JP2002008655A - Negative electrode and non-aqueous electrolyte battery - Google Patents
Negative electrode and non-aqueous electrolyte batteryInfo
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- JP2002008655A JP2002008655A JP2000185070A JP2000185070A JP2002008655A JP 2002008655 A JP2002008655 A JP 2002008655A JP 2000185070 A JP2000185070 A JP 2000185070A JP 2000185070 A JP2000185070 A JP 2000185070A JP 2002008655 A JP2002008655 A JP 2002008655A
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- Prior art keywords
- negative electrode
- active material
- graphite
- electrode active
- carbon
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
(57)【要約】
【課題】 負極活物質として高い放電容量を有する鱗片
状黒鉛を用い、高容量かつ高サイクル特性を有し、大電
流放電においても高い体積エネルギー密度を示す。
【解決手段】 負極活物質である鱗片状黒鉛と、球状黒
鉛、塊状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカーボン
ブラックのうち少なくとも一種類以上の炭素材料とから
なる負極活物質混合体を含有し、当該負極活物質混合体
は、上記一種類以上の炭素材料を１重量％以上、５０重
量％以下の範囲で含有する。
[PROBLEMS] To use flaky graphite having a high discharge capacity as a negative electrode active material, to have a high capacity and a high cycle characteristic, and to exhibit a high volume energy density even in a large current discharge. A negative electrode active material mixture comprising flaky graphite as a negative electrode active material and at least one kind of carbon material among spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black is contained. The negative electrode active material mixture contains the one or more types of carbon materials in a range of 1% by weight or more and 50% by weight or less.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解質電池に
関する。[0001] The present invention relates to a non-aqueous electrolyte battery.
【０００２】[0002]
【従来の技術】近年、携帯電話、ノートブック型パソコ
ンなどをはじめとする電子機器のコードレス化、ポータ
ブル化が進み、薄型、小型、軽量の携帯電子機器が次々
と開発されている。また、機器の多様化によって電力使
用量が増加し、それら電子機器のエネルギー源である電
池、特に二次電池の高容量化に対する需要が高まってい
る。2. Description of the Related Art In recent years, cordless and portable electronic devices such as portable telephones and notebook personal computers have been developed, and thin, small, and lightweight portable electronic devices have been developed one after another. In addition, the diversification of devices has led to an increase in the amount of electric power used, and there has been an increasing demand for higher capacity batteries, particularly secondary batteries, which are energy sources for these electronic devices.
【０００３】従来から使用されてきた二次電池としては
鉛蓄電池、ニッケルカドミウム電池があり、新たな二次
電池としてはニッケル水素電池やリチウムイオン電池が
実用化されている。しかしながら、これらの二次電池は
電解質として液状電解質を使用しているため、電池から
の液漏れの問題があった。そこで、このような問題を解
決すべく開発されたのが、電解液によって膨潤した高分
子ゲルを電解質として使用した固体電解質リチウムイオ
ン二次電池である。この固体電解質リチウムイオン二次
電池の開発により、電池からの液漏れの心配がなくな
り、小型、軽量、薄型であり高いエネルギー密度を有す
る二次電池の開発が可能となった。Conventionally used secondary batteries include a lead storage battery and a nickel cadmium battery, and nickel-metal hydride batteries and lithium ion batteries have been put into practical use as new secondary batteries. However, since these secondary batteries use a liquid electrolyte as an electrolyte, there is a problem of liquid leakage from the batteries. To solve such a problem, a solid electrolyte lithium ion secondary battery using a polymer gel swollen by an electrolyte as an electrolyte has been developed. With the development of this solid electrolyte lithium ion secondary battery, there is no need to worry about liquid leakage from the battery, and it has become possible to develop a small, lightweight, thin secondary battery having a high energy density.
【０００４】上記の固体電解質リチウムイオン二次電池
の構成について説明すると、アルミニウム薄板からなる
正極集電体上に、例えばＬｉＣｏＯ2と黒鉛とを含有す
る正極活物質層が形成されて正極を構成している。ま
た、銅薄板からなる負極集電体の上にはカーボン、コー
クス、グラファイトなどを含有する負極活物質層が形成
されて負極を構成している。The structure of the above-mentioned solid electrolyte lithium ion secondary battery will be described. A positive electrode active material layer containing, for example, LiCoO 2 and graphite is formed on a positive electrode current collector made of a thin aluminum plate to constitute a positive electrode. ing. Further, a negative electrode active material layer containing carbon, coke, graphite, and the like is formed on a negative electrode current collector made of a copper thin plate to form a negative electrode.
【０００５】正極と負極との間にはポリプロピレン、ポ
リエチレンなどからなり、細孔を有する薄膜であるセパ
レータが組み込まれている。そして、これら電極、セパ
レータの間には、ポリアクリロニトリル（ＰＡＮ）、ポ
リエチレンオキサイド（ＰＥＯ）、ポリフッ化ビニリデ
ン（ＰＶＤＦ）のような高分子をリチウム塩を含む電解
液によって膨潤させた、ゲル状電解質が充填されたサン
ドイッチ構造をとっている。また、サンドイッチ構造に
なったこれら素電池（ユニットセル）は、封入用容器と
してアルミニウム箔のような金属薄膜と、ナイロン、ポ
リエチレン、ポリプロピレン、ポリエチレンテレフタレ
ート等のプラスチックフィルムで構成された封入材でパ
ッケージングされる。[0005] A separator made of polypropylene, polyethylene, or the like, which is a thin film having pores, is incorporated between the positive electrode and the negative electrode. And between these electrodes and separators, a gel electrolyte is formed by swelling a polymer such as polyacrylonitrile (PAN), polyethylene oxide (PEO), or polyvinylidene fluoride (PVDF) with an electrolyte containing a lithium salt. It has a filled sandwich structure. In addition, these unit cells with a sandwich structure are packaged with an encapsulating material composed of a metal thin film such as aluminum foil and a plastic film such as nylon, polyethylene, polypropylene and polyethylene terephthalate as an encapsulating container. Is done.
【０００６】さらに負極活物質についてみてみると、黒
鉛自体のリチウム吸蔵、放出能力とともに、電池という
限られた体積の中でいかに多量の黒鉛を詰め込みうるか
という充填性がある。これは黒鉛に限らず、粉末であれ
ばその形状に大きく左右されるものである。黒鉛の粉末
の形状を考えた場合、球状、塊状、鱗片状、繊維状等が
挙げられる。Looking further at the negative electrode active material, graphite has a filling property such as how much graphite can be packed in a limited volume of a battery, in addition to the ability of graphite itself to absorb and release lithium. This is not limited to graphite, but depends greatly on the shape of the powder. Considering the shape of the graphite powder, spherical, massive, flaky, fibrous, and the like can be mentioned.
【０００７】通常、固体電解質負極は、集電体である金
属薄膜の両面、又は片面に黒鉛と結着剤との混合物を塗
布し、これを適宜圧延して形成されるが、上記各形状の
黒鉛のうち鱗片状黒鉛は、圧延によって粒子が同一方向
に配向するという特徴により、緊密性が大きく、充填性
も大となり、これらの点から黒鉛由来の負極材料として
は、鱗片状黒鉛が最も優れた材料であるといえる。Normally, a solid electrolyte negative electrode is formed by applying a mixture of graphite and a binder to both surfaces or one surface of a metal thin film as a current collector and rolling the mixture appropriately, but the above-mentioned shapes are used. Among graphite, flaky graphite is characterized by the fact that particles are oriented in the same direction by rolling, so that the tightness is large and the filling property is also large.From these points, flaky graphite is the most excellent graphite-derived negative electrode material. It can be said that it is a material.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、鱗片状
の黒鉛を負極活物質として用いる場合、解決しなければ
ならない問題がある。第一に、鱗片状黒鉛は配向性が大
きいために、圧延により充填性が上がるが、逆に充填性
が上がりすぎて電極内の空孔部分が制限され、電池の電
極を形成したとき電極内部に電解質が浸透しないため電
極表面部分でした電池反応が行われず、電極の反応利用
率の低下、あるいは高負荷放電に適さないという課題が
生じる（特開平８−２８７９５２号公報）。However, when flaky graphite is used as the negative electrode active material, there is a problem to be solved. First, because flaky graphite has a large orientation, the filling property is increased by rolling, but conversely, the filling property is too high, the pores in the electrode are restricted, and the inside of the electrode is formed when the battery electrode is formed. Since the electrolyte does not penetrate into the electrode, the battery reaction on the surface of the electrode does not take place, causing a problem that the reaction utilization of the electrode is lowered or the electrode is not suitable for high-load discharge (Japanese Patent Application Laid-Open No. 8-287952).
【０００９】特にゲル状電解質を用いた電池において
は、上記のような課題を解決するため、ゲル状電解質自
身が電極中に浸透することが必要とされる。ゲル状電解
質は従来の液系電解質と比較して非常に粘度が高いこと
から、電極塗膜中への浸透は起こりにくい。従って電解
液の浸透のみを考慮すれば解決される液系電解質の場合
と比較して、電極中における適当な空孔を確保すること
はより一層重要となる。Particularly, in a battery using a gel electrolyte, it is necessary that the gel electrolyte permeates into the electrode in order to solve the above-mentioned problems. Since the gel electrolyte has a very high viscosity as compared with the conventional liquid electrolyte, it does not easily penetrate into the electrode coating film. Therefore, it is even more important to secure appropriate pores in the electrode than in the case of a liquid electrolyte which can be solved by considering only the permeation of the electrolyte.
