JP2002164052A - Non-aqueous electrolytic battery - Google Patents

Non-aqueous electrolytic battery

Info

Publication number
JP2002164052A
JP2002164052A JP2000360256A JP2000360256A JP2002164052A JP 2002164052 A JP2002164052 A JP 2002164052A JP 2000360256 A JP2000360256 A JP 2000360256A JP 2000360256 A JP2000360256 A JP 2000360256A JP 2002164052 A JP2002164052 A JP 2002164052A
Authority
JP
Japan
Prior art keywords
negative electrode
battery
weight
carbon
carbon black
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2000360256A
Other languages
Japanese (ja)
Other versions
JP4734707B2 (en
Inventor
Shinji Hatake
真次 畑ヶ
Akira Yamaguchi
晃 山口
Tokuo Komaru
篤雄 小丸
Hiroshi Imoto
浩 井本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sony Corp
Original Assignee
Sony Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sony Corp filed Critical Sony Corp
Priority to JP2000360256A priority Critical patent/JP4734707B2/en
Publication of JP2002164052A publication Critical patent/JP2002164052A/en
Application granted granted Critical
Publication of JP4734707B2 publication Critical patent/JP4734707B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous electrolytic battery with superior charging and discharging characteristic and having high battery capacity even in charging and discharging under a low temperature environment. SOLUTION: In this non-aqueous electrolytic battery composed of a positive electrode 2, and a negative electrode 3 including a negative electrode active material, and a negative electrode material composed of fibrous carbon and carbon black, 0.1 wt.% or more and 10 wt.% or less fibrous carbon is included in the negative electrode material, 0.02 wt.% or more and 0.2 wt.% or less carbon black is included in the negative pole material, and a weight ratio of fibrous carbon and carbon black is 0.5 or more and 20 or less.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、正極と、負極活物
質を含有する負極と、電解質とを備える非水電解質電池
に関する。The present invention relates to a non-aqueous electrolyte battery including a positive electrode, a negative electrode containing a negative electrode active material, and an electrolyte.

【０００２】[0002]

【従来の技術】電子技術のめざましい進歩により、電子
機器の小型化、軽量化が次々と実現している。これに伴
い、各種電子機器の電源となる電池に対して、小型化、
軽量化及び高エネルギー密度化が要求されている。2. Description of the Related Art With remarkable progress in electronic technology, electronic devices have been successively reduced in size and weight. Along with this, the size of batteries, which are the power sources for various electronic devices, has been reduced,
Light weight and high energy density are required.

【０００３】現在、一般に用いられている電池として
は、鉛電池、ニッケル・カドミウム電池等の水溶液系二
次電池が主流となっている。これらの電池は、最低限必
要とされるサイクル特性を備えているものの、所望の電
池重量の実現やエネルギー密度の向上が困難である。At present, aqueous secondary batteries such as lead batteries and nickel-cadmium batteries are mainly used as batteries generally used. Although these batteries have the minimum required cycle characteristics, it is difficult to achieve a desired battery weight and improve the energy density.

【０００４】そこで、正極活物質として放電電圧の高い
ＬｉＣｏＯ２に代表されるリチウム含有複合酸化物を用
い、負極材料としてリチウム或いはリチウム合金等を用
いる非水電解液電池が提案されている。Therefore, a non-aqueous electrolyte battery using a lithium-containing composite oxide represented by LiCoO 2 having a high discharge voltage as a positive electrode active material and using lithium or a lithium alloy as a negative electrode material has been proposed.

【０００５】負極材料としてリチウム或いはリチウム合
金等を用いる非水電解液二次電池は、自己放電が少な
く、軽量であるという優れた特性を有しているが、充放
電サイクルの進行に伴い、負極からリチウムがデンドラ
イト状に結晶成長して正極に到達し、電池内部でショー
トが生じるという欠点を有している。このため、負極材
料としてリチウム或いはリチウム合金等を用いる非水電
解液電池では、実用的な急速充放電ができない。A non-aqueous electrolyte secondary battery using lithium or a lithium alloy or the like as an anode material has excellent characteristics such as low self-discharge and light weight. Has a disadvantage in that lithium grows in a dendrite form and reaches the positive electrode, and short-circuit occurs inside the battery. For this reason, in a non-aqueous electrolyte battery using lithium or a lithium alloy or the like as a negative electrode material, practical rapid charging and discharging cannot be performed.

【０００６】そこで、負極活物質として炭素材料等を用
い、負極材料層間へのリチウムのドープ／脱ドープ反応
を負極反応に利用した非水電解質電池、いわゆるリチウ
ムイオン電池が提案されている。リチウムイオン電池
は、充放電サイクルの進行に伴い負極にリチウムが析出
することがなく、良好なサイクル特性を示すという利点
を有している。このような利点を有することから、リチ
ウムイオン電池の研究開発が盛んにおこなわれ、実用化
されている。Therefore, a non-aqueous electrolyte battery using a carbon material or the like as a negative electrode active material and utilizing the doping / dedoping reaction of lithium between the negative electrode material layers for the negative electrode reaction, a so-called lithium ion battery, has been proposed. Lithium ion batteries have the advantage that lithium does not precipitate on the negative electrode as the charge / discharge cycle progresses, and good cycle characteristics are exhibited. Because of these advantages, research and development of lithium ion batteries have been actively conducted and put to practical use.

【０００７】[0007]

【発明が解決しようとする課題】近年、リチウムイオン
電池は、常温環境下のみならず、低温環境下で使用され
る電子機器の駆動用電源として用いられることもある。
しかしながら、従来のリチウムイオン電池を低温環境下
において充放電した場合、負極におけるリチウムイオン
の拡散が滞り、内部抵抗が増加して分極が生じることが
ある。このため、低温環境下においてリチウムイオン電
池を充放電すると、充放電特性が低下して、所望の電池
容量が実現されないという問題がある。In recent years, lithium ion batteries have been used as a power source for driving electronic equipment used not only in a normal temperature environment but also in a low temperature environment.
However, when a conventional lithium-ion battery is charged and discharged in a low-temperature environment, diffusion of lithium ions in the negative electrode may be delayed, causing an increase in internal resistance and polarization. For this reason, when a lithium ion battery is charged and discharged in a low-temperature environment, there is a problem that charge and discharge characteristics are deteriorated and a desired battery capacity cannot be realized.

【０００８】また、リチウムイオン電池の負極には、絶
縁体である結着剤に絡め取られている負極活物質が存在
している。結着剤に絡め取られている負極活物質は、電
気的に孤立してしまうので、充放電反応に寄与できな
い。このため、負極では、本来の容量が十分に引き出さ
れず、リチウムイオン電池としては、本来のエネルギー
密度を十分に引き出すことができないという問題があ
る。The negative electrode of a lithium ion battery contains a negative electrode active material entangled with a binder which is an insulator. The negative electrode active material entangled in the binder is electrically isolated and cannot contribute to the charge / discharge reaction. For this reason, in the negative electrode, the original capacity is not sufficiently extracted, and the lithium ion battery has a problem that the original energy density cannot be sufficiently extracted.

