JP2010244911A - Electrode cell and lithium ion secondary battery - Google Patents

Electrode cell and lithium ion secondary battery Download PDF

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JP2010244911A
JP2010244911A JP2009093547A JP2009093547A JP2010244911A JP 2010244911 A JP2010244911 A JP 2010244911A JP 2009093547 A JP2009093547 A JP 2009093547A JP 2009093547 A JP2009093547 A JP 2009093547A JP 2010244911 A JP2010244911 A JP 2010244911A
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voids
thin film
electrode cell
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lithium ion
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Hiroki Nakamura
博樹 中村
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Mitsubishi Rayon Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode cell high in safety in which high-speed charging and discharging are possible and risk of ignition or the like is reduced, and a lithium ion secondary battery using this. <P>SOLUTION: The electrode cell and the lithium ion secondary battery using this are provided in which the surface of a carbon material thin film having voids is covered by an electrolyte, and the positive electrode active material is filled into these voids. It is preferable that the carbon material thin film having the voids is a nonwoven fabric obtained by laminating carbon fibers. By this, the electrode cell is obtained in which a negative electrode material and a positive electrode material are adjacent and of which the surface area is large, and the high-speed charging and discharging become possible. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、電極セル及び電極セルを用いたリチウムイオン二次電池に関する。   The present invention relates to an electrode cell and a lithium ion secondary battery using the electrode cell.

近年、携帯情報端末、携帯電子機器、家庭用小型電量貯蔵装置、電気自動車、ハイブリッド電気自動車等に用いられるリチウムイオン二次電池の需要が増加している。
リチウムイオン二次電池の負極材としては、一般に、リチウムイオンのドーピング・脱ドーピングが可能な天然黒鉛粒子、コークスやピッチ等を黒鉛化した人造黒鉛粒子等の炭素材料が用いられている。 In recent years, there has been an increasing demand for lithium ion secondary batteries used in portable information terminals, portable electronic devices, small household energy storage devices, electric vehicles, hybrid electric vehicles, and the like.
As a negative electrode material for a lithium ion secondary battery, carbon materials such as natural graphite particles capable of doping / dedoping lithium ions and artificial graphite particles graphitized from coke and pitch are generally used.

電解質に対する化学的安定性、ドーピングに伴う体積膨張に対する構造安定性、繰り返し充放電特性等に優れることから、炭素繊維又は炭素繊維構造体等の炭素材料も提案されている（特許文献１〜３）。
しかしながら、特許文献１〜３に提案された炭素材料を用いたリチウムイオン二次電池は、電解質としてエチレンカーボネート、プロピレンカーボネート等の有機溶媒を用いるため発火等の危険性があり、更なる改善が求められている。 Carbon materials such as carbon fibers or carbon fiber structures have also been proposed because of their excellent chemical stability to electrolytes, structural stability against volume expansion accompanying doping, and repeated charge / discharge characteristics (Patent Documents 1 to 3). .
However, since the lithium ion secondary battery using the carbon material proposed in Patent Documents 1 to 3 uses an organic solvent such as ethylene carbonate and propylene carbonate as an electrolyte, there is a risk of ignition and further improvement is required. It has been.

発火等の危険性を低減するため、電解質に固体電解質を用いるリチウムイオン二次電池が提案されている（特許文献４）。
固体電解質を用いるリチウムイオン二次電池は、有機溶媒を用いないことから発火等の危険性は低減するが、電解質のイオン伝導度が充分ではないため、充放電等の電池特性を向上する必要がある。 In order to reduce the risk of ignition and the like, a lithium ion secondary battery using a solid electrolyte as an electrolyte has been proposed (Patent Document 4).
Lithium ion secondary batteries using solid electrolytes reduce the risk of ignition and the like because they do not use organic solvents, but the ionic conductivity of the electrolyte is not sufficient, so it is necessary to improve battery characteristics such as charge and discharge is there.