【００１０】第二に、負極活物質として鱗片状黒鉛のみ
を用いて電極を形成した場合、集電体と活物質との間の
結着性が、球状黒鉛などのそれと比較して低いため、活
物質が充放電を繰り返す際の膨張収縮などによって電極
からの活物質の剥離が生じサイクル特性が低下する。こ
れを防ぐために結着剤成分を増加させることは、結果と
して電極の充放電容量を低下させることになるという問
題が生じる。Second, when an electrode is formed using only flaky graphite as the negative electrode active material, the binding property between the current collector and the active material is lower than that of spherical graphite or the like. The active material peels off from the electrode due to expansion and contraction when the active material is repeatedly charged and discharged, and the cycle characteristics are deteriorated. Increasing the binder component to prevent this results in a problem that the charge / discharge capacity of the electrode is reduced.
【００１１】本発明はこのような従来の実情に鑑みて提
案されたものであり、負極活物質として高い放電容量を
有する鱗片状黒鉛を用い、高容量かつ高サイクル特性を
有し、大電流放電においても高い体積エネルギー密度を
示す負極及びそれを用いた非水電解質電池を提供するこ
とを目的とする。The present invention has been proposed in view of such a conventional situation, and uses flaky graphite having a high discharge capacity as a negative electrode active material, has a high capacity and a high cycle characteristic, and has a large current discharge. It is another object of the present invention to provide a negative electrode exhibiting a high volume energy density and a nonaqueous electrolyte battery using the same.
【００１２】[0012]
【課題を解決するための手段】本発明の負極は、負極活
物質である鱗片状黒鉛と、球状黒鉛、塊状黒鉛、繊維状
黒鉛、難黒鉛化炭素又はカーボンブラックのうち少なく
とも一種類以上の炭素材料とからなる負極活物質混合体
を含有し、当該負極活物質混合体は、上記一種類以上の
炭素材料を１重量％以上、５０重量％以下の範囲で含有
することを特徴とする。Means for Solving the Problems The negative electrode of the present invention comprises flaky graphite, which is a negative electrode active material, and at least one kind of carbon selected from spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon and carbon black. And a negative electrode active material mixture comprising the above-mentioned one or more carbon materials in a range of 1% by weight or more and 50% by weight or less.
【００１３】上述したような本発明に係る負極では、負
極活物質である鱗片状黒鉛に、球状黒鉛、塊状黒鉛、繊
維状黒鉛、難黒鉛化炭素又はカーボンブラックの、他の
形状の黒鉛が混合されているので、結着剤成分を増加さ
せることなく負極活物質層と負極集電体との結着性を高
めるとともに、負極活物質の利用効率が向上する。In the negative electrode according to the present invention as described above, flaky graphite as the negative electrode active material is mixed with graphite of another shape such as spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black. Therefore, the binding efficiency between the negative electrode active material layer and the negative electrode current collector is increased without increasing the binder component, and the utilization efficiency of the negative electrode active material is improved.
【００１４】また、本発明の非水電解質電池は、リチウ
ムをドープ・脱ドープ可能な正極活物質を有する正極
と、リチウムをドープ・脱ドープ可能な負極活物質を有
する負極と、正極と負極との間に介在される非水電解質
とを備える。そして、本発明の非水電解質電池は、上記
負極が、負極活物質である鱗片状黒鉛と、球状黒鉛、塊
状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカーボンブラッ
クのうち少なくとも一種類以上の炭素材料とからなる負
極活物質混合体を含有し、当該負極活物質混合体は、上
記一種類以上の炭素材料を１重量％以上、５０重量％以
下の範囲で含有することを特徴とする。Further, the nonaqueous electrolyte battery of the present invention comprises a positive electrode having a positive electrode active material capable of doping and undoping lithium, a negative electrode having a negative electrode active material capable of doping and undoping lithium, a positive electrode and a negative electrode. And a non-aqueous electrolyte interposed therebetween. And the nonaqueous electrolyte battery of the present invention is characterized in that the negative electrode has at least one kind of carbon such as flaky graphite as a negative electrode active material, spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black. And a negative electrode active material mixture comprising the above-mentioned one or more carbon materials in a range of 1% by weight or more and 50% by weight or less.
【００１５】上述したような本発明に係る非水電解質電
池では、負極活物質である鱗片状黒鉛に、球状黒鉛、塊
状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカーボンブラッ
クの、他の形状の黒鉛が混合されているので、結着剤成
分を増加させなくても、負極活物質層と負極集電体との
結着性を高めるとともに、負極活物質の利用効率が向上
する。そして、そのような負極を用いた本発明に係る非
水電解質電池は、高容量かつ高負荷、高サイクル特性を
有するものとなる。In the non-aqueous electrolyte battery according to the present invention as described above, flaky graphite as a negative electrode active material is replaced with spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black. Since graphite is mixed, the binding efficiency between the negative electrode active material layer and the negative electrode current collector can be improved without increasing the binder component, and the utilization efficiency of the negative electrode active material can be improved. The nonaqueous electrolyte battery according to the present invention using such a negative electrode has high capacity, high load, and high cycle characteristics.
【００１６】[0016]
【発明の実施の形態】以下、本発明の実施の形態につい
て説明する。Embodiments of the present invention will be described below.
【００１７】本実施の形態に係るゲル状電解質電池１の
一構成例を図１及び図２に示す。このゲル状電解質電池
１は、帯状の正極２と、正極２と対向して配された帯状
の負極３と、正極２及び負極３上に形成されたゲル状電
解質層４とを備える。FIGS. 1 and 2 show one structural example of the gel electrolyte battery 1 according to the present embodiment. The gel electrolyte battery 1 includes a band-shaped positive electrode 2, a band-shaped negative electrode 3 disposed to face the positive electrode 2, and a gel electrolyte layer 4 formed on the positive electrode 2 and the negative electrode 3.
【００１８】そして、このゲル状電解質電池１は、ゲル
状電解質層４が形成された正極２とゲル状電解質層４が
形成された負極３とが積層されるとともに長手方向に巻
回された、図３に示す電極巻回体５が、絶縁材料からな
る外装フィルム６により覆われて密閉されている。そし
て、正極２には正極端子７が、負極３には負極端子８が
それぞれ接続されており、これらの正極端子７と負極端
子８とは、外装フィルム６の周縁部である封口部に挟み
込まれている。In the gel electrolyte battery 1, the positive electrode 2 on which the gel electrolyte layer 4 is formed and the negative electrode 3 on which the gel electrolyte layer 4 is formed are laminated and wound in the longitudinal direction. The electrode winding body 5 shown in FIG. 3 is covered and sealed by an exterior film 6 made of an insulating material. A positive electrode terminal 7 is connected to the positive electrode 2, and a negative electrode terminal 8 is connected to the negative electrode 3. The positive electrode terminal 7 and the negative electrode terminal 8 are sandwiched by a sealing portion that is a peripheral portion of the exterior film 6. ing.
【００１９】正極２は、正極活物質を含有する正極活物
質層が、正極集電体の両面上に形成されている。この正
極集電体としては、例えばアルミニウム箔等の金属箔が
用いられる。The positive electrode 2 has a positive electrode active material layer containing a positive electrode active material formed on both surfaces of a positive electrode current collector. As the positive electrode current collector, for example, a metal foil such as an aluminum foil is used.
【００２０】正極活物質としては、目的とする電池の種
類に応じて、金属酸化物、金属硫化物、又は特定の高分
子を使用することができる。As the positive electrode active material, a metal oxide, a metal sulfide, or a specific polymer can be used depending on the type of the intended battery.
【００２１】例えば、リチウムの溶解・析出を利用した
リチウム電池とする場合、ＴｉＳ2、ＭｏＳ2、ＮｂＳｅ
2、Ｖ2Ｏ5等のリチウムを含まない金属硫化物あるいは
酸化物、さらにはポリアセチレン、ポリピロール等の高
分子を使用することもできる。For example, when a lithium battery utilizing lithium dissolution / precipitation is used, TiS 2 , MoS 2 , NbSe
2 , metal sulfides or oxides not containing lithium such as V 2 O 5 , and polymers such as polyacetylene and polypyrrole can also be used.
【００２２】リチウムイオンのドープ・脱ドープを利用
したリチウムイオン電池とする場合には、ＬｉxＭＯ
2（式中Ｍは一種以上の遷移金属を表し、ｘは電池の充
放電状態によって異なり、通常０．０５以上、１．１０
以下である。）を主体とするリチウム複合酸化物等を使
用することができる。このリチウム複合酸化物を構成す
る遷移金属Ｍとしては、Ｃｏ、Ｎｉ、Ｍｎ等が好まし
い。このようなリチウム複合酸化物の具体例としてはＬ
ｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＮｉyＣｏ1-yＯ2（式
中、０＜ｙ＜１である。）、ＬｉＭｎ2Ｏ4、ＬｉＭＰＯ
4（式中、ＭはＦｅ等、一種以上の遷移金属を表す）等
を挙げることができる。これらのリチウム複合酸化物
は、一種類を単独で用いてもよいし、複数種を混合して
用いてもよい。When a lithium ion battery utilizing doping / dedoping of lithium ion is used, Li x MO
2 (wherein M represents one or more transition metals, x varies depending on the charge / discharge state of the battery, and is usually 0.05 or more, 1.10
It is as follows. ) Can be used. As the transition metal M constituting the lithium composite oxide, Co, Ni, Mn, or the like is preferable. Specific examples of such a lithium composite oxide include L
iCoO 2 , LiNiO 2 , LiNi y Co 1-y O 2 (where 0 <y <1), LiMn 2 O 4 , LiMPO
4 (wherein M represents one or more transition metals such as Fe). One of these lithium composite oxides may be used alone, or a plurality of them may be used as a mixture.