【０００９】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、低温環境下で充放電した場合で
も、良好な充放電特性を有し、電池容量が高い非水電解
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 conventional circumstances, and has good charge / discharge characteristics even when charged and discharged in a low-temperature environment, and has a high battery capacity. The purpose is to provide.

【００１０】[0010]

【課題を解決するための手段】上述の目的を達成するた
めに、本発明に係る非水電解質電池は、リチウムをドー
プ／脱ドープ可能な正極活物質を含有する正極と、リチ
ウムをドープ／脱ドープ可能な負極活物質、繊維状炭素
およびカーボンブラックからなる負極材料を含有する負
極と、非水電解質とを備えることを特徴とする。In order to achieve the above-mentioned object, a non-aqueous electrolyte battery according to the present invention comprises a positive electrode containing a positive electrode active material capable of doping / dedoping lithium, and a lithium doped / dedoped lithium active material. It is characterized by comprising a negative electrode containing a negative electrode active material that can be doped, a negative electrode material composed of fibrous carbon and carbon black, and a non-aqueous electrolyte.

【００１１】以上のように構成された本発明に係る非水
電解質電池では、繊維状炭素が負極活物質の粒子間に介
在し、負極活物質粒界の導電性を高めている。これによ
り、負極に存在する全ての負極活物質が、例えば結着剤
に絡め取られていたとしても電気的に孤立することが無
くなり充放電反応に寄与する。In the non-aqueous electrolyte battery according to the present invention having the above-described structure, fibrous carbon is interposed between particles of the negative electrode active material to increase the conductivity of the negative electrode active material grain boundary. Thereby, even if all the negative electrode active materials present in the negative electrode are entangled with, for example, the binder, they are not electrically isolated and contribute to the charge / discharge reaction.

【００１２】また、カーボンブラックが負極活物質と繊
維状炭素との間に介在して、負極における電解質の保液
性を高める。これにより、非水電解質電池を低温環境下
において充放電した場合であっても、負極では、負極活
物質の粒子間に存在する限られた空隙でのイオン伝導が
速やかになり、リチウムイオンのドープ／脱ドープ反応
が円滑に行われて、内部抵抗が低減し、分極が防止され
る。Further, carbon black is interposed between the negative electrode active material and the fibrous carbon to enhance the liquid retention of the electrolyte in the negative electrode. As a result, even when the nonaqueous electrolyte battery is charged and discharged in a low-temperature environment, in the negative electrode, ionic conduction in the limited voids existing between the particles of the negative electrode active material is accelerated, and lithium ion doping is performed. / The dedoping reaction is performed smoothly, the internal resistance is reduced, and the polarization is prevented.

【００１３】[0013]

【発明の実施の形態】以下、本発明に係る非水電解質電
池について、図面を参照しながら詳細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a non-aqueous electrolyte battery according to the present invention will be described in detail with reference to the drawings.

【００１４】本発明を適用した非水電解液二次電池１は
いわゆるリチウムイオン二次電池であり、図１に示すよ
うに、帯状の負極２と帯状の正極３とがセパレータ４を
介して積層され、長手方向に巻回されてなる渦巻型の電
極体が電池缶５に装填され、非水電解液が電池缶５に注
入されてなる。A non-aqueous electrolyte secondary battery 1 to which the present invention is applied is a so-called lithium ion secondary battery. As shown in FIG. 1, a strip-shaped negative electrode 2 and a strip-shaped positive electrode 3 are laminated with a separator 4 interposed therebetween. Then, a spiral electrode body wound in the longitudinal direction is loaded in the battery can 5, and a non-aqueous electrolyte is injected into the battery can 5.

【００１５】負極２は、ドープ／脱ドープ可能な負極活
物質、繊維状炭素およびカーボンブラックからなる負極
材料を含有する負極材料と、結着剤とを混合して調製さ
れた負極合剤を負極集電体６上に塗布して乾燥させたも
のである。The negative electrode 2 comprises a negative electrode mixture prepared by mixing a negative electrode material containing a negative electrode active material capable of being doped / undoped, a negative electrode material composed of fibrous carbon and carbon black, and a binder. It is applied on the current collector 6 and dried.

【００１６】負極材料に含有される負極活物質として
は、リチウムをドープ／脱ドープ可能な炭素材料、結晶
質、非結晶質金属酸化物等が用いられる。炭素材料とし
ては、コークスやガラス状炭素等の難黒鉛化性炭素材
料、結晶構造が発達した高結晶性炭素材料の黒鉛類等が
挙げられ、具体的には、熱分解炭素類、コークス類、
（ピッチコークス、ニードルコークス、石油コークス
等）、グラファイト類、ガラス状炭素類、有機高分子化
合物焼成体（フェノール樹脂、フラン樹脂等を適当な温
度で焼成し炭素化したもの）、炭素繊維、及び活性炭等
が挙げられる。As the negative electrode active material contained in the negative electrode material, a carbon material capable of doping / dedoping lithium, a crystalline or non-crystalline metal oxide, or the like is used. Examples of the carbon material include non-graphitizable carbon materials such as coke and glassy carbon, and graphites of a highly crystalline carbon material with a developed crystal structure.Specifically, pyrolytic carbons, cokes,
(Pitch coke, needle coke, petroleum coke, etc.), graphites, glassy carbons, organic polymer compound fired bodies (phenol resins, furan resins, etc. fired at appropriate temperatures and carbonized), carbon fibers, and Activated carbon etc. are mentioned.

【００１７】なお、高結晶性炭素材料の黒鉛類は、結晶
性の低い難黒鉛化性炭素材料と比較すると真密度が高い
ので、この黒鉛類を負極材料として用いた負極２は、活
物資の充填密度がより高く、より高エネルギー密度であ
る電池を実現できる。また、この黒鉛類を負極材料とす
る非水電解液二次電池１は、高エネルギー密度を有する
と共に、放電カーブが平坦であるため電子機器での電圧
変化に際してエネルギーロスがないといった長所も有す
る。Incidentally, graphite, which is a highly crystalline carbon material, has a higher true density than a non-graphitizable carbon material having low crystallinity. Therefore, the negative electrode 2 using this graphite as a negative electrode material can be used as an active material. A battery having a higher filling density and a higher energy density can be realized. In addition, the nonaqueous electrolyte secondary battery 1 using the graphite as a negative electrode material has an advantage that it has a high energy density and has a flat discharge curve so that there is no energy loss when a voltage is changed in an electronic device.