特開昭６０−３６３１５号公報JP 60-36315 A 特開平７−６７５４号公報Japanese Patent Laid-Open No. 7-6754 特開平８−１０２３１５号公報JP-A-8-102315 特開平２−２３０６６７号公報JP-A-2-230667

本発明の目的は、高速充放電することが可能で、且つ発火等の危険性が低減された、安全性の高い電極セル及びこれを用いたリチウムイオン二次電池を提供することである。   An object of the present invention is to provide a highly safe electrode cell capable of high-speed charge / discharge and reduced risk of ignition and the like, and a lithium ion secondary battery using the same.

本発明は、空隙を有する炭素材料薄膜の表面が電解質によって被覆され、その空隙内に正極活物質が充填された電極セルを要旨とする。空隙を有する炭素材料薄膜が、炭素繊維を積層して得られる不織布であることが好ましい。
また、本発明は、上記の電極セルを用いたリチウムイオン二次電池を要旨とする。 The gist of the present invention is an electrode cell in which the surface of a carbon material thin film having voids is coated with an electrolyte, and the positive electrode active material is filled in the voids. The carbon material thin film having voids is preferably a nonwoven fabric obtained by laminating carbon fibers.
Moreover, this invention makes a summary the lithium ion secondary battery using said electrode cell.

本発明により、負極材と正極材の近接した電極表面積の大きな電極セルが得られる。この電極セルを用いたリチウムイオン二次電池は、高速充放電の効果があり、安全性が高い。   According to the present invention, an electrode cell having a large electrode surface area close to the negative electrode material and the positive electrode material can be obtained. A lithium ion secondary battery using this electrode cell has an effect of high-speed charging / discharging and has high safety.

本発明の電極セルの一例を示す模式断面図である。It is a schematic cross section which shows an example of the electrode cell of this invention. 本発明のリチウムイオン二次電池の一例を示す模式断面図である。It is a schematic cross section which shows an example of the lithium ion secondary battery of this invention.

以下、本発明について詳細に説明する。
本発明の電極セルは、空隙を有する炭素材料薄膜の表面が電解質によって被覆され、その空隙内に正極活物質が充填されている。 Hereinafter, the present invention will be described in detail.
In the electrode cell of the present invention, the surface of the carbon material thin film having voids is coated with an electrolyte, and the positive electrode active material is filled in the voids.

空隙を有する炭素材料薄膜は、多孔質なプラスチックフィルムを焼成して炭素化する方法、炭素繊維を積層化して不織布とする方法等により得ることができるが、得られる炭素材料薄膜の機械強度や空隙の径の制御が良好であることから、炭素繊維を積層して得られる不織布（以下、「炭素繊維不織布」という。）が好ましい。   The carbon material thin film having voids can be obtained by a method of baking and carbonizing a porous plastic film, a method of laminating carbon fibers to form a nonwoven fabric, and the like. Therefore, a nonwoven fabric obtained by laminating carbon fibers (hereinafter referred to as “carbon fiber nonwoven fabric”) is preferable.

炭素繊維不織布に用いる炭素繊維としては、例えば、ポリアクリロニトリル又はアクリロニトリル共重合体から得られるポリアクリロニトリル系炭素繊維；セルロースから得られるセルロース系炭素繊維；低分子量有機物の気体から得られる気相成長炭素繊維；ポリビニルアルコール、ポリイミド、リグニン、ポリ塩化ビニル、フェノール樹脂、フルフリルアルコール樹脂等を焼成炭化して得られる炭素繊維が挙げられる。これらは、１種を単独で又は２種以上を併用することができる。
これらの中では、機械強度が高いことから、ポリアクリロニトリル系炭素繊維が好ましい。 Examples of carbon fibers used for the carbon fiber nonwoven fabric include polyacrylonitrile-based carbon fibers obtained from polyacrylonitrile or acrylonitrile copolymers; cellulose-based carbon fibers obtained from cellulose; vapor-grown carbon fibers obtained from gases of low molecular weight organic substances Carbon fibers obtained by firing and carbonizing polyvinyl alcohol, polyimide, lignin, polyvinyl chloride, phenol resin, furfuryl alcohol resin, and the like. These can be used alone or in combination of two or more.
Of these, polyacrylonitrile-based carbon fibers are preferred because of their high mechanical strength.