【００２３】リチウム複合酸化物は、高電圧を発生で
き、エネルギー密度的に優れた正極活物質となる。正極
活物質には、これらの正極活物質の複数種を併せて使用
してもよい。また、以上のような正極活物質を使用して
正極活物質層を形成するときには、公知の導電剤や結着
剤等を添加することができる。The lithium composite oxide can generate a high voltage and is a positive electrode active material excellent in energy density. A plurality of these positive electrode active materials may be used in combination as the positive electrode active material. When a positive electrode active material layer is formed using the above-described positive electrode active material, a known conductive agent, a binder, and the like can be added.
【００２４】また、負極３は、負極活物質と結着剤とを
含有する負極活物質層が、負極集電体の両面上に形成さ
れている。この負極集電体としては、例えば銅箔等の金
属箔が用いられる。負極活物質にはリチウムをドープ、
脱ドープできる炭素材料が用いられる。The negative electrode 3 has a negative electrode active material layer containing a negative electrode active material and a binder formed on both surfaces of a negative electrode current collector. As the negative electrode current collector, for example, a metal foil such as a copper foil is used. Dope lithium into the negative electrode active material,
A carbon material that can be undoped is used.
【００２５】リチウムをドープ、脱ドープできる炭素材
料としては、具体的には後述するが、鱗片状黒鉛が用い
られる。そして、このゲル状電解質電池では、負極活物
質である鱗片状黒鉛と、当該鱗片状黒鉛に加えて、球状
黒鉛、塊状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカーボ
ンブラックのうち少なくとも一種類以上の炭素材料とを
含有する。また、以上のような負極活物質を使用して負
極活物質層を形成するときには、公知の結着剤等を添加
することができる。As a carbon material which can be doped and dedoped with lithium, flake graphite is used, which will be specifically described later. And in this gel electrolyte battery, in addition to the flaky graphite as the negative electrode active material, the flaky graphite, at least one or more of spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black And a carbon material. When forming the negative electrode active material layer using the above-described negative electrode active material, a known binder or the like can be added.
【００２６】ところで、負極活物質層に用いられる結着
剤は、負極活物質のようにリチウム吸蔵放出能力を持た
ない。そのため、結着剤量の増加は負極活物質の充填量
低下につながり、充放電容量を低下させてしまう。By the way, the binder used for the negative electrode active material layer does not have a lithium storage / release capability unlike the negative electrode active material. Therefore, an increase in the amount of the binder leads to a decrease in the filling amount of the negative electrode active material, which lowers the charge / discharge capacity.
【００２７】本発明者らは、鋭意検討を行った結果、負
極活物質である鱗片状黒鉛に他の形状の黒鉛を少なくと
も１種類混合することで、結着剤成分を増加させること
なく、負極活物質層と負極集電体との結着性を高めると
ともに負極活物質の利用効率を向上することができ、そ
れにより高容量かつ高負荷、高サイクル特性を示す非水
電解質電池を実現できることを見出した。As a result of intensive studies, the present inventors have found that by mixing at least one type of graphite of another shape with flaky graphite, which is a negative electrode active material, the negative electrode active material is not increased without increasing the binder component. It is possible to improve the binding property between the active material layer and the negative electrode current collector and improve the utilization efficiency of the negative electrode active material, thereby realizing a non-aqueous electrolyte battery having high capacity, high load, and high cycle characteristics. I found it.
【００２８】すなわち、本実施の形態に係るゲル状電解
質電池１では、負極活物質である鱗片状黒鉛と、当該鱗
片状黒鉛に加えて、球状黒鉛、塊状黒鉛、繊維状黒鉛、
難黒鉛化炭素又はカーボンブラックのうち少なくとも一
種類以上の炭素材料とを含有する。That is, in the gel electrolyte battery 1 according to the present embodiment, flaky graphite as a negative electrode active material, and in addition to the flaky graphite, spherical graphite, massive graphite, fibrous graphite,
It contains at least one or more types of carbon material out of non-graphitizable carbon or carbon black.
【００２９】鱗片状黒鉛に加えて混合される、球状黒
鉛、塊状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカーボン
ブラックは、鱗片状黒鉛と同様に、それ自身がリチウム
吸蔵放出能力を有する。これらの炭素材料の少なくとも
一種類以上を混合することで、結着剤成分を増加させる
ことなく、負極活物質層と負極集電体との結着性を高め
ることができた。さらに、炭素材料の少なくとも一種類
以上を混合することで、適当な適当な空孔を形成するこ
とになり、負極活物質である鱗片状黒鉛へのリチウムイ
オンのドープ・脱ドープが行われやすい構造となる。こ
れにより、鱗片状黒鉛の利用率を向上させて、高い充放
電容量を保持したまま、高負荷特性、高サイクル特性を
示す電池を得ることができる。Spheroidal graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black, which is mixed in addition to flaky graphite, itself has a lithium storage / release capability, like flaky graphite. By mixing at least one of these carbon materials, the binding property between the negative electrode active material layer and the negative electrode current collector could be increased without increasing the binder component. Furthermore, by mixing at least one kind of carbon material, a suitable hole is formed, and a structure in which doping and undoping of lithium ion to flaky graphite as a negative electrode active material is easily performed. Becomes As a result, it is possible to improve the utilization rate of the flaky graphite and obtain a battery exhibiting high load characteristics and high cycle characteristics while maintaining high charge / discharge capacity.
【００３０】負極活物質である鱗片状黒鉛と混合される
球状黒鉛、塊状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカ
ーボンブラックの量は、鱗片状黒鉛と混合される上記一
種類以上の炭素材料とからなる負極活物質混合体の全体
に対して１重量部以上、５０重量部以下の範囲であるこ
とが好ましい。The amount of the spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black mixed with the flaky graphite as the negative electrode active material depends on the amount of the one or more carbon materials mixed with the flaky graphite. Is preferably in the range of 1 part by weight or more and 50 parts by weight or less based on the whole negative electrode active material mixture consisting of
【００３１】球状黒鉛、塊状黒鉛、繊維状黒鉛又は難黒
鉛化炭素又はカーボンブラックの混合量が、負極活物質
混合体全体に対して１重量部未満だと、負極集電体と負
極活物質層との密着性を高める効果が不十分であり、長
期充電サイクルに伴い負極集電体と負極活物質層との界
面で剥離が生じ、サイクル特性が低下してしまう。If the amount of the spheroidal graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black is less than 1 part by weight with respect to the whole negative electrode active material mixture, the negative electrode current collector and the negative electrode active material layer The effect of increasing the adhesion to the negative electrode current collector is insufficient, and peeling occurs at the interface between the negative electrode current collector and the negative electrode active material layer with a long-term charge cycle, and the cycle characteristics deteriorate.
【００３２】また、球状黒鉛、塊状黒鉛、繊維状黒鉛又
は難黒鉛化炭素又はカーボンブラックの混合量が、負極
活物質混合体全体に対して５０重量部を超えると、こん
どは負極活物質である鱗片状黒鉛の割合が減少してしま
い、容量低下を招いてしまう。なお、球状黒鉛、塊状黒
鉛、繊維状黒鉛又は難黒鉛化炭素又はカーボンブラック
の混合量が、負極活物質混合体全体に対して２０重量部
を超えると、負極集電体と負極活物質層との結着性はそ
れ以上は大きく向上しない。また、十分に大きい値とな
る。If the amount of the spheroidal graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black exceeds 50 parts by weight with respect to the whole negative electrode active material mixture, the mixture becomes the negative electrode active material. The proportion of flaky graphite decreases, which leads to a decrease in capacity. Incidentally, when the mixing amount of the spherical graphite, massive graphite, fibrous graphite or non-graphitizable carbon or carbon black exceeds 20 parts by weight with respect to the whole negative electrode active material mixture, the negative electrode current collector and the negative electrode active material layer Does not significantly improve. In addition, the value is sufficiently large.
【００３３】さらに、鱗片状黒鉛に球状黒鉛又はカーボ
ンブラックを混合する場合、これら球状黒鉛又はカーボ
ンブラックの単位重量当たりの充放電容量は、鱗片状黒
鉛の充放電容量と比較して低いことから、鱗片状黒鉛の
割合減少に伴い、容量増加の効果が半減してしまう。さ
らに、鱗片状黒鉛の減少は、電極塗布膜厚の増加を招く
ことから、これは、電池の体積エネルギー密度の減少を
招く。また、鱗片状黒鉛に難黒鉛化炭素を混合する場
合、容量低下は生じないものの、難黒鉛化炭素特有のな
だらかな放電曲線を示すことから、携帯電話等の用途に
用いるには適当ではない。Further, when spheroidal graphite or carbon black is mixed with flaky graphite, the charge / discharge capacity per unit weight of the spheroidal graphite or carbon black is lower than the charge / discharge capacity of flaky graphite. As the proportion of flaky graphite decreases, the effect of increasing the capacity is reduced by half. Furthermore, the reduction of flaky graphite leads to an increase in the electrode coating film thickness, which leads to a decrease in the volume energy density of the battery. Further, when flake graphite is mixed with non-graphitizable carbon, the capacity is not reduced, but since it shows a gentle discharge curve peculiar to non-graphitizable carbon, it is not suitable for use in mobile phones and the like.
