を含む第１の導電層を構成する物質のみを含む成分からグラファイトライクカーボンのみを含む成分へと、第１の導電層から第２の導電層へと向かうにつれて変化する」とは、混在層内におけるグラファイトライクカーボンの含有率が、第１の導電層から第２の導電層へと向かう方向について単調に増加する、ということを必ずしも意味するものではない。製造技術上の限界により生じる各成分濃度のばらつき等に応じて、混在層内の各位置における実際の成分はさまざまに変わりうる。しかしながら、好ましくは、第１の導電層から第２の導電層へと向かうにつれてグラファイトライクカーボンの含有率が連続的に上昇するように、混在層が形成される。 In the above description, “the component of the mixed layer is changed from the component containing only the substance constituting the first conductive layer containing metal to the component containing only graphite-like carbon, and from the first conductive layer to the second conductive layer. “Changes toward the layer” means that the content of graphite-like carbon in the mixed layer monotonously increases in the direction from the first conductive layer to the second conductive layer. It is not a thing. The actual component at each position in the mixed layer can vary depending on the variation in the concentration of each component caused by the limitations in manufacturing technology. However, preferably, the mixed layer is formed so that the content of graphite-like carbon continuously increases from the first conductive layer to the second conductive layer.
上記第１の導電層は、Ｔａ、Ｔｉ、Ｃｒ、Ａｌ、Ｎｂ、Ｖ、Ｗ、Ｈｆ、Ｃｕと、これらの金属の窒化物とのうちいずれかを含むものであってよい。本発明の集電体を構成する第１の導電層に用いることができる物質はこれらに限られないが、金属を含む基材としてアルミニウム箔を用いる場合には、エネルギー効率やアルミニウム箔との密着性の観点から上記列挙された物質を用いることが好ましく、特にＴｉ、Ａｌを始めとする金属（基材との密着性や第１の導電層における電気伝導性を損なわない限り、合金等、複数の成分を含むものであってもよい。）を用いることが望ましい。 The first conductive layer may include one of Ta, Ti, Cr, Al, Nb, V, W, Hf, Cu, and nitrides of these metals. Although the substance which can be used for the 1st conductive layer which comprises the electrical power collector of this invention is not restricted to these, When using aluminum foil as a base material containing a metal, energy efficiency and contact | adherence with aluminum foil From the viewpoint of safety, it is preferable to use the above-listed substances, and in particular, metals such as Ti and Al (as long as the adhesion to the base material and the electrical conductivity in the first conductive layer are not impaired, a plurality of such as alloys It is desirable to use the following component.
炭素材料の中でも特に電気伝導性に優れたグラファイトライクカーボンは、蓄電素子の出力密度を高める上で、第２の導電層に用いるカーボンとして、より好ましい。また製造コストの面でも好ましい。ここで、グラファイトライクカーボンとは、ダイヤモンド結合（炭素同士のｓｐ3混成軌道結合）とグラファイト結合（炭素同士のｓｐ2混成軌道結合）の両方の結合が混在しているアモルファス構造をとるカーボンのうち、グラファイト結合の割合が過半数以上のものをいう。ただし、アモルファス構造以外に、部分的にグラファイト構造からなる結晶構造（すなわちｓｐ2混成軌道結合からなる六方晶系結晶構造）からなる相を有するものも含む。 Graphite-like carbon, particularly excellent in electrical conductivity among carbon material for increasing the output density of the electric storage device, as the carbon used for the second conductive layer, more preferably. Moreover, it is preferable also in terms of manufacturing cost. Here, graphite-like carbon is a carbon having an amorphous structure in which both diamond bonds (sp 3 hybrid orbital bonds between carbons) and graphite bonds (sp 2 hybrid orbital bonds between carbons) are mixed. In this case, the ratio of graphite bonds is more than a majority. However, in addition to the amorphous structure, those having a phase composed of a crystal structure partially composed of a graphite structure (that is, a hexagonal crystal structure composed of sp 2 hybrid orbital bonds) are also included.
金属を含む基材として用いることのできる材料は、アルミニウムに限られるわけではなく、Ｔｉ、Ｃｕ、Ｎｉ、Ｈｆ、ステンレス等、その他の任意の材料、あるいはアルミニウムにそれら任意の材料が添加されたアルミニウム合金等からなる金属箔を用いることもできる。各蓄電素子の正極電極及び負極電極に用いる集電体としての金属箔は、それぞれ、電解質と、活物質の動作電位を考慮した上で、電気化学安定性や電気伝導性、重量、加工性、製造コスト等の観点から選択される。蓄電素子が電気二重層キャパシタの場合は、正極用及び負極用共にアルミニウム箔が、ハイブリッドキャパシタ及び二次電池の場合には、正極用にアルミニウム箔、負極用にアルミニウム箔又は銅箔を供することがより好ましい。 Materials which can be used as the substrate containing metal is not limited to the aluminum, Ti, Cu, Ni, Hf, stainless steel, any other material or aluminum any material which aluminum has been added, A metal foil made of an alloy or the like can also be used. The metal foil as the current collector used for the positive electrode and the negative electrode of each power storage element, respectively, in consideration of the operating potential of the electrolyte and the active material, electrochemical stability, electrical conductivity, weight, workability, It is selected from the viewpoint of manufacturing cost. When the storage element is an electric double layer capacitor, an aluminum foil may be used for both the positive electrode and the negative electrode. When a hybrid capacitor and a secondary battery are used, an aluminum foil for the positive electrode and an aluminum foil or a copper foil for the negative electrode may be provided. More preferred.
本発明の集電体において、金属を含む基材を粗面化することは必須の要件ではないが、後述の実施例において性能試験データを用いて説明するとおり、本発明の集電体を作製するにあたっては基材を粗面化した方が、集電体と電極層との密着性や集電能力が高まるため、出力密度や寿命特性の向上に対して、より有利である。これは、金属を含む第１の導電層、混在層、及び第２の導電層に関するこれまで上述した効果に加えて、集電体と電極層との間における、物理的なアンカー効果による密着強度の向上と、両者の接触面積の増大による接触抵抗の低減効果によるところが大きい。特に、活物質がイオンの吸蔵（インターカレーション）及び放出（ディインターカレーション）による体積膨張及び収縮を繰り返すハイブリッドキャパシタと二次電池においては、基材の粗面化が、より有効である。粗面化の手段は制限しないが、基材の材料として上述のとおりアルミニウム箔や銅箔を用いる場合には、電極層とのアンカー効果による密着性向上に効果的な細孔構造を実現し易く、生産性にも優れた手法である、酸やアルカリ溶液を用いた化学的又は電気化学的エッチング等により粗面化を行うことが好ましい。なおリチウムイオンキャパシタ等のハイブリッドキャパシタやリチウムイオン二次電池等の二次電池において、アルカリ金属イオン又はアルカリ土類金属イオンを素子内の正極電極及び／又は負極電極の活物質へ万遍なく吸蔵させるプレドープ操作が必要な場合には、その製造手法の形態や生産都合に応じて、金属箔に貫通孔を施しておいてもよい。 In the current collector of the present invention, it is not an indispensable requirement to roughen the substrate containing metal, but the current collector of the present invention is produced as described using performance test data in the examples described later. In doing so, roughening the base material increases the adhesion between the current collector and the electrode layer and the current collecting ability, and is therefore more advantageous for improving the output density and life characteristics. In addition to the effects described above regarding the first conductive layer containing metal, the mixed layer, and the second conductive layer, the adhesion strength due to the physical anchor effect between the current collector and the electrode layer This is largely due to the improvement in the contact resistance and the effect of reducing the contact resistance due to the increase in the contact area between the two. In particular, in a hybrid capacitor and a secondary battery in which the active material repeatedly undergoes volume expansion and contraction due to ion storage (intercalation) and release (deintercalation), roughening the base material is more effective. The surface roughening means is not limited, but when using an aluminum foil or copper foil as the base material as described above, it is easy to realize a pore structure effective for improving the adhesion due to the anchor effect with the electrode layer. It is preferable to roughen the surface by chemical or electrochemical etching using an acid or alkali solution, which is a method with excellent productivity. In addition, in a secondary battery such as a hybrid capacitor such as a lithium ion capacitor or a lithium ion secondary battery, alkali metal ions or alkaline earth metal ions are uniformly stored in the active material of the positive electrode and / or the negative electrode in the element. When a pre-doping operation is required, through holes may be provided in the metal foil according to the form of the manufacturing method and production convenience.