炭素繊維の平均直径は、表面平滑性及び導電性の観点から３〜３０μｍが好ましく、４〜２０μｍがより好ましく、４〜８μｍが更に好ましい。また、異なる平均直径の炭素繊維を２種類以上用いることも、表面平滑性及び導電性の観点から好ましい。
炭素繊維の長さは、得られる炭素繊維不織布の機械強度が向上することから、１〜１２ｍｍが好ましく、２〜９ｍｍがより好ましい。 The average diameter of the carbon fibers is preferably 3 to 30 μm, more preferably 4 to 20 μm, and still more preferably 4 to 8 μm from the viewpoint of surface smoothness and conductivity. It is also preferable to use two or more types of carbon fibers having different average diameters from the viewpoint of surface smoothness and conductivity.
The length of the carbon fiber is preferably 1 to 12 mm, and more preferably 2 to 9 mm, because the mechanical strength of the obtained carbon fiber nonwoven fabric is improved.

炭素繊維は、硫酸、燐酸、塩酸等を用いた酸処理により、表面に水酸基やカルボキシル基等の官能基を導入したものや、水酸化ナトリウム、水酸化カリウムを用いたアルカリ処理により、表面賦活化等の処理を行なったものであってもよい。   Carbon fiber is surface-activated by acid treatment using sulfuric acid, phosphoric acid, hydrochloric acid, etc., with functional groups such as hydroxyl and carboxyl groups introduced on the surface, or alkali treatment using sodium hydroxide or potassium hydroxide. Such processing may be performed.

炭素繊維不織布は、積層した炭素繊維をバインダー樹脂で結着し、６００〜３０００℃で焼成することにより得られる。
バインダー樹脂は、焼成後に炭素化する樹脂であればよく、例えば、フェノール樹脂、エポキシ樹脂、フラン樹脂、ポリアクリロニトリル樹脂が挙げられる。これらは、１種を単独で又は２種以上を併用することができる。
これらの中では、焼成による炭素化の際の炭化率が高いことから、フェノール樹脂が好ましい。 The carbon fiber non-woven fabric is obtained by binding laminated carbon fibers with a binder resin and firing at 600 to 3000 ° C.
The binder resin may be any resin that is carbonized after firing, and examples thereof include phenol resins, epoxy resins, furan resins, and polyacrylonitrile resins. These can be used alone or in combination of two or more.
In these, since the carbonization rate in the case of carbonization by baking is high, a phenol resin is preferable.

炭素材料薄膜が有する空隙の径は、１００ｎｍ以上１００μｍ以下が好ましく、１〜５０μｍがより好ましく、３〜２０μｍが更に好ましい。
炭素材料薄膜が有する空隙の径が１００ｎｍ以上であれば、空隙内への正極活物質の充填が容易となり、１００μｍ以下であれば、炭素材料薄膜の機械強度が低下しない。 The pore diameter of the carbon material thin film is preferably 100 nm to 100 μm, more preferably 1 to 50 μm, and still more preferably 3 to 20 μm.
If the diameter of the voids of the carbon material thin film is 100 nm or more, the positive electrode active material can be easily filled into the voids, and if it is 100 μm or less, the mechanical strength of the carbon material thin film does not decrease.

本発明で用いる電解質は、イオン伝導性を有するものであり、例えば、無機系高分子、有機系高分子、ゲル高分子等の高分子にリチウム塩を配合したものが挙げられる。   The electrolyte used in the present invention has ion conductivity, and examples thereof include a lithium salt blended with a polymer such as an inorganic polymer, an organic polymer, or a gel polymer.