【００１８】負極材料中に含有される繊維状炭素は、負
極活物質の粒子間に介在して負極活物質粒界の導電性を
高めている。このような維状炭素としては、繊維状に紡
糸された高分子やピッチ等のプリカーサを熱処理するこ
とで得られるものや、温度を１０００℃程度となされた
基板上にベンゼン等の有機物蒸気を直接流し、鉄微粒子
等を触媒として炭素結晶を成長させることで得られる気
相成長炭素等がある。The fibrous carbon contained in the negative electrode material is interposed between the particles of the negative electrode active material to increase the conductivity of the negative electrode active material grain boundaries. Such fibrous carbon is obtained by heat-treating a precursor such as a polymer or pitch spun into a fibrous form, or an organic vapor such as benzene is directly applied to a substrate at a temperature of about 1000 ° C. There is vapor-grown carbon and the like obtained by flowing and growing carbon crystals using iron fine particles as a catalyst.

【００１９】熱処理によって繊維状炭素を得る場合、高
分子系のプリカーサとしては、ポリアクリロニトリルや
レーヨン、ポリアミド、リグニン、ポリビニルアルコー
ル等を使用できる。When fibrous carbon is obtained by heat treatment, polyacrylonitrile, rayon, polyamide, lignin, polyvinyl alcohol, or the like can be used as a polymer precursor.

【００２０】ピッチとしては、コールタール、エチレン
ボトム油、原油等を高温で熱分解して得られるタール
類、アスファルト等より蒸留（真空蒸留、常圧蒸留、ス
チーム蒸留）、熱重縮合、抽出、化学重縮合等の操作に
よって得られるものや、木材乾留時に生成するものを使
用できる。As the pitch, distillation (vacuum distillation, normal pressure distillation, steam distillation) from tar, asphalt, etc. obtained by pyrolyzing coal tar, ethylene bottom oil, crude oil, etc. at a high temperature, hot polycondensation, extraction, Those obtained by operations such as chemical polycondensation and those produced during wood carbonization can be used.

【００２１】また、ピッチとなる出発原料としては、ポ
リ塩化ビニル樹脂、ポリビニルアセテート、ポリビニル
ブチラート、３，５−ジメチルフェノール樹脂等を使用
できる。Further, as a starting material for forming the pitch, polyvinyl chloride resin, polyvinyl acetate, polyvinyl butyrate, 3,5-dimethylphenol resin and the like can be used.

【００２２】これら石炭やピッチは、炭素化の途中、最
高４００℃程度で液状として存在し、その温度で保持す
ることで芳香環同士が縮合、多環化して積層配向した状
態となり、その後、５００℃程度以上の温度になると固
体の炭素前駆体、すなわちセミコークスを形成する。こ
のような過程は液相炭素化過程と呼ばれ、易黒鉛化炭素
の典型的な生成過程である。During the carbonization, these coals and pitches exist as liquids at a maximum of about 400 ° C., and when held at that temperature, aromatic rings are condensed and polycyclic to form a laminated orientation. At temperatures above about ° C, a solid carbon precursor, ie, semi-coke, is formed. Such a process is called a liquid phase carbonization process and is a typical production process of graphitizable carbon.

【００２３】その他、ナフタレン、フェナントレン、ア
ントラセン、トリフェニレン、ピレン、ペリレン、ペン
タフェン、ペンタセン等の縮合多環炭化水素化合物及び
その他の誘導体（例えばこれらのカルボン酸、カルボン
酸無水物、カルボン酸イミド等）或いは混合物、アセナ
フチレン、インドール、イソインドール、キノリン、イ
ソキノリン、キノキサリン、フタラジン、カルバゾー
ル、アクリジン、フェナジン、フェナントリジン等の縮
合複素環化合物及びその他の誘導体等も、易黒鉛化炭素
の原料として使用できる。In addition, condensed polycyclic hydrocarbon compounds such as naphthalene, phenanthrene, anthracene, triphenylene, pyrene, perylene, pentaphen, and pentacene, and other derivatives (eg, carboxylic acids, carboxylic anhydrides, carboxylic imides, etc.) or Mixtures, condensed heterocyclic compounds such as acenaphthylene, indole, isoindole, quinoline, isoquinoline, quinoxaline, phthalazine, carbazole, acridine, phenazine, phenanthridine and other derivatives can also be used as raw materials for graphitizable carbon.

【００２４】高分子系のプリカーサおよびピッチ系のプ
リカーサは、不融化あるいは安定化という工程を経た
後、高温中で熱処理されることにより、繊維状炭素とな
る。[0024] The polymer-based precursor and the pitch-based precursor are subjected to a process of infusibility or stabilization, and then heat-treated at a high temperature to become fibrous carbon.

【００２５】なお、この不融化あるいは安定化の工程と
は、高分子等が炭素化の際に溶融や熱分解を起こさない
よう、繊維表面を酸や酸素、オゾン等を用いて酸化する
工程である。この際、処理方法はプリカーサの種類によ
って適宜選択される。ただし、処理温度はプリカーサの
融点以下を選択する必要がある。また、必要に応じて複
数回処理を繰り返し、安定化が十分に施されるようにし
てもよい。The infusibilizing or stabilizing step is a step of oxidizing the fiber surface with an acid, oxygen, ozone, or the like so that the polymer or the like does not melt or thermally decompose during carbonization. is there. At this time, the processing method is appropriately selected depending on the type of the precursor. However, the processing temperature must be selected to be lower than the melting point of the precursor. Further, the processing may be repeated a plurality of times as necessary, so that sufficient stabilization is performed.

【００２６】繊維状炭素を得るには、まず、高分子系の
プリカーサあるいはピッチ系のプリカーサに上述した不
融化あるいは安定化を施す。ついで、不融化あるいは安
定化が施された高分子系またはピッチ系のプリカーサ
を、窒素等の不活性ガス気流中において温度を３００℃
〜７００℃として炭化した後、不活性ガス気流中におい
て昇温速度を毎分１℃〜１００℃として到達温度９００
℃〜１５００℃まで昇温し、この到達温度にて保持時間
０〜３０時間程度の条件でか焼する。これにより、繊維
状炭素が得られる。なお、場合によっては炭化を省略し
ても良い。In order to obtain fibrous carbon, first, the above-mentioned infusibilization or stabilization is applied to a polymer-based precursor or a pitch-based precursor. Next, the insoluble or stabilized polymer-based or pitch-based precursor is heated to 300 ° C. in an inert gas stream such as nitrogen.
After the carbonization at ~ 700 ° C, the temperature reached 900 ° C per minute in an inert gas stream at an ultimate temperature of 900 ° C.
The temperature is raised to from 1500 to 1500 ° C, and calcination is performed at this ultimate temperature under the condition of a holding time of about 0 to 30 hours. Thereby, fibrous carbon is obtained. In some cases, carbonization may be omitted.

【００２７】繊維状炭素を気相成長法によって得る場
合、出発原料としては、気体状となり得る有機物をいず
れも使用できる。例えば、常温環境下において気体とし
て存在するエチレン、プロパン等、あるいは熱分解温度
以下の温度で加熱気化できる有機物を使用できる。When fibrous carbon is obtained by a vapor phase growth method, any organic substance which can be in a gaseous state can be used as a starting material. For example, ethylene, propane, or the like which exists as a gas in a normal temperature environment, or an organic substance which can be heated and vaporized at a temperature equal to or lower than the thermal decomposition temperature can be used.