なお、上記第１の導電層から第２の導電層までの、混在層を含む合計の層厚は特に制限されないが、これを、例えば４５ｎｍ以下とすれば、集電体と電極層との電子伝導距離が長くなることを防ぎ、内部抵抗の低減効果をさらに高めることができる。特に、上述のとおり金属箔に粗面化を施す場合、このように合計の膜厚が小さくなるよう集電体を作製すれば、エッチング等によって金属箔に形成した微細で緻密な細孔構造が、その上に形成される被膜で埋められることはなく、上述のアンカー効果や接触面積増大の効果を損なうこともないし、さらには、細孔構造の内壁へ万遍なく、第１，第２の導電層を形成することができる。なお、上記集電体をハイブリッドキャパシタ又は二次電池の負極電極側に用いる場合には、第２の導電層をなすカーボンそのものが、アルカリ金属イオン又はアルカリ土類金属イオンのいずれかを吸蔵及び放出可能な活物質になり得る。しかしながら、蓄電素子として充分なエネルギー密度（Ｗｈ／ｋｇ、Ｗｈ／Ｌ）を得るためには、活物質を含む電極層は少なくとも１μｍ以上の層厚を有することが要求されるが、第２の導電層を、活物質として用いるべく１μｍ程度の厚さまで形成させることは、生産性や製造コストの面等で好ましくない。好ましくは、本願発明の集電体を構成する上記第２の導電層とは別個の層として、活物質を含む電極層が形成される。 The total layer thickness including the mixed layer from the first conductive layer to the second conductive layer is not particularly limited, but if this is, for example, 45 nm or less, the electrons between the current collector and the electrode layer It is possible to prevent the conduction distance from becoming long and further enhance the effect of reducing the internal resistance. In particular, when the metal foil is roughened as described above, if the current collector is prepared so that the total film thickness is reduced in this way, the fine and dense pore structure formed in the metal foil by etching or the like is obtained. In addition, it is not filled with a film formed thereon, does not impair the above-mentioned anchor effect and the effect of increasing the contact area, and further, the first and second are uniformly distributed to the inner wall of the pore structure. A conductive layer can be formed. When the current collector is used on the negative electrode side of a hybrid capacitor or a secondary battery, the carbon that forms the second conductive layer occludes and releases either alkali metal ions or alkaline earth metal ions. It can be a possible active material. However, in order to obtain a sufficient energy density (Wh / kg, Wh / L) as a power storage element, the electrode layer containing the active material is required to have a layer thickness of at least 1 μm. Forming the layer to a thickness of about 1 μm to be used as an active material is not preferable in terms of productivity and manufacturing cost. Preferably, an electrode layer containing an active material is formed as a layer separate from the second conductive layer constituting the current collector of the present invention.
本発明は、アルカリ金属又はアルカリ土類金属のいずれかを含む遷移金属酸化物又は遷移金属リン酸化合物を含む活物質と、導電助剤と、バインダーと、からなる電極層を形成した正極電極と、アルカリ金属イオン又はアルカリ土類金属イオンのいずれかを吸蔵及び放出可能な炭素材料、Ｓｎ、Ｓｉ又は酸化ケイ素、Ｓ又は硫化物、及びチタン酸化物のいずれかを含む活物質と、導電助剤と、バインダーと、からなる電極層を形成した負極電極を備えた、例えば、リチウムイオン二次電池やナトリウムイオン二次電池、マグネシウムイオン二次電池、カルシウムイオン二次電池等の二次電池において、上述の集電体を用いたことを特徴とする電極および、当該電極を正極ならびに負極に用いた二次電池を提供する。ここで、上述の二次電池に用いる正極活物質に含まれる、アルカリ金属又はアルカリ土類金属のいずれかを含む遷移金属酸化物又は遷移金属リン酸化合物としては、例えば、ＬｉＣｏＯ2、ＬｉＭｎ2Ｏ4、ＬｉＮｉＯ2、Ｌｉ（Ｎｉ−Ｍｎ−Ｃｏ）Ｏ2、Ｌｉ（Ｎｉ−Ｃｏ−Ａｌ）Ｏ2、ＬｉＦｅＰＯ4、ＮａＣｒＯ2、ＮａＦｅＯ2、ＭｇＨｆ（ＭｏＯ4）3、Ｃａ3Ｃｏ2Ｏ6、Ｃａ3ＣｏＭｎＯ6等が挙げられる。 The present invention provides a positive electrode having an electrode layer formed of an active material containing a transition metal oxide or a transition metal phosphate compound containing either an alkali metal or an alkaline earth metal, a conductive additive, and a binder. , A carbon material that can occlude and release either alkali metal ions or alkaline earth metal ions, an active material containing any of Sn, Si or silicon oxide, S or sulfide, and titanium oxide, and a conductive additive In a secondary battery such as a lithium ion secondary battery, a sodium ion secondary battery, a magnesium ion secondary battery, a calcium ion secondary battery, or the like, provided with a negative electrode formed with an electrode layer composed of a binder. Provided are an electrode using the above-described current collector, and a secondary battery using the electrode as a positive electrode and a negative electrode. Here, as the transition metal oxide or transition metal phosphate compound containing either alkali metal or alkaline earth metal contained in the positive electrode active material used in the secondary battery described above, for example, LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , Li (Ni—Mn—Co) O 2 , Li (Ni—Co—Al) O 2 , LiFePO 4 , NaCrO 2 , NaFeO 2 , MgHf (MoO 4 ) 3 , Ca 3 Co 2 O 6 , Examples thereof include Ca 3 CoMnO 6 .