リチウム塩としては、リチウムイオン二次電池用の電解質成分として公知なものを使用することができ、例えば、ＬｉＣｌＯ４、ＬｉＡｌＣｌ４、ＬｉＢＦ４、ＬｉＰＦ４、ＬｉＮｂＦ６、ＬｉＡｓＦ６、ＬｉＳＣＮ、ＬｉＣｌ、Ｌｉ（ＣＦ３ＳＯ３）、Ｌｉ（Ｃ４Ｆ９ＳＯ３）、ＬｉＩ、Ｌｉ（Ｃ６Ｈ５ＳＯ３）が挙げられる。これらは、１種を単独で又は２種以上を併用することができる。 Examples of the lithium salt can be used known ones as an electrolyte component for a lithium ion secondary battery, for example, LiClO 4, LiAlCl 4, LiBF 4, LiPF 4, LiNbF 6, LiAsF 6, LiSCN, LiCl, Li (CF 3 SO 3), Li (C 4 F 9 SO 3), LiI, Li (C 6 H 5 SO 3) and the like. These can be used alone or in combination of two or more.

リチウム塩を配合する高分子としては、リチウム塩と均一に配合できることから、有機系高分子が好ましい。
有機系高分子としては、例えば、ポリエチレンオキサイドを側鎖に有する単量体とスチレンを重合して得られるブロック共重合体（特開平２−２３０６６７号公報に開示）、ポリアルキレンオキサイドを側鎖に有する単量体を重合して得られる共重合体（特開２００２−２１６８４５号公報に開示）、ヒドロキシル基、ニトリル基、カルボキシル基、アミノ基等の官能基を有する単量体を重合して得られるブロック共重合体（特開平１１−２４０９９８号公報に開示）、及びこれらの組成物が挙げられる。 As the polymer for blending the lithium salt, an organic polymer is preferable because it can be blended uniformly with the lithium salt.
Examples of the organic polymer include a block copolymer obtained by polymerizing a monomer having polyethylene oxide in the side chain and styrene (disclosed in JP-A-2-230667), and a polyalkylene oxide in the side chain. Obtained by polymerizing a monomer having a functional group such as a hydroxyl group, a nitrile group, a carboxyl group, and an amino group (disclosed in JP-A No. 2002-216845) obtained by polymerizing the monomer having And block copolymers (disclosed in JP-A-11-240998) and compositions thereof.

リチウム塩と有機系高分子を均一に配合する方法としては、例えば、リチウム塩と有機系高分子を溶媒に溶解させて均一混合する方法、有機系高分子にリチウム塩を添加して常温又は加熱下に機械的に混練する方法、リチウム塩を溶解した溶液を有機系高分子に含浸させる方法が挙げられる。
空隙を有する炭素材料薄膜として炭素繊維不織布を用いる場合、表面が充分に被覆されることから、リチウム塩と有機系高分子を溶媒に溶解させて均一混合する方法が好ましい。 Examples of a method for uniformly blending a lithium salt and an organic polymer include, for example, a method in which a lithium salt and an organic polymer are dissolved in a solvent and uniformly mixed, and a lithium salt is added to an organic polymer at room temperature or heating. Examples thereof include a method of mechanically kneading and a method of impregnating an organic polymer with a solution in which a lithium salt is dissolved.
When a carbon fiber nonwoven fabric is used as the carbon material thin film having voids, a method of uniformly mixing a lithium salt and an organic polymer in a solvent is preferable because the surface is sufficiently covered.