【００３４】従って、鱗片状黒鉛に対する、球状黒鉛、
塊状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカーボンブラ
ックの混合量を、負極活物質混合体全体に対して１重量
部以上、５０重量部以下の範囲とすることで、高い充放
電容量を保持したまま、負極活物質層と負極集電体との
結着性を高めるとともに、負極活物質の利用効率を向上
させて高負荷特性、高サイクル特性を実現することがで
きる。また、球状黒鉛、塊状黒鉛、繊維状黒鉛、難黒鉛
化炭素又はカーボンブラックの混合量のより好ましい混
合量は、負極活物質混合体全体に対して５重量部以上、
３０重量部以下の範囲である。Therefore, spheroidal graphite, flaky graphite,
High charge / discharge capacity is maintained by setting the mixing amount of massive graphite, fibrous graphite, non-graphitizable carbon or carbon black in the range of 1 part by weight or more and 50 parts by weight or less based on the whole negative electrode active material mixture. As it is, the binding property between the negative electrode active material layer and the negative electrode current collector can be improved, and the utilization efficiency of the negative electrode active material can be improved to achieve high load characteristics and high cycle characteristics. Further, the more preferable mixing amount of the spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black is at least 5 parts by weight based on the whole negative electrode active material mixture,
The range is 30 parts by weight or less.
【００３５】ゲル状電解質層４は、電解質塩と、マトリ
クスポリマと、可塑剤としての膨潤溶媒とを含有する。The gel electrolyte layer 4 contains an electrolyte salt, a matrix polymer, and a swelling solvent as a plasticizer.
【００３６】電解質塩としては、ＬｉＰＦ6、ＬｉＢ
Ｆ4、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＮ（ＣＦ3Ｓ
Ｏ2）2、又はＬｉＣＦ3ＳＯ3等のリチウム化合物を単独
又は混合して使用することができる。その中でも、イオ
ン伝導性等の観点から、ＬｉＰＦ6を使用することが好
ましい。As the electrolyte salt, LiPF 6 , LiB
F 4 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 S
Lithium compounds such as O 2 ) 2 or LiCF 3 SO 3 can be used alone or in combination. Among them, it is preferable to use LiPF 6 from the viewpoint of ion conductivity and the like.
【００３７】また、マトリクスポリマとは、ポリマ単体
もしくはこれを用いたゲル状電解質が、室温で１ｍＳ／
ｃｍ以上のイオン伝導度を示すものであれば、特に化学
的な構造は限定されない。このマトリクスポリマとして
は、ビニリデンフルオライド、アクリロニトリル、エチ
レンオキシド、プロピレンオキシド、又はメタクリルニ
トリルのうちの少なくとも１つが、繰り返し単位として
含まれる化合物が使用される。具体的には、ポリビニリ
デンフルオライド、ポリアクリロニトリル、ポリエチレ
ンオキシド、ポリプロピレンオキシド、又はポリメタク
リルニトリルなどが挙げられる。The matrix polymer refers to a polymer alone or a gel electrolyte using the same at room temperature of 1 mS /
The chemical structure is not particularly limited as long as it has an ion conductivity of not less than cm. As the matrix polymer, a compound containing at least one of vinylidene fluoride, acrylonitrile, ethylene oxide, propylene oxide, and methacrylonitrile as a repeating unit is used. Specific examples include polyvinylidene fluoride, polyacrylonitrile, polyethylene oxide, polypropylene oxide, and polymethacrylonitrile.
【００３８】また膨潤溶媒としては、エチレンカーボネ
ート、プロピレンカーボネート、ジメチルカーボネー
ト、エチルメチルカーボネート、ジエチルカーボネー
ト、γ−ブチロラクトン、エチルプロピルカーボネー
ト、ジプロピルカーボネート、ブチルプロピルカーボネ
ート、ジブチルカーボネート、１，２−ジメトキシエタ
ン、１，２−ジエトキシエタン等の非水溶媒を単独又は
混合して用いることができる。Examples of the swelling solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, γ-butyrolactone, ethyl propyl carbonate, dipropyl carbonate, butyl propyl carbonate, dibutyl carbonate and 1,2-dimethoxyethane. , 1,2-diethoxyethane and other non-aqueous solvents can be used alone or in combination.
【００３９】電極巻回体５は、このような正極２及び負
極３のそれぞれの片面に上述したゲル状電解質層４を塗
布した後、ゲル状電解質層４を塗布した面を合わせるこ
とによって形成される。The wound electrode body 5 is formed by coating the above-mentioned gel electrolyte layer 4 on one surface of each of the positive electrode 2 and the negative electrode 3 and then matching the surfaces on which the gel electrolyte layer 4 has been coated. You.
【００４０】外装フィルム６は、上記電極巻回体５を収
容する。外装フィルム６は、例えば、外装保護層と、ア
ルミニウム層と、熱溶着層（ラミネート最内層）とから
なるヒートシールタイプのシート状ラミネートフィルム
により形成されている。The outer film 6 accommodates the above-mentioned electrode winding body 5. The exterior film 6 is formed of, for example, a heat-sealing type sheet-like laminated film including an exterior protection layer, an aluminum layer, and a heat welding layer (the innermost layer of the laminate).
【００４１】ここで、熱溶着層及び外部保護層の材質と
しては、プラスチックフィルムなどを挙げることができ
る。熱溶着層を形成するプラスチックフィルムには、ポ
リエチレン、ポリプロピレン、ナイロン（商品名）など
が用いられるが、熱可塑性のプラスチック材料であれば
その原料を問わない。Here, examples of the material of the heat welding layer and the external protective layer include a plastic film. Polyethylene, polypropylene, nylon (trade name) and the like are used for the plastic film forming the heat-welding layer, and any raw material may be used as long as it is a thermoplastic plastic material.
【００４２】上述したような本実施の形態に係るゲル状
電解質電池１は、負極活物質である鱗片状黒鉛に他の形
状の黒鉛を少なくとも１種類混合することで、結着剤成
分を増加させることなく、負極活物質層と負極集電体と
の結着性を高めとともに負極活物質の利用効率を向上さ
せることができ、それにより高容量かつ高負荷、高サイ
クル特性を示すものとなる。In the gel electrolyte battery 1 according to the present embodiment as described above, the binder component is increased by mixing at least one type of graphite of another shape with flaky graphite as the negative electrode active material. Without increasing the binding property between the negative electrode active material layer and the negative electrode current collector, the utilization efficiency of the negative electrode active material can be improved, thereby exhibiting high capacity, high load, and high cycle characteristics.
【００４３】そして、上述したような本実施の形態に係
るゲル状電解質電池１は、つぎのようにして製造され
る。Then, the gel electrolyte battery 1 according to the present embodiment as described above is manufactured as follows.
【００４４】まず、正極２としては、正極活物質と結着
剤とを含有する正極合剤を、正極集電体となる例えばア
ルミニウム箔等の金属箔上に均一に塗布、乾燥すること
により正極活物質層が形成されて正極シートが作製され
る。上記正極合剤の結着剤としては、公知の結着剤を用
いることができるほか、上記正極合剤に公知の添加剤等
を添加することができる。First, as the positive electrode 2, a positive electrode mixture containing a positive electrode active material and a binder is uniformly coated on a metal foil such as an aluminum foil serving as a positive electrode current collector and dried to dry the positive electrode. An active material layer is formed to produce a positive electrode sheet. Known binders can be used as the binder of the positive electrode mixture, and known additives and the like can be added to the positive electrode mixture.
【００４５】次に、正極シートを帯状に切り出す。そし
て、正極活物質層の非形成部分にリード線を溶接して正
極端子７とする。正極端子７に使用される材料の例とし
ては、アルミニウム、チタン、或いはこれらの合金など
が挙げられる。このようにして帯状の正極２が得られ
る。Next, the positive electrode sheet is cut out in a strip shape. Then, a lead wire is welded to a portion where the positive electrode active material layer is not formed to form a positive electrode terminal 7. Examples of the material used for the positive electrode terminal 7 include aluminum, titanium, and alloys thereof. Thus, the belt-shaped positive electrode 2 is obtained.
【００４６】また、負極３は、負極活物質と結着剤とを
含有する負極合剤を、負極集電体となる例えば銅箔等の
金属箔上に均一に塗布、乾燥することにより負極活物質
層が形成されて負極シートが作製される。ここで、この
負極合剤には、負極活物質である鱗片状黒鉛と、当該鱗
片状黒鉛に加えて、球状黒鉛、塊状黒鉛、繊維状黒鉛、
難黒鉛化炭素又はカーボンブラックのうち少なくとも一
種類以上の炭素材料とからなる負極活物質混合体が用い
られる。また、上記負極合剤の結着剤としては、公知の
結着剤を用いることができるほか、上記負極合剤に公知
の添加剤等を添加することができる。The negative electrode 3 is formed by uniformly applying a negative electrode mixture containing a negative electrode active material and a binder on a metal foil such as a copper foil serving as a negative electrode current collector and drying the same. The material layer is formed to produce a negative electrode sheet. Here, in the negative electrode mixture, flaky graphite as a negative electrode active material, in addition to the flaky graphite, spherical graphite, massive graphite, fibrous graphite,
A negative electrode active material mixture composed of at least one kind of carbon material of non-graphitizable carbon or carbon black is used. As the binder for the negative electrode mixture, a known binder can be used, and a known additive or the like can be added to the negative electrode mixture.
【００４７】次に、負極シートを帯状に切り出す。そし
て、負極集電体の負極活物質層の非形成部分にリード線
を溶接して負極端子８とする。負極端子８に使用される
材料の例としては、銅、ニッケル、又はこれらの合金な
どが挙げられる。このようにして帯状の負極３が得られ
る。Next, the negative electrode sheet is cut out in a band shape. Then, a lead wire is welded to a portion of the negative electrode current collector where the negative electrode active material layer is not formed to form a negative electrode terminal 8. Examples of the material used for the negative electrode terminal 8 include copper, nickel, and alloys thereof. Thus, the strip-shaped negative electrode 3 is obtained.