本発明は、活性炭又はカーボンナノチューブのいずれかを含む活物質と、導電助剤と、バインダーと、からなる電極層を形成した正極電極、及び同様の層構造を形成した負極電極を用いた電気二重層キャパシタにおいて、上述の集電体を用いたことを特徴とする電極、及び、当該電極を正極ならびに負極に用いた電気二重層キャパシタを提供する。 The present invention relates to an electric electrode using an active material containing either activated carbon or carbon nanotubes, a positive electrode formed with an electrode layer composed of a conductive additive and a binder, and a negative electrode formed with a similar layer structure. In a multilayer capacitor, an electrode characterized by using the above-described current collector, and an electric double layer capacitor using the electrode as a positive electrode and a negative electrode are provided.
また、本発明は、活性炭又はカーボンナノチューブのいずれかを含む活物質と、導電助剤と、バインダーと、からなる電極層を形成した正極電極と、アルカリ金属イオン又はアルカリ土類金属イオンのいずれかを吸蔵及び放出可能な炭素材料、Ｓｎ、Ｓｉ又は酸化ケイ素、Ｓ又は硫化物、及びチタン酸化物のいずれかを含む活物質と、導電助剤と、バインダーと、からなる電極層を形成した負極電極を備えた、例えば、リチウムイオンキャパシタ等のハイブリッドキャパシタにおいて、上述の集電体を用いたことを特徴とする電極及び、当該電極を正極ならびに負極に用いたハイブリッドキャパシタを提供する。 The present invention also provides a positive electrode having an electrode layer formed of an active material containing either activated carbon or carbon nanotubes, a conductive aid, and a binder, and either an alkali metal ion or an alkaline earth metal ion. Formed with an electrode layer comprising a carbon material capable of occluding and releasing carbon, an active material containing any of Sn, Si or silicon oxide, S or sulfide, and titanium oxide, a conductive auxiliary agent, and a binder In a hybrid capacitor having an electrode, for example, a lithium ion capacitor, an electrode characterized by using the above-described current collector, and a hybrid capacitor using the electrode as a positive electrode and a negative electrode are provided.
本発明の集電体においては、基材上に形成される第１及び第２の導電層間に混在層を形成することによって層間の密着性及び電気伝導性、化学安定性が向上するため、基材表面及び第１の導電層を構成する物質それぞれの酸化等の化学変化による変質が防止される。さらに、第１又は第２の導電層と混在層との境界領域において、混在層は当該第１又は第２の導電層を構成する成分のみから構成されるのであり、これにより、境界領域において電極材料の成分が急激に変化することによる界面抵抗の上昇も起こらない。このような集電体上に、活物質、導電助剤、及びバインダーからなる電極層を形成した正極電極又は負極電極は、電気伝導性が良く電極層から集電体への集電能力に優れ、且つ化学安定性にも優れており、集電体と電極層との高い密着性を長期に亘り維持する。これらの電極を用いた、二次電池、電気二重層キャパシタ、ハイブリッドキャパシタなどの蓄電素子においては、出力密度が向上すると共に充放電時の電圧降下が小さく、大電流で充放電させた際の素子の温度上昇を抑えることができるため、長時間連続的に急速充放電を行うことが可能となり、充放電サイクル寿命の大幅な延長が達成される。 In the current collector of the present invention, the formation of the mixed layer between the first and second conductive layers formed on the substrate improves the adhesion, electrical conductivity, and chemical stability between the layers. Alteration due to chemical changes such as oxidation of the materials constituting the material surface and the first conductive layer is prevented. Furthermore, in the boundary region between the first or second conductive layer and the mixed layer, the mixed layer is composed of only the components constituting the first or second conductive layer, whereby the electrode is formed in the boundary region. There is no increase in interfacial resistance due to abrupt changes in material composition. A positive electrode or negative electrode in which an electrode layer composed of an active material, a conductive additive, and a binder is formed on such a current collector has good electrical conductivity and excellent current collecting ability from the electrode layer to the current collector. Moreover, it is excellent in chemical stability, and maintains high adhesion between the current collector and the electrode layer for a long period of time. In power storage devices such as secondary batteries, electric double layer capacitors, and hybrid capacitors using these electrodes, the output density is improved and the voltage drop during charging and discharging is small, and the device is charged and discharged with a large current. Therefore, rapid charge / discharge can be performed continuously for a long time, and a significant extension of the charge / discharge cycle life can be achieved.
以下、本発明の一実施形態として、Ｔｉ又はＡｌからなる第１の導電層と、Ｔｉ又はＡｌとグラファイトライクカーボン（以下ＧＬＣと表記する場合がある）とが混在してなる混在層と、ＧＬＣからなる第２の導電層と、が粗面化したアルミニウム箔上に形成された集電体、及び、当該集電体を用いて作製したリチウムイオン二次電池について説明する。ただし、既に述べたとおり、集電体の基材として用いるアルミニウム箔、及び第１の導電層を形成するためのＴｉ又はＡｌは他の材料により代替可能であるし、また後に性能試験データを用いて説明するとおり、基材表面が粗面化されていなかったとしても、本発明の集電体は良好な特性を有する。また、既に述べたとおり、本発明の集電体の用途もリチウムイオン二次電池に限られるわけではなく、その他の二次電池、電気二重層キャパシタ、ハイブリッドキャパシタなど、任意の蓄電素子の電極用に、当該集電体を用いることができる。 Hereinafter, as one embodiment of the present invention, a first conductive layer made of Ti or Al, a mixed layer in which Ti or Al and graphite-like carbon (hereinafter sometimes referred to as GLC) are mixed, and GLC A current collector formed on a roughened aluminum foil, and a lithium ion secondary battery manufactured using the current collector will be described. However, as described above, the aluminum foil used as the current collector base material and Ti or Al for forming the first conductive layer can be replaced by other materials, and the performance test data will be used later. As described above, even if the surface of the substrate is not roughened, the current collector of the present invention has good characteristics. Further, as already described, the use of the current collector of the present invention is not limited to lithium ion secondary batteries, but for electrodes of any storage element such as other secondary batteries, electric double layer capacitors, hybrid capacitors, etc. In addition, the current collector can be used.
本発明の集電体
図１は、上記一実施形態としての集電体５の層構造を表わす断面図である。集電体５は、酸性溶液中で電気化学的なエッチング処理を行うことにより粗面化をほどこしたアルミニウム箔である、金属箔１と、当該金属箔１上に形成された、Ｔｉ又はＡｌの金属被膜からなる金属層２と、金属層２上に形成された、当該Ｔｉ又はＡｌとＧＬＣとが混在してなる混在層３と、混在層３上に形成された、ＧＬＣからなるカーボン層４と、から構成される。
Current Collector of the Present Invention FIG. 1 is a cross-sectional view showing the layer structure of a current collector 5 as one embodiment. The current collector 5 is a metal foil 1 which is an aluminum foil roughened by performing an electrochemical etching process in an acidic solution, and Ti or Al formed on the metal foil 1. A metal layer 2 made of a metal film, a mixed layer 3 formed on the metal layer 2 in which Ti or Al and GLC are mixed, and a carbon layer 4 made of GLC formed on the mixed layer 3 And.