リチウム塩と有機系高分子を配合する場合、有機系高分子に対するリチウム塩の比率は、有機系高分子を構成するポリエチレンオキサイドやポリアルキレンオキサイド等のリチウム配位ユニットに対して、０．００１〜１００ｍｏｌ％が好ましく、０．００５〜８０ｍｏｌ％がより好ましく、０．０１〜５０ｍｏｌ％が更に好ましい。
リチウム塩の比率が０．００１〜１００ｍｏｌ％の範囲であれば、リチウムイオンの解離、拡散が充分に行なわれ、電池として用いた場合に充分な性能が得られる。 When blending a lithium salt and an organic polymer, the ratio of the lithium salt to the organic polymer is 0.001 to the lithium coordination unit such as polyethylene oxide or polyalkylene oxide constituting the organic polymer. 100 mol% is preferable, 0.005 to 80 mol% is more preferable, and 0.01 to 50 mol% is still more preferable.
When the ratio of the lithium salt is in the range of 0.001 to 100 mol%, the lithium ions are sufficiently dissociated and diffused, and sufficient performance is obtained when used as a battery.

本発明の空隙を有する炭素材料薄膜の表面は、電解質によって被覆されている。ここで、炭素材料薄膜の表面とは、空隙の側面部を含むものである。
空隙を有する炭素材料薄膜が、炭素繊維不織布である場合には、炭素繊維及びバインダー樹脂の炭化物の表面が、電解質によって被覆されていることをいう。 The surface of the carbon material thin film having voids of the present invention is covered with an electrolyte. Here, the surface of the carbon material thin film includes a side surface portion of a void.
When the carbon material thin film having voids is a carbon fiber nonwoven fabric, it means that the surfaces of carbon fibers and the carbide of the binder resin are covered with an electrolyte.

空隙を有する炭素材料薄膜の表面を電解質で被覆する方法としては、例えば、電解質を溶解した溶液中に空隙を有する炭素材料薄膜を浸漬させた後に乾燥させる方法が挙げられる。   Examples of the method of coating the surface of the carbon material thin film having voids with an electrolyte include a method in which the carbon material thin film having voids is immersed in a solution in which the electrolyte is dissolved and then dried.

電解質を溶解させる溶媒は、電解質が均一に溶解できるものであればよく、電解質として使用するリチウム塩及び有機系高分子に応じて、種々の溶媒を選択して使用することができる。
溶媒としては、例えば、ジメチルホルムアミド、ジメチルアセトアミド、ジメトシキメタン、ジメトキシエタン、トルエン、キシレン、アセトン、アセトニトリルが挙げられる。これらは、１種を単独で又は２種以上を併用することができる。 The solvent for dissolving the electrolyte is not particularly limited as long as the electrolyte can be uniformly dissolved, and various solvents can be selected and used according to the lithium salt and the organic polymer used as the electrolyte.
Examples of the solvent include dimethylformamide, dimethylacetamide, dimethoxymethane, dimethoxyethane, toluene, xylene, acetone, and acetonitrile. These can be used alone or in combination of two or more.

電解質を溶媒に溶解させる濃度は、溶媒を乾燥除去後に得られる電解質膜の厚みに応じて調整することができ、５〜３０質量％が好ましい。
溶媒の乾燥は、使用する溶媒に応じて、熱風乾燥機等を用いて乾燥することができる。尚、空隙を有する炭素材料薄膜の電解質を溶解した溶液への浸漬、乾燥の工程は、好ましい電解質膜の厚みが得られるよう、繰り返し行なうことができる。 The concentration at which the electrolyte is dissolved in the solvent can be adjusted according to the thickness of the electrolyte membrane obtained after drying and removing the solvent, and is preferably 5 to 30% by mass.
The solvent can be dried using a hot air dryer or the like depending on the solvent used. It should be noted that the steps of immersing and drying the carbon material thin film having voids in the solution in which the electrolyte is dissolved can be repeatedly performed so that a preferable thickness of the electrolyte membrane is obtained.

電解質膜の厚みは、５００ｎｍ以上１００μｍ以下であることが好ましく、１〜５０μｍがより好ましく、１０〜３０μｍが更に好ましい。
電解質膜の厚みが５００ｎｍ以上であれば、電解質膜自体の強度が低下せず、電池充放電時に短絡が生じることがない。電解質膜の厚みが１００μｍ以下であれば、イオン伝導性が低下することがない。 The thickness of the electrolyte membrane is preferably 500 nm or more and 100 μm or less, more preferably 1 to 50 μm, and still more preferably 10 to 30 μm.
If the thickness of the electrolyte membrane is 500 nm or more, the strength of the electrolyte membrane itself does not decrease, and a short circuit does not occur during battery charge / discharge. If the thickness of the electrolyte membrane is 100 μm or less, the ionic conductivity is not lowered.