【００４８】次に、正極活物質層及び負極活物質層上に
ゲル状電解質層４を形成する。ゲル状電解質層４を形成
するには、まず、非水溶媒に電解質塩を溶解させて非水
電解液を作製する。そして、この非水電解液にマトリク
スポリマを添加し、よく攪拌してマトリクスポリマを溶
解させてゾル状の電解質溶液を得る。Next, a gel electrolyte layer 4 is formed on the positive electrode active material layer and the negative electrode active material layer. To form the gel electrolyte layer 4, first, an electrolyte salt is dissolved in a non-aqueous solvent to prepare a non-aqueous electrolyte. Then, a matrix polymer is added to the non-aqueous electrolyte, and the mixture is stirred well to dissolve the matrix polymer to obtain a sol electrolyte solution.
【００４９】次に、この電解質溶液を正極活物質層及び
負極活物質上に所定量塗布する。続いて、室温にて冷却
することによりマトリクスポリマがゲル化して、正極活
物質層及び負極活物質上にゲル状電解質層４が形成され
る。Next, a predetermined amount of this electrolyte solution is applied on the positive electrode active material layer and the negative electrode active material. Subsequently, the matrix polymer is gelled by cooling at room temperature, and the gel electrolyte layer 4 is formed on the positive electrode active material layer and the negative electrode active material.
【００５０】そして、以上のようにして作製された帯状
の正極２と負極３とを、ゲル状電解質層４を介して張り
合わせてプレスし、電極積層体とする。さらに、この電
極積層体を長手方向に巻回して電極巻回体５とする。Then, the strip-shaped positive electrode 2 and negative electrode 3 produced as described above are bonded together via the gel electrolyte layer 4 and pressed to obtain an electrode laminate. Further, the electrode laminate is wound in the longitudinal direction to form an electrode wound body 5.
【００５１】最後に、この電極巻回体５を、絶縁材料か
らなる外装フィルム６で挟み、そして、外装フィルム６
の外周縁部を封口し、正極端子７と負極端子８とを外装
フィルム６の封口部に挟み込むとともに電極巻回体５を
外装フィルム６中に密閉する。さらに、外装フィルム６
によってパックされた状態で、電極巻回体５に対して熱
処理を施す。以上のようにしてゲル状電解質電池１が完
成する。Finally, the electrode winding body 5 is sandwiched between exterior films 6 made of an insulating material.
Is sealed, the positive electrode terminal 7 and the negative electrode terminal 8 are sandwiched between the sealing portions of the exterior film 6, and the wound electrode body 5 is hermetically sealed in the exterior film 6. Furthermore, the exterior film 6
In the state where the electrode winding body 5 is packed, heat treatment is performed on the electrode winding body 5. As described above, the gel electrolyte battery 1 is completed.
【００５２】なお、上述した実施の形態では、帯状の正
極２と帯状の負極３とを積層し、さらに長手方向に巻回
して電極巻回体６とした場合を例に挙げて説明したが、
本発明はこれに限定されるものではなく、矩形状の正極
２と矩形状の負極３とを積層して電極積層体とした場合
や、電極積層体を交互に折り畳んだ場合にも適用可能で
ある。In the above-described embodiment, the case where the strip-shaped positive electrode 2 and the strip-shaped negative electrode 3 are stacked and wound in the longitudinal direction to form the electrode winding body 6 has been described as an example.
The present invention is not limited to this, and is also applicable to a case where a rectangular positive electrode 2 and a rectangular negative electrode 3 are laminated to form an electrode laminate, or a case where the electrode laminate is alternately folded. is there.
【００５３】また、上述した実施の形態では、非水電解
質電池として、ゲル状電解質を用いたゲル状電解質電池
１を例に挙げて説明したが、本発明はこれに限定される
ものではなく、非水電解液を用いた非水電解液電池や、
膨潤溶媒を含まない固体電解質を用いた固体電解質電池
についても適用可能である。In the above-described embodiment, the gel electrolyte battery 1 using a gel electrolyte has been described as an example of the nonaqueous electrolyte battery. However, the present invention is not limited to this. Non-aqueous electrolyte batteries using non-aqueous electrolytes,
The present invention is also applicable to a solid electrolyte battery using a solid electrolyte containing no swelling solvent.
【００５４】さらに、本発明に係る非水電解質電池は、
シート型、円筒型、角型、コイン型等、その形状につい
ては特に限定されることはなく、また、薄型、大型等の
種々の大きさにすることができる。また、本発明は、一
次電池についても二次電池についても適用可能である。Further, the non-aqueous electrolyte battery according to the present invention
There is no particular limitation on the shape such as a sheet type, a cylindrical type, a square type, a coin type and the like, and it can be formed into various sizes such as a thin type and a large type. Further, the present invention is applicable to both primary batteries and secondary batteries.
【００５５】[0055]
【実施例】つぎに、本発明の効果を確認すべく行った実
施例について説明するが、本発明はこれに限定されるも
のではない。EXAMPLES Next, examples will be described in which the effects of the present invention are confirmed, but the present invention is not limited to these examples.
【００５６】〈実施例１〉まず、負極をつぎのようにし
て作製した。Example 1 First, a negative electrode was manufactured as follows.
【００５７】負極活物質である粉砕した鱗片状黒鉛を９
９重量部と、球状黒鉛を１重量部とを混合した粉末から
なる負極活物質混合体を９０重量部と、結着剤としてポ
リ（ビニリデンフルオライド−ｃｏ−ヘキサフルオロプ
ロピレン）を１０重量部とを混合して負極合剤を調製
し、さらにこれをＮ−メチル−２−ピロリドンに分散さ
せてスラリー状とした。そして、このスラリーを負極集
電体である厚さ２０μｍの帯状銅箔の両面に均一に塗布
し、乾燥後、ロールプレス機で圧縮成型し、負極を作製
した。なお、負極集電体の負極活物質層の非形成部分
に、例えばニッケル製のリード線を溶接して負極端子と
した。The crushed flaky graphite as the negative electrode active material was mixed with 9
90 parts by weight of a negative electrode active material mixture comprising 9 parts by weight and a powder obtained by mixing 1 part by weight of spheroidal graphite, and 10 parts by weight of poly (vinylidene fluoride-co-hexafluoropropylene) as a binder. Was mixed to prepare a negative electrode mixture, which was further dispersed in N-methyl-2-pyrrolidone to form a slurry. Then, this slurry was uniformly applied to both surfaces of a 20 μm-thick strip-shaped copper foil as a negative electrode current collector, dried, and then compression-molded with a roll press machine to produce a negative electrode. Note that a lead wire made of, for example, nickel was welded to a portion of the negative electrode current collector where the negative electrode active material layer was not formed, to form a negative electrode terminal.
【００５８】また、正極をつぎのようにして作製した。A positive electrode was produced as follows.
【００５９】まず、炭酸リチウムと炭酸コバルトとをモ
ル比で０．５：１の割合で混合し、空気中９００℃で５
時間焼成して、正極活物質となるＬｉＣｏＯ2を得た。First, lithium carbonate and cobalt carbonate were mixed at a molar ratio of 0.5: 1, and were mixed in air at 900 ° C. for 5 minutes.
After firing for a period of time, LiCoO 2 serving as a positive electrode active material was obtained.
【００６０】次に、得られたＬｉＣｏＯ2を９１重量部
と、導電剤として黒鉛を６重量部と、結着剤としてポリ
（ビニリデンフルオライド−ｃｏ−ヘキサフルオロプロ
ピレン）を１０重量部とを混合して正極合剤を調製し、
さらにこれをＮ−メチル−２−ピロリドンに分散させて
スラリー状とした。そして、このスラリーを正極集電体
である厚さ２０μｍの帯状アルミニウム箔の両面に均一
に塗布し、乾燥後、ロールプレス機で圧縮成型し、正極
を作製した。なお、正極集電体の正極活物質層の非形成
部分に、例えばアルミニウム製のリード線を溶接して正
極端子とした。Next, 91 parts by weight of the obtained LiCoO 2 , 6 parts by weight of graphite as a conductive agent, and 10 parts by weight of poly (vinylidene fluoride-co-hexafluoropropylene) as a binder were mixed. To prepare a positive electrode mixture,
This was further dispersed in N-methyl-2-pyrrolidone to form a slurry. Then, the slurry was uniformly applied to both sides of a 20 μm-thick strip-shaped aluminum foil as a positive electrode current collector, dried, and then compression-molded with a roll press to produce a positive electrode. In addition, a lead wire made of, for example, aluminum was welded to a portion of the positive electrode current collector where the positive electrode active material layer was not formed to form a positive electrode terminal.
【００６１】次に、ゲル状電解質層をつぎのようにして
得た。Next, a gel electrolyte layer was obtained as follows.
【００６２】まずエチレンカーボネートを４２．５重量
部と、プロピレンカーボネートを４２．５重量部と、Ｌ
ｉＰＦ6を１５重量部とを混合して可塑剤を調製した。
この可塑剤の３０重量部に、ポリ（ビニリデンフルオラ
イド−ｃｏ−ヘキサフルオロプロピレン）を１０重量部
と、ジメチルカーボネートを６０重量部とを混合して電
解質溶液を調製した。First, 42.5 parts by weight of ethylene carbonate, 42.5 parts by weight of propylene carbonate, L
A plasticizer was prepared by mixing iPF 6 with 15 parts by weight.
To 30 parts by weight of this plasticizer, 10 parts by weight of poly (vinylidene fluoride-co-hexafluoropropylene) and 60 parts by weight of dimethyl carbonate were mixed to prepare an electrolyte solution.
【００６３】この電解質溶液を正極活物質層、負極活物
質層上に均一に塗布し、含浸させ、常温で８時間放置
し、ジメチルカーボネートを気化、除去してゲル状電解
質層を得た。This electrolyte solution was uniformly applied on the positive electrode active material layer and the negative electrode active material layer, impregnated, and allowed to stand at room temperature for 8 hours to vaporize and remove dimethyl carbonate to obtain a gel electrolyte layer.