【００２８】気化した有機物は、高温の基板状に直接放
出されることで、繊維状炭素として結晶成長する。この
際、基板の温度は、出発原料として用いる有機物の種類
によって適宜選択されるが、４００℃〜１５００℃とす
ることが好ましい。また、基板の種類は、出発原料とし
て用いる有機物の種類によって適宜選択されるが、石英
やニッケル等が好ましい。The vaporized organic substance is directly released into a high-temperature substrate state, and grows as fibrous carbon. At this time, the temperature of the substrate is appropriately selected depending on the kind of the organic substance used as a starting material, but is preferably 400 ° C to 1500 ° C. The type of the substrate is appropriately selected depending on the type of the organic substance used as the starting material, but quartz or nickel is preferable.

【００２９】また、触媒を用いて、結晶成長を促進させ
ることが可能である。触媒としては、鉄やニッケル、ま
たはこれらの混合物等を微粒子化したものや、黒鉛化触
媒と称される金属やその酸化物を使用できる。なお、こ
れらの触媒は、出発原料として用いる有機物の種類によ
って適宜選択される。Further, it is possible to promote crystal growth by using a catalyst. As the catalyst, iron or nickel, or a mixture thereof or the like in the form of fine particles, a metal called a graphitization catalyst, or an oxide thereof can be used. Note that these catalysts are appropriately selected depending on the type of the organic substance used as a starting material.

【００３０】繊維状炭素の外形や長さは、調製条件によ
って適宜選択可能である。例えば、高分子系のプリカー
サを原料にする場合、繊維状に成形するときの吹き出し
ノズル内径等や、吹き出し速度によって適当な繊維径や
長さを得ることができる。気相成長法による場合、基板
や触媒など結晶成長の核となる部分の大きさを適宜選択
することで最適な繊維径を得ることができる。また、原
料となるエチレン、プロパン等の有機物の供給量を規定
することにより繊維径や直線性を調整することが可能で
ある。The outer shape and length of the fibrous carbon can be appropriately selected depending on the preparation conditions. For example, when a polymer precursor is used as a raw material, an appropriate fiber diameter and length can be obtained depending on the inner diameter of a blowing nozzle or the like and the blowing speed when forming into a fibrous shape. In the case of the vapor phase growth method, an optimal fiber diameter can be obtained by appropriately selecting the size of a portion that becomes a nucleus of crystal growth such as a substrate and a catalyst. Further, the fiber diameter and the linearity can be adjusted by regulating the supply amounts of organic substances such as ethylene and propane as raw materials.

【００３１】繊維状炭素の繊維長と繊維径との比である
アスペクト比は、１０以上であることが好ましい。アス
ペクト比が１０未満である場合、繊維状炭素は、負極活
物質粒子間をつないで導電性を高める役割を果たすが、
その一方で負極活物質粒子間の空隙を埋めてしまい、負
極２における電解液の保液力を低下させる虞がある。こ
のため、非水電解席二次電池１としては、低温度負荷特
性が低下する可能性がある。したがって、アスペクト比
が１０以上であることにより、負極２における電解液の
保液力を低下させること無く、負極活物質粒界の導電性
を高めることが可能となる。なお、繊維状炭素とは、ア
スペクト比が１０以上であるものを指すことにする。The aspect ratio, which is the ratio between the fiber length and the fiber diameter of the fibrous carbon, is preferably 10 or more. When the aspect ratio is less than 10, the fibrous carbon plays a role of connecting the negative electrode active material particles to increase the conductivity,
On the other hand, the voids between the negative electrode active material particles may be filled, and the liquid retaining power of the electrolytic solution in the negative electrode 2 may be reduced. Therefore, the low temperature load characteristics of the non-aqueous electrolytic secondary battery 1 may be reduced. Therefore, when the aspect ratio is 10 or more, it is possible to increase the conductivity of the negative electrode active material grain boundary without lowering the liquid retaining ability of the electrolytic solution in the negative electrode 2. Note that fibrous carbon refers to carbon having an aspect ratio of 10 or more.

【００３２】また、繊維状炭素の繊維長は、０．５μｍ
以上であることが好ましい。繊維状炭素の繊維長が０．
５μｍ未満である場合、負極活物質粒子間の距離よりも
繊維長が短いため、負極活物質粒界の導電性を高める作
用が得られない虞がある。したがって、繊維状炭素の繊
維長が０．５μｍ以上であることにより、負極活物質粒
界の導電性を高める作用を確実に得ることができる。The fiber length of the fibrous carbon is 0.5 μm
It is preferable that it is above. The fiber length of the fibrous carbon is 0.
If it is less than 5 μm, the fiber length is shorter than the distance between the negative electrode active material particles, and therefore, there is a possibility that the effect of increasing the conductivity of the negative electrode active material grain boundary cannot be obtained. Therefore, when the fiber length of the fibrous carbon is 0.5 μm or more, the effect of increasing the conductivity of the negative electrode active material grain boundary can be reliably obtained.

【００３３】なお、このようにして得られた繊維状炭素
を、不活性ガス気流中において、昇温速度を毎分１℃〜
１００℃として、到達温度２０００℃以上、好ましくは
２５００℃以上まで昇温し、この到達温度にて保持時間
０〜３０時間程度の条件で黒鉛化処理してもよい。The fibrous carbon thus obtained was heated in an inert gas stream at a rate of 1 ° C./min.
As 100 ° C., the temperature may be raised to an ultimate temperature of 2000 ° C. or higher, preferably 2500 ° C. or higher, and the graphitizing treatment may be performed at the ultimate temperature for a holding time of about 0 to 30 hours.

【００３４】また、電極の厚みや活物質の粒径等に合わ
せて繊維状炭素を粉砕しても良く、紡糸時に単繊維とな
った繊維状炭素も使用可能である。なお、繊維状炭素の
粉砕は、炭化、か焼の前後あるいは黒鉛化前の昇温過程
の間、何れで行われても良い。Further, fibrous carbon may be pulverized in accordance with the thickness of the electrode, the particle size of the active material, and the like, and fibrous carbon which has become a single fiber during spinning may be used. The pulverization of the fibrous carbon may be performed before or after carbonization or calcination or during the heating process before graphitization.