本発明で用いる正極活物質は、炭素材料薄膜の空隙内に充填するものであり、例えば、バナジウム酸化物、バナジウム硫化物、モリブテン酸化物、モリブデン硫化物、マンガン酸化物、マンガン硫化物、クロム酸化物、チタン酸化物、チタン硫化物、これらの複合酸化物、複合硫化物等の金属カルコゲン化合物、リチウムコバルト酸化物、リチウムニッケル酸化物、リチウムマンガン酸化物、リチウムニッケルコバルト酸化物等の複合酸化物、これらに他の金属元素（Ａｌ、Ｆｅ、Ｍｎ、Ｍｇ、Ｃｏ、Ｓｉ等）を添加した複合酸化物、ポリアニリン、ポリピロール等の導電性ポリマーが挙げられる。これらは、１種を単独で又は２種以上を併用することができる。
これらの中では、電池に用いた場合に電圧を高くとれることから、リチウムコバルト酸化物、リチウムニッケル酸化物、リチウムマンガン酸化物、リチウムニッケルコバルト酸化物等の複合酸化物が好ましい。 The positive electrode active material used in the present invention fills the voids of the carbon material thin film. For example, vanadium oxide, vanadium sulfide, molybdenum oxide, molybdenum sulfide, manganese oxide, manganese sulfide, chromium oxidation Products, titanium oxides, titanium sulfides, composite oxides of these, metal chalcogen compounds such as composite sulfides, composite oxides such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and lithium nickel cobalt oxide These include composite oxides obtained by adding other metal elements (Al, Fe, Mn, Mg, Co, Si, etc.), conductive polymers such as polyaniline and polypyrrole. These can be used alone or in combination of two or more.
Among these, composite oxides such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and lithium nickel cobalt oxide are preferable because the voltage can be increased when used in a battery.

本発明では、粒子状の正極活物質を用いる。
空隙を有する炭素材料薄膜として炭素繊維不織布を用いる場合、正極活物質の粒子径は、炭素繊維不織布の空隙の径よりも小さい必要があり、炭素繊維不織布の空隙の径に対して、１／１００〜１／１０の大きさであることが好ましい。
具体的には、正極活物質の粒子径は０．０５〜１０μｍであることが好ましい。 In the present invention, a particulate positive electrode active material is used.
When a carbon fiber nonwoven fabric is used as the carbon material thin film having voids, the particle diameter of the positive electrode active material needs to be smaller than the void diameter of the carbon fiber nonwoven fabric, and is 1/100 of the void diameter of the carbon fiber nonwoven fabric. A size of ˜1 / 10 is preferred.
Specifically, the particle diameter of the positive electrode active material is preferably 0.05 to 10 μm.

電解質によって被覆された炭素材料薄膜の空隙内に正極活物質を充填する方法としては、例えば、電解質によって被覆された炭素材料薄膜と、正極活物質を水媒体中でそれぞれ負、正に帯電させ、正極活物質を炭素材料薄膜の空隙内及び表面に泳導させる方法、正極活物質を分散させた溶液を、加圧条件下で炭素材料薄膜の空隙内に充填する方法が挙げられる。   As a method of filling the positive electrode active material in the voids of the carbon material thin film coated with the electrolyte, for example, the carbon material thin film coated with the electrolyte and the positive electrode active material are negatively and positively charged in an aqueous medium, respectively. Examples thereof include a method in which the positive electrode active material is introduced into the gap and the surface of the carbon material thin film, and a method in which the solution in which the positive electrode active material is dispersed is filled in the gap in the carbon material thin film under pressure.