【００６４】そして、以上のようにして作製された正極
と負極とを、ゲル状電解質層が形成された側を対向させ
て張り合わせ、長手方向に巻回することで、５ｃｍ×４
ｃｍ×０．４ｃｍの電極巻回体を得た。Then, the positive electrode and the negative electrode produced as described above are bonded together with the side on which the gel electrolyte layer is formed facing each other, and wound in the longitudinal direction to obtain a 5 cm × 4
An electrode wound body of cm × 0.4 cm was obtained.
【００６５】この電極巻回体を、ポリプロピレン／アル
ミニウム／ナイロンの３層構造からなるラミネートフィ
ルムにて密閉することによりゲル状電解質電池を得た。
なお、このとき、正極端子と負極端子とを外装フィルム
の封口部に挟み込んだ。The wound electrode body was sealed with a laminate film having a three-layer structure of polypropylene / aluminum / nylon to obtain a gel electrolyte battery.
At this time, the positive electrode terminal and the negative electrode terminal were sandwiched between the sealing portions of the exterior film.
【００６６】〈実施例２〉負極活物質混合体を構成する
鱗片状黒鉛と球状黒鉛との比を９５：５の割合としたこ
と以外は、実施例１と同様にして負極を作製し、この負
極を用いてゲル状電解質電池を作製した。Example 2 A negative electrode was prepared in the same manner as in Example 1 except that the ratio of the scale-like graphite to the spherical graphite constituting the negative electrode active material mixture was 95: 5. A gel electrolyte battery was prepared using the negative electrode.
【００６７】〈実施例３〉負極活物質混合体を構成する
鱗片状黒鉛と球状黒鉛との比を８０：２０の割合とした
こと以外は、実施例１と同様にして負極を作製し、この
負極を用いてゲル状電解質電池を作製した。Example 3 A negative electrode was prepared in the same manner as in Example 1 except that the ratio of flaky graphite to spherical graphite constituting the negative electrode active material mixture was set at a ratio of 80:20. A gel electrolyte battery was prepared using the negative electrode.
【００６８】〈実施例４〉負極活物質混合体を構成する
鱗片状黒鉛と球状黒鉛との比を７０：３０の割合とした
こと以外は、実施例１と同様にして負極を作製し、この
負極を用いてゲル状電解質電池を作製した。Example 4 A negative electrode was prepared in the same manner as in Example 1 except that the ratio of flaky graphite to spherical graphite constituting the negative electrode active material mixture was set to 70:30. A gel electrolyte battery was prepared using the negative electrode.
【００６９】〈実施例５〉負極活物質混合体を構成する
鱗片状黒鉛と球状黒鉛との比を６０：４０の割合とした
こと以外は、実施例１と同様にして負極を作製し、この
負極を用いてゲル状電解質電池を作製した。Example 5 A negative electrode was prepared in the same manner as in Example 1, except that the ratio of flaky graphite to spherical graphite constituting the negative electrode active material mixture was set at a ratio of 60:40. A gel electrolyte battery was prepared using the negative electrode.
【００７０】〈実施例６〉負極活物質混合体を構成する
鱗片状黒鉛と球状黒鉛との比を５０：５０の割合とした
こと以外は、実施例１と同様にして負極を作製し、この
負極を用いてゲル状電解質電池を作製した。Example 6 A negative electrode was prepared in the same manner as in Example 1 except that the ratio of the scale-like graphite and the spherical graphite constituting the negative electrode active material mixture was set to 50:50. A gel electrolyte battery was prepared using the negative electrode.
【００７１】〈実施例７〉球状黒鉛に代えて塊状黒鉛を
用い、負極活物質混合体を構成する鱗片状黒鉛と塊状黒
鉛との比を８０：２０の割合としたこと以外は、実施例
１と同様にして負極を作製し、この負極を用いてゲル状
電解質電池を作製した。Example 7 Example 1 was repeated except that massive graphite was used instead of spheroidal graphite and the ratio of flake graphite to massive graphite constituting the negative electrode active material mixture was 80:20. In the same manner as in the above, a negative electrode was produced, and a gel electrolyte battery was produced using the negative electrode.
【００７２】〈実施例８〉球状黒鉛に代えて塊状黒鉛を
用い、負極活物質混合体を構成する鱗片状黒鉛と塊状黒
鉛との比を６０：４０の割合としたこと以外は、実施例
１と同様にして負極を作製し、この負極を用いてゲル状
電解質電池を作製した。Example 8 Example 1 was repeated except that massive graphite was used instead of spheroidal graphite, and the ratio of flaky graphite to massive graphite constituting the negative electrode active material mixture was 60:40. In the same manner as in the above, a negative electrode was produced, and a gel electrolyte battery was produced using the negative electrode.
【００７３】〈実施例９〉球状黒鉛に代えて繊維状黒鉛
を用い、負極活物質混合体を構成する鱗片状黒鉛と繊維
状黒鉛との比を８０：２０の割合としたこと以外は、実
施例１と同様にして負極を作製し、この負極を用いてゲ
ル状電解質電池を作製した。<Example 9> A fibrous graphite was used in place of the spherical graphite, and the ratio of the scale-like graphite and the fibrous graphite constituting the negative electrode active material mixture was set to a ratio of 80:20. A negative electrode was produced in the same manner as in Example 1, and a gel electrolyte battery was produced using this negative electrode.
【００７４】〈実施例１０〉球状黒鉛に代えて難黒鉛化
炭素を用い、負極活物質混合体を構成する鱗片状黒鉛と
難黒鉛化炭素との比を８０：２０の割合としたこと以外
は、実施例１と同様にして負極を作製し、この負極を用
いてゲル状電解質電池を作製した。Example 10 Except that spheroidal graphite was replaced with non-graphitizable carbon and the ratio of flaky graphite to non-graphitizable carbon constituting the negative electrode active material mixture was set at a ratio of 80:20. A negative electrode was prepared in the same manner as in Example 1, and a gel electrolyte battery was prepared using the negative electrode.
【００７５】〈実施例１１〉球状黒鉛に代えてカーボン
ブラックを用い、負極活物質混合体を構成する鱗片状黒
鉛とカーボンブラックとの比を８０：２０の割合とした
こと以外は、実施例１と同様にして負極を作製し、この
負極を用いてゲル状電解質電池を作製した。<Example 11> Example 1 was repeated except that carbon black was used in place of the spheroidal graphite, and the ratio of flaky graphite and carbon black constituting the negative electrode active material mixture was 80:20. In the same manner as in the above, a negative electrode was produced, and a gel electrolyte battery was produced using the negative electrode.
【００７６】〈実施例１２〉鱗片状黒鉛と球状黒鉛とカ
ーボンブラックとが８０：１５：５の比で混合されてな
る負極活物質混合体を用いたこと以外は、実施例１と同
様にして負極を作製し、この負極を用いてゲル状電解質
電池を作製した。Example 12 The same procedure as in Example 1 was carried out except that a negative electrode active material mixture in which flaky graphite, spherical graphite, and carbon black were mixed at a ratio of 80: 15: 5 was used. A negative electrode was prepared, and a gel electrolyte battery was prepared using the negative electrode.
【００７７】〈実施例１３〉鱗片状黒鉛と球状黒鉛と繊
維状黒鉛とが８０：１５：５の比で混合されてなる負極
活物質混合体を用いたこと以外は、実施例１と同様にし
て負極を作製し、この負極を用いてゲル状電解質電池を
作製した。Example 13 The same procedure as in Example 1 was performed except that a negative electrode active material mixture in which flaky graphite, spherical graphite, and fibrous graphite were mixed at a ratio of 80: 15: 5 was used. Thus, a negative electrode was prepared, and a gel electrolyte battery was prepared using the negative electrode.
【００７８】〈比較例１〉負極活物質として鱗片状黒鉛
のみを用いたこと以外は、実施例１と同様にして負極を
作製し、この負極を用いてゲル状電解質電池を作製し
た。Comparative Example 1 A negative electrode was prepared in the same manner as in Example 1 except that only flaky graphite was used as the negative electrode active material, and a gel electrolyte battery was prepared using the negative electrode.
【００７９】〈比較例２〉負極活物質混合体を構成する
鱗片状黒鉛と球状黒鉛との比を９９．５：０．５の割合
としたこと以外は、実施例１と同様にして負極を作製
し、この負極を用いてゲル状電解質電池を作製した。Comparative Example 2 A negative electrode was prepared in the same manner as in Example 1 except that the ratio of the scale-like graphite and the spherical graphite constituting the negative electrode active material mixture was 99.5: 0.5. Then, a gel electrolyte battery was manufactured using the negative electrode.
【００８０】〈比較例３〉負極活物質混合体を構成する
鱗片状黒鉛と球状黒鉛との比を３０：７０の割合とした
こと以外は、実施例１と同様にして負極を作製し、この
負極を用いてゲル状電解質電池を作製した。Comparative Example 3 A negative electrode was prepared in the same manner as in Example 1 except that the ratio of flaky graphite to spherical graphite constituting the negative electrode active material mixture was set at a ratio of 30:70. A gel electrolyte battery was prepared using the negative electrode.
【００８１】〈比較例４〉負極活物質として球状黒鉛の
みを用いたこと以外は、実施例１と同様にして負極を作
製し、この負極を用いてゲル状電解質電池を作製した。Comparative Example 4 A negative electrode was produced in the same manner as in Example 1 except that only spherical graphite was used as the negative electrode active material, and a gel electrolyte battery was produced using this negative electrode.