アルミニウム箔としては、市販の高純度アルミニウム箔を用いることができる。アルミニウム箔の厚みは特に限定されないが、加工性や電気伝導性、重量、体積、コスト等に鑑みれば、５μｍ以上５０μｍ以下がより好ましい。 A commercially available high purity aluminum foil can be used as the aluminum foil. The thickness of the aluminum foil is not particularly limited, but is preferably 5 μm or more and 50 μm or less in view of workability, electrical conductivity, weight, volume, cost, and the like.
金属層２は、真空チャンバ内に金属箔１、及び蒸発源であるＴｉ又はＡｌの金属材料を配置した上で、電子ビーム及びプラズマ発生電極等によりＴｉ又はＡｌを蒸発・イオン化させ、これにより発生した金属陽イオンを当該金属箔１へと導くことにより形成される。成膜方法の一例としては、イオンプレーティング法等の物理的蒸着法（ＰＶＤ）が挙げられる。なお、金属箔１上にＴｉ又はＡｌ等の金属の窒化物からなる層を形成する態様においては、上記方法を窒素ガス等の雰囲気中で行うことによって第１の導電層を形成すればよい。 The metal layer 2 is generated by arranging the metal foil 1 in the vacuum chamber and the Ti or Al metal material that is the evaporation source, and evaporating and ionizing Ti or Al using an electron beam and a plasma generating electrode. It is formed by guiding the metal cation thus produced to the metal foil 1. As an example of the film forming method, a physical vapor deposition method (PVD) such as an ion plating method can be given. In addition, in the aspect which forms the layer which consists of metal nitrides, such as Ti or Al, on the metal foil 1, what is necessary is just to form a 1st conductive layer by performing the said method in atmosphere, such as nitrogen gas.
また、金属層２を形成するための方法として、イオンプレーティング法以外の物理的蒸着法としては、真空蒸着法やスパッタリング法等が挙げられる。熱ＣＶＤや光ＣＶＤ、プラズマＣＶＤ、有機金属気相成長法等の化学的蒸着（ＣＶＤ）法を用いてもよい。 Moreover, as a method for forming the metal layer 2, examples of the physical vapor deposition method other than the ion plating method include a vacuum vapor deposition method and a sputtering method. Chemical vapor deposition (CVD) methods such as thermal CVD, photo CVD, plasma CVD, and metal organic chemical vapor deposition may be used.
混在層３は、金属層２と同様にイオンプレーティング法等で形成することができる。すなわち、蒸発源としてはＴｉ又はＡｌの金属材料に加えてグラファイト材料を用意し、これら２つの蒸発源を同時に用いて成膜処理を行えばよい。このような混在層３を導入することにより金属とＧＬＣとの密着性及び化学安定性が高まり、金属の化学反応による変質が防止される。 The mixed layer 3 can be formed by an ion plating method or the like, similarly to the metal layer 2. That is, a graphite material may be prepared as an evaporation source in addition to a Ti or Al metal material, and film formation may be performed using these two evaporation sources simultaneously. By introducing such a mixed layer 3, adhesion between the metal and GLC and chemical stability are increased, and alteration due to the chemical reaction of the metal is prevented.
なお、混在層３は、金属層２との境界領域においてはＴｉ又はＡｌのみを含み、カーボン層４との境界領域においてはカーボン（ＧＬＣ）のみを含むように、そして、特に金属層２からカーボン層４へと向かうにつれてＧＬＣの含有率が連続的に上昇するよう構成することが好ましい。このような混在層３は、一例として、
（i）混在層３の成膜開始時には金属材料のみに電子ビームを照射してＴｉ又はＡｌのみの被膜を形成し、
（ii）時間の経過に応じて徐々に当該金属材料への電子ビーム照射量を下げ、同時にグラファイト材料への電子ビーム照射量を上げることにより、金属とＧＬＣとが混在し、且つＧＬＣの含有率が上層へ向かうにつれて上昇するような混在被膜を形成し、
（iii）成膜の終了時には金属材料への電子ビーム照射量をゼロとしてＧＬＣのみの被膜を形成する
ことにより、形成することが可能である。その他、スパッタリング法により混在層３を形成する場合には、時間の経過と共に金属ターゲットに印加する電圧を下げていき（金属ターゲットのスパッタ速度を下げていき）、グラファイトターゲットに印加する電圧を上げていく（グラファイトターゲットのスパッタ速度を上げていく）など、任意の方法によってそのような好ましい態様の混在層３を形成することができる。
The mixed layer 3 includes only Ti or Al in the boundary region with the metal layer 2, and includes only carbon (GLC) in the boundary region with the carbon layer 4. It is preferable to configure so that the content of GLC continuously increases toward the layer 4. An example of such a mixed layer 3 is as follows:
(I) At the start of film formation of the mixed layer 3, only a metal material is irradiated with an electron beam to form a film of only Ti or Al,
(Ii) By gradually decreasing the electron beam irradiation amount to the metal material as time elapses and simultaneously increasing the electron beam irradiation amount to the graphite material, the metal and GLC are mixed, and the content of GLC Forms a mixed film that rises toward the upper layer,
(Iii) At the end of the film formation, the metal material can be formed by forming a GLC-only film with an electron beam irradiation amount of zero. In addition, when the mixed layer 3 is formed by the sputtering method, the voltage applied to the metal target is lowered with time (the sputtering speed of the metal target is lowered), and the voltage applied to the graphite target is raised. The mixed layer 3 having such a preferable mode can be formed by an arbitrary method such as going up (increasing the sputtering speed of the graphite target).
なお、後述の性能試験データ中、実施例１〜４のデータは、上述のイオンプレーティング法を用いて、特に金属層２からカーボン層４へと向かうにつれて連続的にＧＬＣ含有率が上昇するよう混在層３を形成してなる集電体５、を用いて得たものである。しかしながら、混在層３において、例えばカーボン層４に向かうにつれてＧＬＣ含有率が減少する領域が一部存在していたとしても（成膜技術の限界等に起因して、このようなことは起こりうると考えられる。）、従来技術の集電体と比較しての優れた特性は同様に得られるものと推定される。そのような領域においてもＴｉ又はＡｌとＧＬＣとが混在することにより成分間の密着性が向上されているのであり、それゆえＴｉ又はＡｌの酸化等の化学反応による変質が防止され、集電体と電極層との接触抵抗が長期に亘り低く抑えられるからである。 In addition, in the performance test data described later, the data of Examples 1 to 4 seem to increase the GLC content continuously as it goes from the metal layer 2 to the carbon layer 4 using the ion plating method described above. This is obtained by using a current collector 5 formed with a mixed layer 3. However, even if there is a part of the mixed layer 3 where the GLC content decreases, for example, toward the carbon layer 4 (because of such limitations due to film formation technology limitations) It is conceivable that excellent characteristics compared to the current collector of the prior art are obtained in the same way. Even in such a region, Ti or Al and GLC are mixed to improve the adhesion between components, and therefore, alteration due to chemical reaction such as oxidation of Ti or Al is prevented, and the current collector This is because the contact resistance between the electrode layer and the electrode layer can be kept low for a long time.