【００３５】繊維状炭素は、負極材料中に０．１重量％
以上、１０重量％以下の範囲で含有されることが好まし
い。繊維状炭素が負極材料中に０．１重量％より少なく
含有されている場合、負極活物質粒界の導電性を十分に
高めることができない虞がある。一方、繊維状炭素が負
極材料中に１０重量％より多く含有されている場合、負
極２中の負極活物質量が少なくなるので、非水電解液二
次電池１の電池容量が低下する虞がある。従って、繊維
状炭素は、負極材料中に０．１重量％以上、１０重量％
以下の範囲で含有されることにより、非水電解液二次電
池１の電池容量を低下させることなく、全ての負極活物
質に電子伝導性を確実に与えることができる。なお、負
極材料中に含有される繊維状炭素の含有量としては、
０．３重量％以上、５重量％以下の範囲であることがよ
り好ましく、０．５重量％以上、２重量％以下の範囲で
あることが最も好ましい。The fibrous carbon is 0.1% by weight in the negative electrode material.
Preferably, it is contained in the range of 10% by weight or less. When the amount of the fibrous carbon is less than 0.1% by weight in the negative electrode material, the conductivity of the negative electrode active material grain boundary may not be sufficiently increased. On the other hand, when the amount of the fibrous carbon is more than 10% by weight in the negative electrode material, the amount of the negative electrode active material in the negative electrode 2 is reduced, so that the battery capacity of the nonaqueous electrolyte secondary battery 1 may be reduced. is there. Therefore, fibrous carbon accounts for 0.1% by weight or more and 10% by weight in the negative electrode material.
By being contained in the following range, all the negative electrode active materials can be given electron conductivity without lowering the battery capacity of the nonaqueous electrolyte secondary battery 1. Incidentally, as the content of fibrous carbon contained in the negative electrode material,
It is more preferably in the range of 0.3% by weight or more and 5% by weight or less, and most preferably in the range of 0.5% by weight or more and 2% by weight or less.

【００３６】負極材料中に含有されるカーボンブラック
は、負極活物質と繊維状炭素との間に介在して、負極２
における電解質の保液性を高めている。カーボンブラッ
クとしては、原料炭化水素が熱分解法により生成された
ものや、不完全燃焼法により生成されたものを用いる。
熱分解法としては、サーマル法、アセチレン分解法等が
挙げられる。不完全燃焼法としては、コンタクト法、ラ
ンプ・末煙法、ガスファーネス法、オイルファーネス法
等が挙げられる。The carbon black contained in the negative electrode material is interposed between the negative electrode active material and the fibrous carbon to form the negative electrode 2.
The liquid retention of the electrolyte is improved. As the carbon black, those obtained by pyrolysis of a raw material hydrocarbon or those obtained by incomplete combustion are used.
Examples of the thermal decomposition method include a thermal method and an acetylene decomposition method. Examples of the incomplete combustion method include a contact method, a lamp / smoke method, a gas furnace method, and an oil furnace method.

【００３７】これらの生成法により生成されるカーボン
ブラックとしては、アセチレンブラック、ケッチェンブ
ラック、サーマルブラック、ファーネスブラック等が挙
げられる。これらのカーボンブラックの内、特に、アセ
チレンブラックやケッチェンブラック等のような導電性
カーボンブラックを使用することが好ましい。The carbon black produced by these production methods includes acetylene black, Ketjen black, thermal black, furnace black and the like. Among these carbon blacks, it is particularly preferable to use a conductive carbon black such as acetylene black or Ketjen black.

【００３８】カーボンブラックのＤＢＰ給油量は、１０
０ｍｌ／１００ｇ以上であることが好ましい。カーボン
ブラックのＤＢＰ給油量が１００ｍｌ／１００ｇ未満で
ある場合、負極２における電解液の保液量が不充分とな
る虞がある。ＤＢＰ給油量が１００ｍｌ／１００ｇ未満
であるカーボンブラックを用いて所望の電解液保液力を
有する負極を作製するならば、負極材料中にカーボンブ
ラックを２重量％より多く添加する必要がある。しか
し、負極材料中におけるカーボンブラックの含有量が２
重量％を超える場合、詳細は後述するが、非水電解液二
次電池１の電池容量が低下してしまう。したがって、Ｄ
ＢＰ給油量が１００ｍｌ／１００ｇ以上であるカーボン
ブラックを用いることにより、非水電解液二次電池１の
電池容量を低下させることなく、負極２の電解液保液力
を高めることが可能となる。The DBP lubrication amount of carbon black is 10
It is preferably 0 ml / 100 g or more. If the DBP lubrication amount of carbon black is less than 100 ml / 100 g, there is a possibility that the amount of electrolyte retained in the negative electrode 2 may be insufficient. If a negative electrode having a desired electrolyte retention capacity is produced using carbon black having a DBP lubrication amount of less than 100 ml / 100 g, it is necessary to add carbon black in an amount of more than 2% by weight to the negative electrode material. However, when the content of carbon black in the negative electrode material is 2
When the content is more than 10% by weight, the battery capacity of the nonaqueous electrolyte secondary battery 1 is reduced, as will be described in detail later. Therefore, D
By using carbon black having a BP oiling amount of 100 ml / 100 g or more, it is possible to increase the electrolyte retaining ability of the negative electrode 2 without reducing the battery capacity of the nonaqueous electrolyte secondary battery 1.

【００３９】また、カーボンブラックの平均粒径は、
０．１μｍ以下であることが好ましい。カーボンブラッ
クの平均粒径が０．１μｍより大きい場合、負極材料中
における嵩密度が小さくなるので、負極２に電解液を十
分に保液できない虞がある。したがって、カーボンブラ
ックの平均粒径が０．１μｍ以下であることにより、負
極２に電解液を十分に保液することができる。The average particle size of carbon black is as follows:
It is preferably 0.1 μm or less. When the average particle size of the carbon black is larger than 0.1 μm, the bulk density in the negative electrode material becomes small, and therefore, the electrolyte may not be sufficiently retained in the negative electrode 2. Therefore, when the average particle size of the carbon black is 0.1 μm or less, the electrolyte can be sufficiently retained in the negative electrode 2.

【００４０】このカーボンブラックは、負極材料中に
０．０２重量％以上、２重量％以下の範囲で含有される
ことが好ましい。カーボンブラックが負極材料中に０．
０２重量％より少なく含有されている場合、負極２に電
解液を十分に保液することができない虞がある。一方、
カーボンブラックが負極材料中に２重量％より多く含有
されている場合、負極２中の負極活物質量が減少するた
め、非水電解液二次電池１の電池容量が低下する虞があ
る。従って、カーボンブラックが負極材料中に０．０２
重量％以上、２重量％以下の範囲で含有されることによ
り、非水電解液二次電池１の電池容量を低下させること
なく、負極２に十分な電解液を保液することができる。
なお、負極材料中に含有されるカーボンブラックの含有
量としては、０．１重量％以上、１．５重量％以下の範
囲であることがより好ましく、０．２重量％以上、１．
０重量％以下の範囲であることが最も好ましい。The carbon black is preferably contained in the negative electrode material in a range of 0.02% by weight or more and 2% by weight or less. Carbon black is contained in the negative electrode material in an amount of 0.1%.
If the content is less than 02% by weight, the electrolyte may not be sufficiently retained in the negative electrode 2. on the other hand,
When carbon black is contained in the negative electrode material in an amount of more than 2% by weight, the amount of the negative electrode active material in the negative electrode 2 is reduced, so that the battery capacity of the nonaqueous electrolyte secondary battery 1 may be reduced. Therefore, carbon black is contained in the anode material in an amount of 0.02%.
When the content is in the range of not less than 2% by weight and not more than 2% by weight, a sufficient amount of electrolyte can be retained in the negative electrode 2 without reducing the battery capacity of the nonaqueous electrolyte secondary battery 1.
The content of carbon black contained in the negative electrode material is more preferably in the range of 0.1% by weight or more and 1.5% by weight or less, and more preferably in the range of 0.2% by weight or more.
Most preferably, it is in the range of 0% by weight or less.