【００８２】〈比較例５〉球状黒鉛に代えて塊状黒鉛を
用い、負極活物質混合体を構成する鱗片状黒鉛と塊状黒
鉛との比を４０：６０の割合としたこと以外は、実施例
１と同様にして負極を作製し、この負極を用いてゲル状
電解質電池を作製した。Comparative Example 5 Example 1 was repeated except that massive graphite was used instead of spherical graphite, and the ratio of flaky graphite to massive graphite constituting the negative electrode active material mixture was 40:60. In the same manner as in the above, a negative electrode was produced, and a gel electrolyte battery was produced using the negative electrode.
【００８３】〈比較例６〉球状黒鉛に代えて繊維状黒鉛
を用い、負極活物質混合体を構成する鱗片状黒鉛と繊維
状黒鉛との比を４０：６０の割合としたこと以外は、実
施例１と同様にして負極を作製し、この負極を用いてゲ
ル状電解質電池を作製した。<Comparative Example 6> [0083] Except that fibrous graphite was used instead of spherical graphite, and the ratio of flaky graphite to fibrous graphite constituting the negative electrode active material mixture was set to a ratio of 40:60. A negative electrode was produced in the same manner as in Example 1, and a gel electrolyte battery was produced using this negative electrode.
【００８４】〈比較例７〉球状黒鉛に代えて難黒鉛化炭
素を用い、負極活物質混合体を構成する鱗片状黒鉛と難
黒鉛化炭素との比を４０：６０の割合としたこと以外
は、実施例１と同様にして負極を作製し、この負極を用
いてゲル状電解質電池を作製した。<Comparative Example 7> Except that non-graphitizable carbon was used instead of spheroidal graphite, and the ratio of flaky graphite to non-graphitizable carbon constituting the negative electrode active material mixture was set at a ratio of 40:60. A negative electrode was prepared in the same manner as in Example 1, and a gel electrolyte battery was prepared using the negative electrode.
【００８５】〈比較例８〉球状黒鉛に代えてカーボンブ
ラックを用い、負極活物質混合体を構成する鱗片状黒鉛
とカーボンブラックとの比を４０：６０の割合としたこ
と以外は、実施例１と同様にして負極を作製し、この負
極を用いてゲル状電解質電池を作製した。Comparative Example 8 Example 1 was repeated except that carbon black was used in place of spheroidal graphite, and the ratio of flaky graphite and carbon black constituting the negative electrode active material mixture was 40:60. In the same manner as in the above, a negative electrode was produced, and a gel electrolyte battery was produced using the negative electrode.
【００８６】〈比較例９〉鱗片状黒鉛と球状黒鉛とカー
ボンブラックとが４０：４０：２０の比で混合されてな
る負極活物質混合体を用いたこと以外は、実施例１と同
様にして負極を作製し、この負極を用いてゲル状電解質
電池を作製した。Comparative Example 9 The procedure of Example 1 was repeated, except that a negative electrode active material mixture in which flaky graphite, spherical graphite and carbon black were mixed at a ratio of 40:40:20 was used. A negative electrode was prepared, and a gel electrolyte battery was prepared using the negative electrode.
【００８７】そして、以上のようにして作製されたゲル
状電解質電池について、負極集電体−負極活物質層間の
剥離強度、負極活物質の放電容量を測定し、さらに、作
製したゲル状電解質電池についての負荷特性及びサイク
ル特性の特性評価試験を行った。The peel strength between the negative electrode current collector and the negative electrode active material layer and the discharge capacity of the negative electrode active material were measured for the gel electrolyte battery prepared as described above. A characteristic evaluation test of load characteristics and cycle characteristics was carried out.
【００８８】負極集電体−負極活物質層間の剥離強度
は、いわゆるＴ字剥離試験により測定した。The peel strength between the negative electrode current collector and the negative electrode active material layer was measured by a so-called T-shaped peel test.
【００８９】Ｔ字剥離試験は、図４に示すように、幅３
０ｍｍ、長さ２００ｍｍの負極３の、負極活物質層３ａ
表面に粘着テープ１０を貼り、さらにこの負極集電体３
ｂ側をステンレス板１１上に貼り付け、図４中Ａ部分を
固定した。この一部を剥がし、その剥がした端をステン
レス板１１に対して水平方向、すなわち図４中矢印Ｂ方
向に引っ張ることによって１０ｃｍ剥がした。この時に
要した力の平均値を剥離強度とした。As shown in FIG.
Negative electrode active material layer 3a of negative electrode 3 having a length of 0 mm and a length of 200 mm
An adhesive tape 10 is attached to the surface, and the negative electrode current collector 3
The b side was pasted on the stainless steel plate 11 and the portion A in FIG. 4 was fixed. This part was peeled off, and the peeled end was pulled in a horizontal direction with respect to the stainless steel plate 11, that is, in the direction of arrow B in FIG. The average value of the force required at this time was defined as the peel strength.
【００９０】負極活物質の放電容量については、同じ負
極活物質混合体を用いて図５に示すようなコイン型電池
２０を作製し、このコイン型電池２０を用いて評価し
た。With respect to the discharge capacity of the negative electrode active material, a coin-type battery 20 as shown in FIG.
【００９１】コイン型電池２０の作成方法としては、ま
ず上述の方法と同様にして得られる負極合剤を集電体と
なるニッケルメッシュ（ニッケル繊維径２０μｍ）上に
塗布し、乾燥して負極活物質層を形成した。そして、負
極活物質層が形成されたニッケルメッシュを、直径１
５．５ｍｍの円板状に打ち抜くことによりペレット状の
負極２１とした。As a method of manufacturing the coin-type battery 20, first, a negative electrode mixture obtained in the same manner as described above is applied on a nickel mesh (nickel fiber diameter: 20 μm) serving as a current collector, dried, and dried. A material layer was formed. Then, the nickel mesh on which the negative electrode active material layer was formed was crushed to a diameter of 1 mm.
The negative electrode 21 in the form of a pellet was punched out into a 5.5 mm disc.
【００９２】また、リチウム金属箔を負極と略同形に打
ち抜くことにより正極２２とした。Further, a positive electrode 22 was obtained by punching a lithium metal foil into substantially the same shape as the negative electrode.
【００９３】また、エチレンカーボネートと、プロピレ
ンカーボネートとの等容量混合溶媒中に、ＬｉＰＦ6を
１ｍｏｌ／ｌの濃度で溶解させることにより非水電解液
を調製した。A non-aqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1 mol / l in a mixed solvent of ethylene carbonate and propylene carbonate in equal volumes.
【００９４】以上のようにして得られた負極２１を負極
缶２３に収容し、正極２２を正極缶２４に収容し、正極
２２と負極２１との間に、ポリプロピレン製多孔質膜か
らなるセパレータ２５を配した。 正極缶２４及び負極
缶２３内に非水電解液を注入し、正極缶２４と負極缶２
３とを絶縁ガスケット２６を介してかしめて固定するこ
とにより、直径が２０ｍｍ、厚さが２．５ｍｍのコイン
型電池２０を作製した。The negative electrode 21 obtained as described above is accommodated in a negative electrode can 23, the positive electrode 22 is accommodated in a positive electrode can 24, and a separator 25 made of a porous polypropylene film is interposed between the positive electrode 22 and the negative electrode 21. Was arranged. A non-aqueous electrolyte is injected into the positive electrode can 24 and the negative electrode can 23, and the positive electrode can 24 and the negative electrode can 2
3 was caulked and fixed via an insulating gasket 26 to produce a coin-type battery 20 having a diameter of 20 mm and a thickness of 2.5 mm.
【００９５】そして、得られたコイン型電池２０につい
て、理論容量の１０時間率充電を定電圧定電流充電で下
限０Ｖまで行い、次に１０時間率定電流放電を終止電圧
１．５Ｖ間で行った。この時の放電容量を負極活物質の
放電容量とした。Then, with respect to the obtained coin-type battery 20, a 10-hour rate charging of a theoretical capacity is performed to a lower limit of 0 V by a constant-voltage constant-current charging, and then a 10-hour rate constant-current discharging is performed at a final voltage of 1.5 V. Was. The discharge capacity at this time was defined as the discharge capacity of the negative electrode active material.
【００９６】負荷特性としては、ゲル状電解質電池につ
いて、まず理論容量の１／３時間率放電（３Ｃ）を行
い、つぎのように評価した。まず、各電池に対して、２
３℃、定電流定電圧充電を４．２Ｖまで１０時間行い、
次に３Ｃの定電流放電を終止電圧３．２Ｖ間で行い放電
容量を決定した。そして、これから求められる平均電圧
から各時間率放電での出力を１／５Ｃに対する１００分
率として算出した。また、このときの放電容量に対する
電池の体積エネルギー密度を算出した。Regarding the load characteristics, the gel electrolyte battery was first discharged at a rate of 1/3 of the theoretical capacity (3C), and evaluated as follows. First, for each battery,
Perform constant-current constant-voltage charging at 3 ° C. to 4.2 V for 10 hours,
Next, a constant current discharge of 3 C was performed at a final voltage of 3.2 V to determine a discharge capacity. The output at each time rate discharge was calculated from the average voltage obtained as a percentage of 1 / 5C. Further, the volume energy density of the battery with respect to the discharge capacity at this time was calculated.
【００９７】サイクル特性としては、各電池に対して、
２３℃で定電流定電圧充電を上限４．２Ｖまで行い、次
に、理論容量の２時間率放電（１／２Ｃ）の定電流放電
を終止電圧３．２Ｖ間で行った。これを１サイクルとし
て５００サイクル繰り返した。そして、これから求めら
れる平均電圧から時間率放電での出力をサイクル初期
（第１サイクル目）の１／５Ｃに対する１００分率とし
て算出した。As for the cycle characteristics, for each battery,
At 23 ° C., constant-current constant-voltage charging was performed up to an upper limit of 4.2 V, and then constant-current discharging at a theoretical capacity of 2 hours (1/2 C) was performed at a final voltage of 3.2 V. This was repeated as 500 cycles for one cycle. Then, the output at the time rate discharge was calculated from the average voltage obtained as a percentage of 1 / 5C at the beginning of the cycle (first cycle).