カーボン層４は、金属層２及び混在層３と同様にイオンプレーティング法等で形成することができる。典型的には、上記混在層３の形成過程において金属材料への電子ビーム照射量をゼロまで低下させた後、そのままグラファイト材料のみに電子ビームを照射した状態で被膜形成処理を一定時間続行することにより、カーボン層４を形成することができる。 The carbon layer 4 can be formed by an ion plating method or the like, similarly to the metal layer 2 and the mixed layer 3. Typically, after the amount of electron beam irradiation to the metal material is reduced to zero in the formation process of the mixed layer 3, the film forming process is continued for a certain period of time while only the graphite material is irradiated with the electron beam. Thus, the carbon layer 4 can be formed.
本発明のカーボン層４は、樹脂バインダー等の結着剤へカーボン粒子を分散させた上でこれを塗布すること等により形成するのではなく、上述の金属層２及び混在層３と同様に、例えばイオンプレーティング法等の蒸着法を用いて形成することが好ましい。結着剤と混練して形成されるカーボン粒子の層においては、実質的に混ぜる結着剤の分量だけカーボンの占有率が低下し、また下層のＴｉ又はＡｌとカーボン粒子との接触が点接触となるし、さらに、上述の塗布法では界面の電気伝導性を高めることが難しく、界面抵抗が上昇すると共に密着性も悪くなり、且つ薄く均一に被覆することが困難だからである。カーボン層４は、平滑かつ緊密なＧＬＣ被膜として形成することが望ましい。 The carbon layer 4 of the present invention is not formed by dispersing the carbon particles in a binder such as a resin binder and then applying it, as in the metal layer 2 and the mixed layer 3 described above. For example, it is preferable to form using an evaporation method such as an ion plating method. In the carbon particle layer formed by kneading with the binder, the carbon occupancy decreases substantially by the amount of the binder to be mixed, and the contact between the underlying Ti or Al and the carbon particles is point contact. In addition, it is difficult to increase the electrical conductivity of the interface by the above-described coating method, the interface resistance is increased, the adhesion is deteriorated, and it is difficult to coat thinly and uniformly. The carbon layer 4 is preferably formed as a smooth and tight GLC film.
なお、金属層２、混在層３、及びカーボン層４の厚さは、それぞれ０．１ｎｍ以上１５ｎｍ以下程度で充分であり、少なくともこれら３つの層における厚さの合計が０．３ｎｍ以上であれば、集電体として良好な特性が得られる。ただし、電気伝導性や経済性に支障が無い範囲で各層をこれより厚く形成しても構わないが、金属箔を粗面化する場合には細孔構造内壁への均一な被覆性を考慮して、当該３層の厚さの合計を４５ｎｍ以下に留めることが好ましい。 The thicknesses of the metal layer 2, the mixed layer 3, and the carbon layer 4 are each about 0.1 nm or more and 15 nm or less, and at least the total thickness of these three layers is 0.3 nm or more. Good characteristics as a current collector can be obtained. However, each layer may be formed thicker as long as there is no problem in electrical conductivity and economic efficiency. However, when metal foil is roughened, it is necessary to consider uniform coverage on the inner wall of the pore structure. Thus, it is preferable to keep the total thickness of the three layers at 45 nm or less.
また、金属層２、混在層３、及びカーボン層４のそれぞれを形成する工程は同一の成膜方式で行うことが好ましい。製造工程の簡略化により生産性を高め製造コストを大幅に削減できるからである。ただし、経済性に支障の無い範囲で、これら各層を異なる方式で成膜してもよい。 Moreover, it is preferable to perform the process of forming each of the metal layer 2, the mixed layer 3, and the carbon layer 4 by the same film formation method. This is because simplification of the manufacturing process can increase productivity and greatly reduce manufacturing costs. However, these layers may be formed by different methods within a range where there is no problem in economical efficiency.
本発明の二次電池
図２は、上記集電体５（正極に用いる集電体を正極側集電体５ａとし、負極に用いる集電体を負極側集電体５ｂとする。）を用いて作製した正極電極７，負極電極９の断面図であり、図３ａ，図３ｂは、当該電極７，９を用いて作製した一例としてのリチウムイオン二次電池１６の分解図及び外観図である。リチウムイオン二次電池１６は、
（i）集電体５ａ上に、活物質としてのリン酸鉄リチウム（ＬｉＦｅＰＯ4）、導電助剤としてのアセチレンブラック、及びバインダーとしてのスチレンブタジエンゴム、増粘剤としてのカルボキシメチルセルロースアンモニウム塩、と水とを混練してなる電極層６を形成した正極電極７と、集電体５ｂ上に、活物質としてのグラファイト、導電助剤としてのアセチレンブラック、バインダーとしてのスチレンブタジエンゴム、増粘剤としてのカルボキシメチルセルロースアンモニウム塩、と水とを混練してなる電極層８を形成した負極電極９と、をセパレータを介して重ね、正極側集電体５ａに対しては正極タブ端子１２を、負極側集電体５ｂに対しては負極タブ端子１３を接続した上で、これを複数組み積み重ねて電池素子１４を作製する。
（ii）電池素子１４をケース１５に収容後、電解質１１の六フッ化リン酸リチウム（ＬｉＰＦ6）を有機溶媒のエチレンカーボネート及びジエチルカーボネートの混合溶液に溶解させた電解液を注入した後にケースを封止する。
という方法で作製した。なお、電池の作製に用いる活物質、導電助剤、バインダー、電解液の材質や組み合わせ、ならびに素子構造（コイン型、捲回型、積層型等）はこれらに限ったものではない。
FIG. 2 of the secondary battery of the present invention uses the current collector 5 (the current collector used for the positive electrode is the positive current collector 5a and the current collector used for the negative electrode is the negative current collector 5b). 3A and 3B are an exploded view and an external view of a lithium ion secondary battery 16 as an example manufactured using the electrodes 7 and 9. . The lithium ion secondary battery 16 is
(I) On the current collector 5a, lithium iron phosphate (LiFePO 4 ) as an active material, acetylene black as a conductive additive, styrene butadiene rubber as a binder, carboxymethyl cellulose ammonium salt as a thickener, and On the positive electrode 7 formed with the electrode layer 6 formed by kneading water and the current collector 5b, graphite as an active material, acetylene black as a conductive additive, styrene butadiene rubber as a binder, as a thickener A negative electrode 9 formed with an electrode layer 8 formed by kneading carboxymethylcellulose ammonium salt and water with a separator interposed therebetween, and a positive electrode tab terminal 12 is connected to the negative electrode side current collector 5a. A negative electrode tab terminal 13 is connected to the current collector 5b, and a plurality of these are stacked to produce a battery element 14. .
(Ii) After housing the battery element 14 in the case 15, the case is injected after injecting an electrolytic solution in which lithium hexafluorophosphate (LiPF 6 ) of the electrolyte 11 is dissolved in a mixed solution of ethylene carbonate and diethyl carbonate as an organic solvent. Seal.
It was produced by the method. Note that the materials and combinations of active materials, conductive assistants, binders, electrolytes, and element structures (coin type, wound type, laminated type, etc.) used for manufacturing the battery are not limited to these.