【００４１】負極材料には、上述したような繊維状炭素
およびカーボンブラックが含有されているが、繊維状炭
素の含有量とカーボンブラックの含有量との比、すなわ
ち、繊維状炭素とカーボンブラックとの重量比は、０．
５以上２０以下であることが好ましい。繊維状炭素の重
量比がこの範囲を下回る場合、導電性が不足する可能性
がある。一方、カーボンブラックの重量比がこの範囲を
下回る場合、負極２に電解液を保持する作用が十分に得
られない可能性がある。したがって、繊維状炭素とカー
ボンブラックとの重量比が０．５以上２０以下であるこ
とにより、負極活物質粒界の導電性を高める作用と、負
極２に電解液を保持する作用とを両立して得ることがで
きる。なお、繊維状炭素とカーボンブラックとの重量比
としては、１．０以上、１０以下であることがより好ま
しく、１．５以上、６以下であることが最も好ましい。The negative electrode material contains fibrous carbon and carbon black as described above. The ratio of the content of fibrous carbon to the content of carbon black, that is, the ratio of fibrous carbon to carbon black, Weight ratio is 0.1.
It is preferably 5 or more and 20 or less. If the weight ratio of the fibrous carbon is below this range, the conductivity may be insufficient. On the other hand, when the weight ratio of the carbon black is below this range, there is a possibility that the effect of retaining the electrolytic solution in the negative electrode 2 may not be sufficiently obtained. Therefore, when the weight ratio of fibrous carbon and carbon black is 0.5 or more and 20 or less, the effect of increasing the conductivity of the negative electrode active material grain boundary and the effect of holding the electrolytic solution on the negative electrode 2 are compatible. Can be obtained. The weight ratio between fibrous carbon and carbon black is more preferably 1.0 or more and 10 or less, and most preferably 1.5 or more and 6 or less.

【００４２】負極２に含有される結着剤としては、通常
この種の電池の負極合剤に用いられている公知の結着剤
を用いることができる。また、負極合剤には、必要に応
じて公知の添加剤等を添加してもよい。As the binder contained in the negative electrode 2, a known binder usually used for a negative electrode mixture of this type of battery can be used. Further, a known additive or the like may be added to the negative electrode mixture as needed.

【００４３】正極３は、正極活物質と結着剤とを含む正
極合剤を正極集電体７上に塗布し、乾燥させたものであ
る。The positive electrode 3 is obtained by applying a positive electrode mixture containing a positive electrode active material and a binder onto a positive electrode current collector 7 and drying the mixture.

【００４４】正極活物質としては、リチウムをドープ／
脱ドープ可能であり、十分な量のリチウムを含んでいる
従来公知の正極材料であれば、何れであっても良い。具
体的には、一般式ＬｉＭｘＯｙ（但し、１＜ｘ≦２であ
り、２＜ｙ≦４であり、ＭはＣｏ、Ｎｉ、Ｍｎ、Ｆｅ、
Ａｌ、Ｖ、Ｔｉのうち少なくとも１種類以上を含有す
る。）で表されるリチウムと遷移金属からなる複合金属
酸化物や、リチウムを含んだ層間化合物等を用いること
が好ましい。As the positive electrode active material, lithium is doped /
Any conventionally known cathode material that can be undoped and contains a sufficient amount of lithium may be used. Specifically, a general formula LiM x O y (where 1 <x ≦ 2 and 2 <y ≦ 4, and M is Co, Ni, Mn, Fe,
Contains at least one of Al, V, and Ti. It is preferable to use a composite metal oxide composed of lithium and a transition metal represented by the formula (1), an intercalation compound containing lithium, and the like.

【００４５】正極３に含有される結着剤としては、通常
この種の電池の正極合剤に用いられている公知の結着剤
を用いることができる。また、正極合剤には、必要に応
じて公知の添加剤等を添加してもよい。As the binder contained in the positive electrode 3, a known binder usually used for a positive electrode mixture of this type of battery can be used. Further, a known additive or the like may be added to the positive electrode mixture as needed.

【００４６】非水電解液は、非水溶媒に電解質が溶解さ
れているものである。The non-aqueous electrolyte is one in which the electrolyte is dissolved in a non-aqueous solvent.

【００４７】非水溶媒には、比較的誘電率が高く、負極
を構成する黒鉛により分解されにくいエチレンカーボネ
ート（以下、ＥＣと称する。）等を主溶媒として用い
る。特に、負極に黒鉛材料を用いる場合、主溶媒として
は、ＥＣを用いることが好ましいが、ＥＣの水素原子を
ハロゲン元素で置換した化合物を用いることも可能であ
る。As the non-aqueous solvent, ethylene carbonate (hereinafter referred to as EC) which has a relatively high dielectric constant and is not easily decomposed by the graphite constituting the negative electrode is used as a main solvent. In particular, when a graphite material is used for the negative electrode, it is preferable to use EC as the main solvent, but it is also possible to use a compound in which a hydrogen atom of EC is replaced with a halogen element.

【００４８】また、ＰＣのように黒鉛材料と反応性があ
るものの、主溶媒としてのＥＣやＥＣの水素原子をハロ
ゲン元素で置換した化合物等に対して、その一部を第２
成分溶媒で置換することにより、より良好な特性が得ら
れる。Further, although it is reactive with the graphite material like PC, a part of the compound such as EC as a main solvent or a compound in which a hydrogen atom of EC is replaced with a halogen element is used as a second solvent.
By substituting with the component solvent, better characteristics can be obtained.

【００４９】この第２成分溶媒としては、プロピレンカ
ーボネート、ブチレンカーボネート、ビニレンカーボネ
ート、１，２−ジメトキシエタン、１，２−ジエトキシ
メタン、γ−ブチロラクトン、バレロラクトン、テトラ
ヒドロフラン、２−メチルテトラヒドロフラン、１，３
−ジオキソラン、４−メチル−１，３−ジオキソラン、
スルホラン、メチルスルホラン等が挙げられる。As the second component solvent, propylene carbonate, butylene carbonate, vinylene carbonate, 1,2-dimethoxyethane, 1,2-diethoxymethane, γ-butyrolactone, valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, , 3
Dioxolane, 4-methyl-1,3-dioxolane,
Sulfolane, methylsulfolane and the like can be mentioned.

【００５０】さらに、非水溶媒には、低粘度溶媒を併用
し、導電率を向上させて電流特性を改善し、リチウム金
属との反応性を低下させて安全性を改善することが好ま
しい。Further, it is preferable to use a low-viscosity solvent in combination with the non-aqueous solvent, to improve the electric conductivity by improving the electric conductivity, and to improve the safety by lowering the reactivity with lithium metal.