【００９８】実施例１〜実施例１３、比較例１〜比較例
９の電池についての各電池特性評価結果を表１に示す。Table 1 shows the evaluation results of the battery characteristics of the batteries of Examples 1 to 13 and Comparative Examples 1 to 9.
【００９９】[0099]
【表１】 [Table 1]
【０１００】まず、負極集電体−負極活物質層間の剥離
強度についてみてみると、炭素材料を添加しなかった比
較例１及び添加量が０．５重量％の比較例２では、剥離
強度が極端に低く、負極活物質層が負極集電体から剥離
しやすいことがわかる。添加した炭素材料の割合の増加
に伴って剥離強度も増加するが、炭素材料の割合が２０
重量％程度になると飽和し、それ以降は、炭素材料の添
加割合が増加しても、剥離強度の向上はほとんど見られ
ない。First, regarding the peel strength between the negative electrode current collector and the negative electrode active material layer, in Comparative Example 1 in which no carbon material was added and Comparative Example 2 in which the addition amount was 0.5% by weight, the peel strength was low. It is extremely low, indicating that the negative electrode active material layer is easily separated from the negative electrode current collector. Although the peel strength increases with an increase in the ratio of the added carbon material, the ratio of the carbon material is 20%.
When the content becomes about wt%, the saturation is achieved, and thereafter, even if the addition ratio of the carbon material increases, almost no improvement in the peel strength is observed.
【０１０１】また、負極集電体−負極活物質層間の剥離
強度が大きくなるほど、電池のサイクル特性も良好な値
が得られていることがわかる。It can also be seen that the higher the peel strength between the negative electrode current collector and the negative electrode active material layer, the better the cycle characteristics of the battery.
【０１０２】一方、炭素材料の添加割合が増えるに従っ
て、負極活物質の割合が低下することになり、放電容量
は低下してしまう。また、負荷特性についても、炭素材
料の添加割合が５重量％程度までは向上効果が顕著にみ
られるが、それ以上になると添加炭素材料の特性が強く
現れるようになってしまい、負荷特性の向上効果はそれ
ほど見られなくなる。On the other hand, as the addition ratio of the carbon material increases, the ratio of the negative electrode active material decreases, and the discharge capacity decreases. Also, with respect to the load characteristics, the improvement effect is remarkably seen up to the addition ratio of the carbon material of about 5% by weight, but when it exceeds that, the characteristics of the added carbon material become stronger and the load characteristics are improved. The effect is less noticeable.
【０１０３】また、電池の単位面積あたりの放電容量を
等しくしようとした場合、炭素材料の添加量が増加する
に従って、負極の厚みが厚くなることがわかる。このこ
とは、炭素材料を添加することによって電池の体積エネ
ルギー密度を低下させることを意味する。３Ｃ放電時の
体積エネルギー密度については、炭素材料の添加量が５
重量％以上、３０重量％以下のときに、良好な値が得ら
れていることがわかる。Also, when trying to equalize the discharge capacity per unit area of the battery, it can be seen that the thickness of the negative electrode increases as the addition amount of the carbon material increases. This means that the volume energy density of the battery is reduced by adding the carbon material. Regarding the volume energy density at the time of 3C discharge, the addition amount of the carbon material is 5%.
It can be seen that good values are obtained when the content is not less than 30% by weight and not less than 30% by weight.
【０１０４】以上の結果から、負極活物質である鱗片状
黒鉛に添加する炭素材料の添加量を、１重量％以上、５
０重量％の範囲としたときに、好ましい結果が得られて
いることがわかった。その中でも、炭素材料の添加量を
５重量％以上、３０重量％以下の範囲としたときに特に
好ましい結果が得られていることがわかった。From the above results, it was found that the amount of the carbon material added to the flaky graphite as the negative electrode active material was 1% by weight or more,
It was found that favorable results were obtained when the content was in the range of 0% by weight. Among them, it was found that particularly preferable results were obtained when the addition amount of the carbon material was in the range of 5% by weight or more and 30% by weight or less.
【０１０５】[0105]
【発明の効果】本発明では、負極活物質である鱗片状黒
鉛に、球状黒鉛、塊状黒鉛、繊維状黒鉛、難黒鉛化炭素
又はカーボンブラックのうち少なくとも一種類以上の炭
素材を混合することで、結着剤成分を増加させることな
く、負極活物質層と負極集電体との結着性を高めるとと
もに、負極活物質の利用効率を向上させて、高容量かつ
高負荷、高サイクル特性を有する非水電解質電池を実現
することができる。According to the present invention, at least one kind of carbon material of spheroidal graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black is mixed with flaky graphite as a negative electrode active material. Without increasing the amount of the binder component, the binding property between the negative electrode active material layer and the negative electrode current collector is increased, and the utilization efficiency of the negative electrode active material is improved to achieve high capacity, high load, and high cycle characteristics. The nonaqueous electrolyte battery having the above can be realized.
【図１】本実施の形態に係るゲル状電解質電池の一構成
例を示す斜視図である。FIG. 1 is a perspective view showing one configuration example of a gel electrolyte battery according to the present embodiment.
【図２】図１中、Ｘ1−Ｘ2線における断面図である。FIG. 2 is a sectional view taken along line X 1 -X 2 in FIG.
【図３】正極及び負極が電極巻回体とされた状態を示す
斜視図である。FIG. 3 is a perspective view showing a state in which a positive electrode and a negative electrode are formed into an electrode wound body.
【図４】実施例における剥離強度試験の方法を模式的に
示す断面図である。FIG. 4 is a cross-sectional view schematically showing a method of a peel strength test in an example.
【図５】負極放電容量の評価で用いたコイン型電池の構
成例を示す断面図である。FIG. 5 is a cross-sectional view illustrating a configuration example of a coin-type battery used in evaluation of a negative electrode discharge capacity.
１ ゲル状電解質電池、 ２ 正極、 ３ 負極、 ４
ゲル状電解質層、５ 電極巻回体、 ６ 外装フィル
ム、 ７ 正極端子、 ８ 負極端子1 gel electrolyte battery, 2 positive electrode, 3 negative electrode, 4
Gel electrolyte layer, 5 electrode wound body, 6 exterior film, 7 positive electrode terminal, 8 negative electrode terminal
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原 富太郎 東京都品川区北品川６丁目７番35号 ソニ ー株式会社内 Ｆターム(参考） 5H029 AJ03 AJ05 AK03 AL06 AL07 AL08 AM00 AM03 AM04 AM05 AM07 AM16 BJ03 BJ04 BJ14 5H050 AA07 AA08 BA17 CA07 CA08 CA09 CB07 CB08 CB09 HA01 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tomitaro Hara 6-7-35 Kita Shinagawa, Shinagawa-ku, Tokyo Sony Corporation F-term (reference) 5H029 AJ03 AJ05 AK03 AL06 AL07 AL08 AM00 AM03 AM04 AM05 AM07 AM16 BJ03 BJ04 BJ14 5H050 AA07 AA08 BA17 CA07 CA08 CA09 CB07 CB08 CB09 HA01
Claims (3)
鉛、塊状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカーボン
ブラックのうち少なくとも一種類以上の炭素材料とから
なる負極活物質混合体を含有し、 当該負極活物質混合体は、上記一種類以上の炭素材料を
１重量％以上、５０重量％以下の範囲で含有することを
特徴とする負極。1. A negative electrode active material mixture comprising flaky graphite as a negative electrode active material and at least one kind of carbon material among spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon or carbon black. The negative electrode, wherein the negative electrode active material mixture contains the one or more carbon materials in a range of 1% by weight or more and 50% by weight or less.
活物質を有する正極と、 リチウムをドープ・脱ドープ可能な負極活物質を有する
負極と、 正極と負極との間に介在される非水電解質とを備え、 上記負極は、負極活物質である鱗片状黒鉛と、球状黒
鉛、塊状黒鉛、繊維状黒鉛、難黒鉛化炭素又はカーボン
ブラックのうち少なくとも一種類以上の炭素材料とから
なる負極活物質混合体を含有し、 当該負極活物質混合体は、上記一種類以上の炭素材料を
１重量％以上、５０重量％以下の範囲で含有することを
特徴とする非水電解質電池。2. A positive electrode having a positive electrode active material capable of doping and undoping lithium, a negative electrode having a negative electrode active material capable of doping and undoping lithium, and a non-aqueous electrolyte interposed between the positive electrode and the negative electrode The negative electrode comprises a flaky graphite as a negative electrode active material, and a negative electrode active material comprising at least one or more carbon materials among spherical graphite, massive graphite, fibrous graphite, non-graphitizable carbon, and carbon black. A nonaqueous electrolyte battery comprising a mixture, wherein the negative electrode active material mixture contains the one or more carbon materials in an amount of 1% by weight or more and 50% by weight or less.
を含有する非水電解液がマトリクスポリマによってゲル
状とされてなるゲル状電解質であることを特徴とする請
求項２記載の非水電解質電池。3. The non-aqueous electrolyte according to claim 2, wherein the non-aqueous electrolyte is a gel electrolyte obtained by gelling a non-aqueous electrolyte containing an electrolyte and a swelling solvent with a matrix polymer. Electrolyte battery.
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|---|---|---|---|
| JP2000185070A JP2002008655A (en) | 2000-06-20 | 2000-06-20 | Negative electrode and non-aqueous electrolyte battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000185070A JP2002008655A (en) | 2000-06-20 | 2000-06-20 | Negative electrode and non-aqueous electrolyte battery |
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Family
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