本発明の集電体の性能試験
本発明の集電体の性能試験は、上述のとおり酸性溶液中で電気化学的なエッチング処理を行うことにより粗面化をほどこしたアルミニウム箔を基材として作製した集電体と、粗面化していないアルミニウム箔を基材として作製した集電体と、のそれぞれについて行われた。それぞれの集電体において、金属層にはＴｉ又はＡｌを用い、金属層、混在層、及びカーボン層からなる被膜の厚さを合計で２５ｎｍとした。なお、評価の精確性を高める目的で、性能評価用のリチウムイオン二次電池素子としては、当該集電体上に上述の電極層を形成してなる電極を正極電極として用い、対極にはリチウム板を用いて性能試験用のコイン型電池を作製し、このコイン型電池を用いて、当該正極電極の放電レート特性、及び充放電サイクル寿命特性を測定評価した。
The performance test of the current collector of the present invention The performance test of the current collector of the present invention was produced using a roughened aluminum foil as a base material by performing an electrochemical etching treatment in an acidic solution as described above. It was performed for each of the collected current collector and the current collector prepared using a non-roughened aluminum foil as a base material. In each current collector, Ti or Al was used for the metal layer, and the total thickness of the coating composed of the metal layer, the mixed layer, and the carbon layer was 25 nm. For the purpose of improving the accuracy of evaluation, as a lithium ion secondary battery element for performance evaluation, an electrode formed by forming the above electrode layer on the current collector is used as a positive electrode, and a lithium electrode is used as a counter electrode. A coin type battery for performance test was prepared using the plate, and the discharge rate characteristic and charge / discharge cycle life characteristic of the positive electrode were measured and evaluated using this coin type battery.
正極電極の放電レート特性は、
（i）上記コイン型電池に対し、所定の充電レート電流値にて４．２Ｖまで定電流充電を行い、その後、電流値が０．０１Ｃになるまで定電圧充電を行うことで充電を実施し、
（ii）その後、特定の放電レート電流値にて３．０Ｖまで定電流放電を行うことで放電を実施する、
という充放電を１回ずつ行い、放電レート電流値０．２Ｃにおける放電容量を基準として、各放電レート電流値において測定されたコイン型電池の放電容量の割合から、容量維持率（「各放電レート電流値における放電容量［ｍＡｈ/ｇ］」÷「放電レート電流値０．２Ｃにおける放電容量［ｍＡｈ/ｇ］」×１００）を計算することにより評価された。環境温度を２５℃に設定し、上記放電レート電流値を０．２Ｃから１０Ｃまで変えつつ放電レート特性を評価し、それぞれの放電レート電流値における容量維持率を比較した。なお、上記所定の充電レート電流値は、放電レート電流値が１Ｃ未満の場合には当該放電レート電流値と同じ値とし、放電レート電流値が１Ｃ以上の場合には１Ｃに固定した。ここで、放電レート電流値１Ｃとは電池の全容量を１時間かけて放電する電流値を表し、放電レート電流値１０Ｃとは６分間で全電池容量を放電する急速放電を意味する。
The discharge rate characteristic of the positive electrode is
(I) The coin-type battery is charged by performing constant current charging up to 4.2 V at a predetermined charging rate current value, and then performing constant voltage charging until the current value reaches 0.01 C. ,
(Ii) Thereafter, discharging is performed by performing constant current discharging up to 3.0 V at a specific discharge rate current value.
Charge / discharge is performed once, and based on the discharge capacity at a discharge rate current value of 0.2 C as a reference, the capacity retention rate (“each discharge rate” It was evaluated by calculating “discharge capacity [mAh / g] at current value” ÷ “discharge capacity [mAh / g] at discharge rate current value 0.2 C” × 100). The environmental temperature was set to 25 ° C., the discharge rate characteristics were evaluated while changing the discharge rate current value from 0.2 C to 10 C, and the capacity retention rates at the respective discharge rate current values were compared. The predetermined charge rate current value was the same as the discharge rate current value when the discharge rate current value was less than 1C, and was fixed at 1C when the discharge rate current value was 1C or more. Here, the discharge rate current value 1C represents a current value that discharges the entire capacity of the battery over 1 hour, and the discharge rate current value 10C means rapid discharge that discharges the entire battery capacity in 6 minutes.
正極電極の充放電サイクル寿命特性は、環境温度を２５℃に設定し、充電レート電流値及び放電レート電流値を共に１Ｃに固定した上で、上述の充放電を２０サイクルに亘り繰り返しつつ、１サイクルが終了するたびに、初期（１サイクル目）の放電容量を基準とした容量維持率を計算することにより評価された。 The charge / discharge cycle life characteristics of the positive electrode are as follows: the ambient temperature is set to 25 ° C., the charge rate current value and the discharge rate current value are both fixed at 1 C, and the above charge / discharge cycle is repeated for 20 cycles. Each time the cycle was completed, it was evaluated by calculating a capacity retention rate based on the initial (first cycle) discharge capacity.
集電体と電極層との密着強度に対する、金属箔の粗面化の効果を検証するべく、斜め切削装置としてＳＡＩＣＡＳ（Ｓｕｒｆａｃｅ Ａｎｄ Ｉｎｔｅｒｆａｃｉａｌ Ｃｕｔｔｉｎｇ Ａｎａｌｙｓｉｓ Ｓｙｓｔｅｍ）装置を用いて試験を行った。電極表面から幅１ｍｍのダイヤモンド刃先を有する切刃を一定速度（水平：６μｍ／ｓ、垂直：０．６μｍ／ｓ）で斜めに入れ、集電体と電極層の接合界面に到達後、一定速度（水平：６μｍ／ｓ）で水平移動させた際の切刃にかかる水平応力を剥離強度として比較した。 In order to verify the effect of the roughening of the metal foil on the adhesion strength between the current collector and the electrode layer, a test was performed using a SAICAS (Surface And Interfacial Cutting Analysis System) apparatus as an oblique cutting apparatus. A cutting blade having a diamond blade edge 1 mm wide from the surface of the electrode is obliquely inserted at a constant speed (horizontal: 6 μm / s, vertical: 0.6 μm / s), and after reaching the junction interface between the current collector and the electrode layer, the constant speed The horizontal stress applied to the cutting edge when horizontally moved at (horizontal: 6 μm / s) was compared as peel strength.