【００５１】低粘度溶媒としては、ジエチルカーボネー
ト、ジメチルカーボネート、メチルエチルカーボネー
ト、メチルプロピルカーボネート等の対称あるいは非対
称である鎖状炭酸エステルや、プロピオン酸メチル、プ
ロピオン酸エチル等のカルボン酸エステルや、リン酸ト
リメチル、リン酸トリエチル等のリン酸エステル等を使
用できる。これらの低粘度溶媒は１種類を単独で用いて
も良く、２種類以上を混合して用いることも可能であ
る。Examples of the low-viscosity solvent include symmetric or asymmetric chain carbonates such as diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, and methyl propyl carbonate; carboxylic acid esters such as methyl propionate and ethyl propionate; Phosphate esters such as trimethyl acid and triethyl phosphate can be used. One of these low-viscosity solvents may be used alone, or two or more may be used in combination.

【００５２】電解質としては、非水溶媒に溶解し、イオ
ン伝導性を示すリチウム塩であれば特に限定されること
はなく、例えば、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＡｓ
Ｆ６、ＬｉＢＦ４、ＬｉＢ（Ｃ６Ｈ５）４、ＬｉＣＨ３
ＳＯ３、ＣＦ３ＳＯ３Ｌｉ、ＬｉＣｌ、ＬｉＮ（ＣｎＣ
２ｎ＋１ＳＯ２）２、ＬｉＢｒ等を使用できる。特に、
電解質としてＬｉＰＦ６を用いることが好ましい。これ
らの電解質は、１種類を単独で用いても良く、２種類以
上を混合して用いることも可能である。The electrolyte is not particularly limited as long as it is a lithium salt which dissolves in a non-aqueous solvent and exhibits ionic conductivity. For example, LiPF 6 , LiClO 4 , LiAs
F 6 , LiBF 4 , LiB (C 6 H 5 ) 4 , LiCH 3
SO 3 , CF 3 SO 3 Li, LiCl, LiN (C n C
2n + 1 SO 2 ) 2 , LiBr and the like can be used. In particular,
It is preferable to use LiPF 6 as the electrolyte. One of these electrolytes may be used alone, or two or more of them may be used in combination.

【００５３】電池缶５の材質としては、Ｆｅ、Ｎｉ、ス
テンレス、Ａｌ、Ｔｉ等を使用できる。この電池缶５に
は、電池の充放電にともなう電気化学的な非水電解液に
よる腐食を防止するために、メッキ等が施されていても
良い。As the material of the battery can 5, Fe, Ni, stainless steel, Al, Ti and the like can be used. The battery can 5 may be plated or the like in order to prevent corrosion by an electrochemical non-aqueous electrolyte accompanying charging and discharging of the battery.

【００５４】以上のように構成された非水電解液二次電
池１を作製する際には、まず、上述のようにして得られ
る帯状の負極２と帯状の正極３とを、例えば微孔性ポリ
プロピレンフィルムからなるセパレータ４を介して積層
した後、長手方向に多数回巻き回してなる渦巻型の電極
体を作製する。When the non-aqueous electrolyte secondary battery 1 constructed as described above is manufactured, first, the strip-shaped negative electrode 2 and the strip-shaped positive electrode 3 obtained as described above are, for example, microporous. After laminating via a separator 4 made of a polypropylene film, a spiral electrode body is formed which is wound many times in the longitudinal direction.

【００５５】次に、電極体を、底部に絶縁板８が挿入さ
れており、内側にニッケルメッキが施されている鉄製の
電池缶５に収納する。そして負極２の集電をとるため
に、例えばニッケルからなる負極リード９の一端を負極
２に圧着させ、他端を電池缶５に溶接する。これによ
り、電池缶５は負極２と導通をもつこととなり、非水電
解液二次電池１の外部負極となる。また、正極３の集電
をとるために、例えばアルミニウムからなる正極リード
１０の一端を正極３に取り付け、他端を電流遮断用薄板
を介して電池蓋１１と電気的に接続する。この電流遮断
用薄板は、電池内圧に応じて電流を遮断するものであ
る。これにより、電池蓋１１は正極３と導通をもつこと
となり、非水電解液二次電池１の外部正極となる。Next, the electrode body is housed in an iron battery can 5 having an insulating plate 8 inserted at the bottom and nickel plating on the inside. Then, in order to collect the current of the negative electrode 2, one end of a negative electrode lead 9 made of, for example, nickel is pressed against the negative electrode 2 and the other end is welded to the battery can 5. As a result, the battery can 5 has conductivity with the negative electrode 2 and serves as an external negative electrode of the nonaqueous electrolyte secondary battery 1. In order to collect the current of the positive electrode 3, one end of a positive electrode lead 10 made of, for example, aluminum is attached to the positive electrode 3, and the other end is electrically connected to the battery lid 11 via a current interrupting thin plate. The current interrupting thin plate interrupts the current according to the internal pressure of the battery. As a result, the battery lid 11 has conductivity with the positive electrode 3 and serves as an external positive electrode of the nonaqueous electrolyte secondary battery 1.

【００５６】そして、この電池缶５の中に電解質を非水
溶媒に溶解させて調製した非水電解液を注入した後に、
アスファルトを塗布した絶縁封口ガスケット１２を介し
て電池缶５をかしめることにより、電池蓋１１が固定さ
れた円筒型の非水電解質二次電池１が作製される。Then, after injecting a non-aqueous electrolyte prepared by dissolving an electrolyte in a non-aqueous solvent into the battery can 5,
By caulking the battery can 5 via the insulating sealing gasket 12 coated with asphalt, the cylindrical nonaqueous electrolyte secondary battery 1 to which the battery lid 11 is fixed is manufactured.

【００５７】なお、この非水電解質二次電池１は、電池
内部の圧力が所定値よりも高くなったときに内部の気体
を抜くための安全弁装置１３及び電池内部の温度上昇を
防止するためのＰＴＣ素子１４が設けられている。The non-aqueous electrolyte secondary battery 1 has a safety valve device 13 for bleeding out gas when the pressure inside the battery becomes higher than a predetermined value, and a device for preventing the temperature inside the battery from rising. A PTC element 14 is provided.

【００５８】以上のように作製された非水電解液二次電
池１において、負極２では、負極材料中に含有される繊
維状炭素が負極活物質の粒子間に介在して負極活物質粒
界の導電性を高めているので、負極活物質が、絶縁体で
ある結着剤に絡め取られていたとしても電気的に孤立す
ることが無くなり充放電反応に寄与できる。したがっ
て、非水電解液二次電池１では、負極２が本来の容量を
引き出すことが可能となる。In the non-aqueous electrolyte secondary battery 1 manufactured as described above, in the negative electrode 2, the fibrous carbon contained in the negative electrode material is interposed between the particles of the negative electrode active material and the negative electrode active material Since the conductivity of the negative electrode active material is increased, even if the negative electrode active material is entangled in the binder, which is an insulator, the negative electrode active material does not become electrically isolated and can contribute to the charge / discharge reaction. Therefore, in the non-aqueous electrolyte secondary battery 1, the negative electrode 2 can draw the original capacity.