本発明の電極セルは、空隙を有する炭素材料薄膜と正極活物質の体積比が、５０／５０〜９０／１０であることが好ましく、６０／４０〜８０／２０がより好ましく、６５／３５〜７５／２５が更に好ましい。   In the electrode cell of the present invention, the volume ratio of the carbon material thin film having voids to the positive electrode active material is preferably 50/50 to 90/10, more preferably 60/40 to 80/20, and 65/35 to 35/35. More preferred is 75/25.

図１及び図２を参照しながら本発明の電極セル及び電極セルを用いたリチウムイオン二次電池の形態について詳細に説明する。   With reference to FIG.1 and FIG.2, the form of the lithium ion secondary battery using the electrode cell of this invention and an electrode cell is demonstrated in detail.

図１は、本発明の電極セルの一例を示す模式断面図である。空隙を有する炭素材料薄膜１の表面が電解質２によって被覆され、その空隙内に正極活物質３が充填された構造を有している。尚、図１では、空隙を有する炭素材料薄膜１として、炭素繊維不織布を用いた場合を示している。   FIG. 1 is a schematic cross-sectional view showing an example of an electrode cell of the present invention. The surface of the carbon material thin film 1 having voids is covered with the electrolyte 2, and the positive electrode active material 3 is filled in the voids. In addition, in FIG. 1, the case where a carbon fiber nonwoven fabric is used as the carbon material thin film 1 which has a space | gap is shown.

図２は、本発明のリチウムイオン二次電池の一例を示す模式断面図である。本発明のリチウムイオン二次電池は、空隙を有する炭素材料薄膜の一部に、図１で示す電極セル４を形成させる。電極セル４を形成していない空隙を有する炭素材料薄膜は、負極の集電部位５として使用する。集電部位は、炭素材料薄膜で形成されているので、そのまま集電することもできるが、必要に応じて銅等の金属箔で挟み込み、金属箔を介して集電してもよい。   FIG. 2 is a schematic cross-sectional view showing an example of the lithium ion secondary battery of the present invention. In the lithium ion secondary battery of the present invention, the electrode cell 4 shown in FIG. 1 is formed on a part of a carbon material thin film having voids. The carbon material thin film having voids that do not form the electrode cell 4 is used as the current collecting portion 5 of the negative electrode. Since the current collecting portion is formed of a carbon material thin film, the current collecting portion can be collected as it is.

電極セル４の表面には、アルミニウム等の集電金属箔６を積層させ、正極の集電部位として使用する。電極セル４の表面と、集電金属箔６の密着性を向上させるために、カーボンペースト等の導電助剤を有した接着材等を使用することもできる。   A current collecting metal foil 6 such as aluminum is laminated on the surface of the electrode cell 4 and used as a current collecting portion of the positive electrode. In order to improve the adhesion between the surface of the electrode cell 4 and the current collector metal foil 6, an adhesive having a conductive additive such as a carbon paste may be used.

（１）：空隙を有する炭素材料薄膜
（２）：電解質
（３）：正極活物質
（４）：電極セル
（５）：集電部位
（６）：集電金属箔 (1): Carbon material thin film having voids (2): Electrolyte (3): Positive electrode active material (4): Electrode cell (5): Current collecting part (6): Current collecting metal foil

Claims (3)

空隙を有する炭素材料薄膜の表面が電解質によって被覆され、その空隙内に正極活物質が充填された電極セル。   An electrode cell in which the surface of a carbon material thin film having voids is coated with an electrolyte, and the positive electrode active material is filled in the voids. 空隙を有する炭素材料薄膜が、炭素繊維を積層して得られる不織布である、請求項１記載の電極セル。   The electrode cell according to claim 1, wherein the carbon material thin film having voids is a nonwoven fabric obtained by laminating carbon fibers. 請求項１又は２記載の電極セルを用いたリチウムイオン二次電池。   A lithium ion secondary battery using the electrode cell according to claim 1.
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