比較用の測定を行った二次電池の比較例１〜７、及び本発明の二次電池である実施例１〜４において用いた集電体の構成は、それぞれ以下のとおりである。
（比較例１）
平滑アルミニウム箔からなる集電体。
（比較例２）
平滑アルミニウム箔にエッチング処理をしてなる集電体。
（比較例３）
平滑アルミニウム箔にグラファイトライクカーボン被膜を２０ｎｍ形成してなる集電体。
（比較例４）
平滑アルミニウム箔に、Ｔｉ被膜を１２．５ｎｍ、グラファイトライクカーボン被膜を１２．５ｎｍ形成してなる集電体。
（比較例５）
平滑アルミニウム箔をエッチング処理し、Ｔｉ被膜を１２．５ｎｍ、グラファイトライクカーボン被膜を１２．５ｎｍ形成してなる集電体。
（比較例６）
平滑アルミニウム箔に、Ａｌ被膜を１２．５ｎｍ、グラファイトライクカーボン被膜を１２．５ｎｍ形成してなる集電体。
（比較例７）
平滑アルミニウム箔をエッチング処理し、Ａｌ被膜を１２．５ｎｍ、グラファイトライクカーボン被膜を１２．５ｎｍ形成してなる集電体。
（実施例１）
平滑アルミニウム箔に、Ｔｉ被膜を１０ｎｍ、Ｔｉ及びグラファイトライクカーボンの混在層を５ｎｍ、グラファイトライクカーボン被膜を１０ｎｍ形成してなる集電体。
（実施例２）
平滑アルミニウム箔をエッチング処理し、Ｔｉ被膜を１０ｎｍ、Ｔｉ及びグラファイトライクカーボンの混在層を５ｎｍ、グラファイトライクカーボン被膜を１０ｎｍ形成してなる集電体。
（実施例３）
平滑アルミニウム箔に、Ａｌ被膜を１０ｎｍ、Ａｌ及びグラファイトライクカーボンの混在層を５ｎｍ、グラファイトライクカーボン被膜を１０ｎｍ形成してなる集電体。
（実施例４）
平滑アルミニウム箔をエッチング処理し、Ａｌ被膜を１０ｎｍ、Ａｌ及びグラファイトライクカーボンの混在層を５ｎｍ、グラファイトライクカーボン被膜を１０ｎｍ形成してなる集電体。
The structures of the current collectors used in Comparative Examples 1 to 7 of the secondary batteries that were measured for comparison and Examples 1 to 4 that are secondary batteries of the present invention are as follows.
(Comparative Example 1)
A current collector made of smooth aluminum foil.
(Comparative Example 2)
A current collector obtained by etching a smooth aluminum foil.
(Comparative Example 3)
A current collector formed by forming a graphite-like carbon film of 20 nm on a smooth aluminum foil.
(Comparative Example 4)
A current collector formed by forming a Ti coating on a smooth aluminum foil at 12.5 nm and a graphite-like carbon coating at 12.5 nm.
(Comparative Example 5)
A current collector obtained by etching a smooth aluminum foil to form a Ti film of 12.5 nm and a graphite-like carbon film of 12.5 nm.
(Comparative Example 6)
A current collector formed by forming an Al coating on a smooth aluminum foil at 12.5 nm and a graphite-like carbon coating at 12.5 nm.
(Comparative Example 7)
A current collector formed by etching a smooth aluminum foil to form an Al film of 12.5 nm and a graphite-like carbon film of 12.5 nm.
Example 1
A current collector formed by forming a Ti coating on a smooth aluminum foil with a thickness of 10 nm, a mixed layer of Ti and graphite-like carbon at 5 nm, and a graphite-like carbon coating at 10 nm.
(Example 2)
A current collector obtained by etching a smooth aluminum foil to form a Ti film having a thickness of 10 nm, a mixed layer of Ti and graphite-like carbon having a thickness of 5 nm, and a graphite-like carbon film having a thickness of 10 nm.
(Example 3)
A current collector obtained by forming an Al coating on a smooth aluminum foil with a thickness of 10 nm, a mixed layer of Al and graphite-like carbon at 5 nm, and a graphite-like carbon coating at 10 nm.
Example 4
A current collector obtained by etching a smooth aluminum foil to form an Al film of 10 nm, a mixed layer of Al and graphite-like carbon of 5 nm, and a graphite-like carbon film of 10 nm.
なお、金属箔上への被膜形成は、全て上述のイオンプレーティング法により行った。 In addition, all the film formation on metal foil was performed by the above-mentioned ion plating method.
各比較例、及び実施例についての放電レート特性の試験結果を、表１〜表１１に示す。また、各比較例、実施例について、放電レート電流値ごとに決定された容量維持率を、図４にグラフとして示す。 Tables 1 to 11 show the discharge rate characteristics test results for each of the comparative examples and examples. Moreover, about each comparative example and an Example, the capacity | capacitance maintenance factor determined for every discharge rate electric current value is shown as a graph in FIG.
図４を見れば、比較例１〜７の集電体を用いた場合の放電レート特性に較べて、本発明の集電体を用いた実施例１〜４の放電レート特性の向上は明らかである。 4, the improvement in the discharge rate characteristics of Examples 1 to 4 using the current collector of the present invention is clearer than the discharge rate characteristics when the current collectors of Comparative Examples 1 to 7 are used. is there.
さらに、充放電サイクル寿命特性の試験結果として、比較例１〜７、実施例１〜４の各々について充放電の１サイクルが終了するたびに決定された容量維持率を表１２〜表１３に示し、さらにグラフとして図５に示す。 Furthermore, as a test result of the charge / discharge cycle life characteristics, Tables 12 to 13 show capacity maintenance rates determined each time one charge / discharge cycle is completed for each of Comparative Examples 1 to 7 and Examples 1 to 4. Furthermore, it shows in FIG. 5 as a graph.
図５において、サイクル数の増加に伴い容量維持率の低下が生じる比較例１〜７の集電体を用いた場合の充放電サイクル寿命特性に較べて、本発明の集電体を用いた実施例１〜４では、何れも２０サイクル目まで容量の低下が全く起こらず、充放電サイクル寿命特性の向上は明らかである。 In FIG. 5, compared with the charge / discharge cycle life characteristics when using the current collectors of Comparative Examples 1 to 7 in which the capacity retention ratio decreases as the number of cycles increases, the implementation using the current collector of the present invention was performed. In Examples 1 to 4, the capacity does not decrease at all until the 20th cycle, and the charge / discharge cycle life characteristics are clearly improved.
比較例１及び２、実施例１及び２について、集電体と電極層との密着強度に対する金属箔の粗面化の効果を評価したＳＡＩＣＡＳ試験の結果を、図６に示す。被膜形成の有無に関わらず、電極層間の密着強度に関して金属箔の粗面化の効果は明らかである。 FIG. 6 shows the results of the SAICAS test in which the effects of roughening the metal foil on the adhesion strength between the current collector and the electrode layer were evaluated for Comparative Examples 1 and 2 and Examples 1 and 2. Regardless of whether or not a film is formed, the effect of roughening the metal foil is clear with respect to the adhesion strength between the electrode layers.
以上のとおり、本発明の集電体を用いて作製された電極においては、高放電レートでの使用、及び多数回の繰り返し使用による品質の劣化が極めて小さいことが示された。このような効果は、本発明の集電体が既に述べたとおりの被膜構成を有することにより、界面における高い電気伝導性、及び化学安定性を得たために生じたと考えられる。本発明の被膜構成に起因する電気伝導性及び化学安定性の向上は、集電体の具体的用途に左右されないことが明らかであり、これに鑑みれば、本発明の集電体をリチウムイオン二次電池の負極電極側に用いた時、あるいは、電気二重層キャパシタやハイブリッドキャパシタなどの正極電極側、負極電極側に用いた時にも、同様に品質劣化が抑えられると推定される。 As described above, it has been shown that the electrode manufactured using the current collector of the present invention has very little deterioration in quality due to use at a high discharge rate and repeated use many times. Such an effect is considered to be caused by the fact that the current collector of the present invention has the film configuration as described above, thereby obtaining high electrical conductivity and chemical stability at the interface. It is clear that the improvement in electrical conductivity and chemical stability resulting from the coating composition of the present invention does not depend on the specific application of the current collector. When used on the negative electrode side of a secondary battery, or when used on the positive electrode side or the negative electrode side of an electric double layer capacitor or a hybrid capacitor, it is presumed that quality deterioration can be similarly suppressed.
本発明の集電体は、二次電池、電気二重層キャパシタ、ハイブリッドキャパシタの電極として利用することができる。さらに、本発明の集電体は、電解質を用いて駆動する太陽電池等でも用いることができる。 The current collector of the present invention can be used as an electrode of a secondary battery, an electric double layer capacitor, or a hybrid capacitor. Furthermore, the current collector of the present invention can also be used in a solar cell driven using an electrolyte.
１ 金属箔
２ 金属層
３ 混在層
４ カーボン層
５ 集電体（５ａ 正極側集電体、 ５ｂ 負極側集電体）
６ 正極電極層
７ 正極電極
８ 負極電極層
９ 負極電極
１０ セパレータ
１１ 電解質
１２ 正極端子
１３ 負極端子
１４ リチウムイオン二次電池素子
１５ 電池ケース
１６ リチウムイオン二次電池
DESCRIPTION OF SYMBOLS 1 Metal foil 2 Metal layer 3 Mixed layer 4 Carbon layer 5 Current collector (5a Positive electrode side current collector, 5b Negative electrode side current collector)
6 positive electrode layer 7 positive electrode 8 negative electrode layer 9 negative electrode 10 separator 11 electrolyte 12 positive electrode terminal 13 negative electrode terminal 14 lithium ion secondary battery element 15 battery case 16 lithium ion secondary battery
Claims (12)
前記混在層の成分が、前記金属を含む第１の導電層を構成する物質のみを含む成分からグラファイトライクカーボンのみを含む成分へと、前記金属を含む第１の導電層から前記第２の導電層へと向かうにつれて変化するよう構成されたことを特徴とする、電極用集電体。 A first conductive layer containing a metal, a mixed layer in which a substance constituting the first conductive layer containing the metal and graphite-like carbon are mixed, and graphite-like carbon; A second conductive layer is formed,
The component of the mixed layer is changed from a component containing only the substance constituting the first conductive layer containing the metal to a component containing only the graphite-like carbon, and from the first conductive layer containing the metal to the second conductive layer. A current collector for an electrode, wherein the current collector is configured to change as it goes to a layer.
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012026631A JP5058381B1 (en) | 2012-02-09 | 2012-02-09 | Current collector and electrode, and power storage device using the same |
| KR1020137022863A KR101946658B1 (en) | 2011-02-21 | 2012-02-20 | Electrode foil, current collector, electrode, and electric energy storage element using same |
| US14/000,599 US9418796B2 (en) | 2011-02-21 | 2012-02-20 | Electrode foil, current collector, electrode, and electric energy storage element using same |
| RU2013142759/07A RU2573387C2 (en) | 2011-02-21 | 2012-02-20 | Electrode foil, current tap, electrode and element for electric energy accumulation with their usage |
| CA2827919A CA2827919C (en) | 2011-02-21 | 2012-02-20 | Electrode foil, current collector, electrode, and electric energy storage element using same |
| TW105136251A TWI611443B (en) | 2011-02-21 | 2012-02-20 | Current collector for electrode, positive electrode for non-aqueous electrolytic secondary battery, negative electrode for non-aqueous electrolytic secondary battery, non-aqueous electrolytic secondary battery, electrode for non-aqueous electrolytic elec |
| EP12749545.5A EP2680286B1 (en) | 2011-02-21 | 2012-02-20 | Electrode foil, current collector, electrode, and electric energy storage element using same |
| BR112013021247-0A BR112013021247B1 (en) | 2011-02-21 | 2012-02-20 | ELECTRODE MATERIAL, SOLID ELECTROLYTIC CAPACITOR, CATHODE SHEET FOR USE IN A SOLID ELECTROLYTIC CAPACITOR, CURRENT COLLECTOR FOR AN ELECTRODE, POSITIVE AND NEGATIVE ELECTROLYTIC SECONDARY BATTERY NON-AQUOUS ELECTROLYTIC AND NON-CABORATIC ELECTROLYTIC SECONDARY BATTERY AQUEOUS, ELECTRODE FOR A NON-AQUEOUS DOUBLE ELECTROLYTIC ELECTRIC LAYER CAPACITOR, NON-AQUEOUS DOUBLE ELECTROLYTIC ELECTRIC LAYER CAPACITOR, AND NON-AQUEOUS ELECTROLYTIC HYBRID CAPACITOR |
| HUE12749545A HUE045264T2 (en) | 2011-02-21 | 2012-02-20 | Electrode foil, current collector, electrode, and electric energy storage element using same |
| CN201280009644.6A CN103380469B (en) | 2011-02-21 | 2012-02-20 | Electrode foil, collector, electrode and the storage assembly using these objects |
| AU2012221308A AU2012221308B2 (en) | 2011-02-21 | 2012-02-20 | Electrode foil, current collector, electrode, and energy storage element using same |
| PCT/JP2012/054000 WO2012115050A1 (en) | 2011-02-21 | 2012-02-20 | Electrode foil, current collector, electrode, and energy storage element using same |
| CN201710585330.5A CN107403697B (en) | 2011-02-21 | 2012-02-20 | Electrode foil, collector, electrode and the storage assembly using these objects |
| TW101105414A TWI573157B (en) | 2011-02-21 | 2012-02-20 | Electrode material, solid electrolytic capacitor and cathode foil |
| AU2016277576A AU2016277576B2 (en) | 2011-02-21 | 2016-12-20 | Electrode foil, current collector, electrode, and energy storage element using same |
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| JP2012026631A JP5058381B1 (en) | 2012-02-09 | 2012-02-09 | Current collector and electrode, and power storage device using the same |
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| JP2012129507A Division JP2013165250A (en) | 2012-06-07 | 2012-06-07 | Collector and electrode, and power storage element using the same |
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| WO2014069640A1 (en) * | 2012-11-01 | 2014-05-08 | スペースリンク株式会社 | Carbon nanotube film capacitor |
| EP2989648B1 (en) * | 2013-04-24 | 2017-05-17 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Electrochemical device like supercapacitor with an electrolyte comprising, as conductive salt, at least one alcaline salt other than lithium |
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| WO2015146079A1 (en) * | 2014-03-25 | 2015-10-01 | 三洋電機株式会社 | Negative electrode plate for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
| CN110214386B (en) * | 2017-01-31 | 2022-05-31 | 松下知识产权经营株式会社 | Electrochemical device |
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| EP2989648B1 (en) * | 2013-04-24 | 2017-05-17 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Electrochemical device like supercapacitor with an electrolyte comprising, as conductive salt, at least one alcaline salt other than lithium |
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| JP2013164939A (en) | 2013-08-22 |
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