【００５９】また、負極２では、負極材料中に含有され
るカーボンブラックが負極活物質と繊維状炭素との間に
介在し、負極２における電解質の保液性を高めているの
で、負極活物質の粒子間に存在する限られた空隙でのイ
オン伝導がより速やかになり、リチウムイオンのドープ
／脱ドープ反応がより円滑に行われる。これにより、非
水電解液二次電池１では、内部抵抗がより低減し、分極
が確実に防止される。In the negative electrode 2, the carbon black contained in the negative electrode material is interposed between the negative electrode active material and the fibrous carbon to enhance the liquid retaining property of the electrolyte in the negative electrode 2. The ion conduction in the limited voids existing between the particles becomes faster, and the doping / dedoping reaction of lithium ions is performed more smoothly. Thereby, in the nonaqueous electrolyte secondary battery 1, the internal resistance is further reduced, and the polarization is reliably prevented.

【００６０】したがって、負極活物質と繊維状炭素とカ
ーボンブラックとからなる負極材料を含有する負極２を
備える非水電解液二次電池１は、例えば低温環境下で繰
り返し充放電したとしても、良好な充放電特性を有し、
電池容量が高い。Therefore, the non-aqueous electrolyte secondary battery 1 including the negative electrode 2 containing the negative electrode material composed of the negative electrode active material, the fibrous carbon, and the carbon black is excellent even when repeatedly charged and discharged in a low-temperature environment, for example. With excellent charge and discharge characteristics,
High battery capacity.

【００６１】なお、本発明に係る非水電解質電池は、上
述のように電解質として非水電解液を用いた非水電解液
二次電池１に限定されず、電解質として固体電解質やゲ
ル状の電解質を用いることも可能であり、一次電池につ
いても適用可能である。また、本発明に係る非水電解質
電池では、円筒型、角型、コイン型、ボタン型等、その
形状については特に限定されず、また、薄型、大型等、
何れの大きさとしてもよい。The non-aqueous electrolyte battery according to the present invention is not limited to the non-aqueous electrolyte secondary battery 1 using a non-aqueous electrolyte as an electrolyte as described above. Can be used, and the present invention is also applicable to a primary battery. Further, in the non-aqueous electrolyte battery according to the present invention, cylindrical, square, coin-shaped, button-type, etc., the shape is not particularly limited, and thin, large, etc.
Any size may be used.

【００６２】[0062]

【実施例】以下、本発明に係る非水電解液電池につい
て、具体的な実験結果に基づいて説明する。なお、ここ
では実施例及び比較例として、非水電解液二次電池を複
数作製した。DESCRIPTION OF THE PREFERRED EMBODIMENTS The nonaqueous electrolyte battery according to the present invention will be described below based on specific experimental results. Here, as an example and a comparative example, a plurality of nonaqueous electrolyte secondary batteries were manufactured.

【００６３】＜実験１＞実験１では、負極材料の相違に
よる非水電解液二次電池の容量の違いを評価した。<Experiment 1> In Experiment 1, the difference in capacity of the nonaqueous electrolyte secondary battery due to the difference in the negative electrode material was evaluated.

【００６４】実施例１ 〔負極の作製〕負極活物質を、以下に示すようにして調
整した。まず、フィラーとなる石炭系コークス１００重
量部に対し、バインダーとなるコールタール系ピッチを
３０重量部加え、約１００℃にて混合した後に圧縮成型
することで、炭素成型体の前駆体を得た。ついで、この
前駆体を１０００℃以下で熱処理して炭素成型体とした
後に、２００℃以下で溶融させたバインダーピッチを含
浸させて、更に１０００℃以下で熱処理するという、ピ
ッチ含浸／焼成工程を数回繰り返した。ついで、この炭
素成型体を、不活性雰囲気中において温度２７００℃に
て熱処理し、黒鉛化成型体を得た。そして、この黒鉛化
成型体を粉砕分級することで、負極活物質試料粉末とし
た。 Example 1 [Preparation of Negative Electrode] A negative electrode active material was prepared as described below. First, 30 parts by weight of coal-tar pitch as a binder was added to 100 parts by weight of coal-based coke as a filler, mixed at about 100 ° C., and then compression molded to obtain a precursor of a carbon molded body. . Then, the precursor is heat-treated at 1000 ° C. or less to form a carbon molded body, and then impregnated with a binder pitch melted at 200 ° C. or less, and further heat-treated at 1000 ° C. or less. Repeated times. Then, the carbon molded body was heat-treated at 2700 ° C. in an inert atmosphere to obtain a graphitized molded body. Then, the graphitized molded body was pulverized and classified to obtain a negative electrode active material sample powder.

【００６５】なお、この黒鉛化成型体に対してＸ線回折
測定を行った結果、（００２）面の面間隔が０．３３７
ｎｍであり、（００２）回折線から計算されるＣ軸結晶
子厚みが５０．０ｎｍであった。また、ブタノールを溶
媒とするピクノメータ法による真密度が２．２３ｇ／ｃ
ｍ３であり、嵩密度が０．８３ｇ／ｃｍ３であり、ブル
ナウアーエメットテラー法による比表面積が４．４ｍ２
／ｇであった。また、レーザ回折法による粒度分布の平
均粒径が３１．２μｍであり、累積１０％粒径が１２．
３μｍであり、累積５０％粒径が２９．５μｍであり、
累積９０％粒径が５３．７μｍであり、黒鉛粒子の破壊
強度の平均値が７．１ｋｇｆ／ｍｍ３であった。X-ray diffraction measurement of this graphitized molded product showed that the (002) plane spacing was 0.337.
nm, and the C-axis crystallite thickness calculated from the (002) diffraction line was 50.0 nm. The true density by a pycnometer method using butanol as a solvent is 2.23 g / c.
m 3 , the bulk density is 0.83 g / cm 3 , and the specific surface area according to the Brunauer-Emmett-Teller method is 4.4 m 2.
/ G. The average particle size in the particle size distribution determined by the laser diffraction method is 31.2 μm, and the cumulative 10% particle size is 12.12.
3 μm, the cumulative 50% particle size is 29.5 μm,
The cumulative 90% particle size was 53.7 μm, and the average breaking strength of the graphite particles was 7.1 kgf / mm 3 .

【００６６】次に、負極活物質試料粉末を９８．５重量
％と、繊維状炭素（昭和電工社製、商品名：ＶＧＣＦ）
を１．０重量％と、カーボンブラックとしてアセチレン
ブラックを０．５重量％とを混合してなる負極材料を調
製した。なお、上記繊維状炭素は、平均繊維長が０．２
μｍ、平均繊維長が１０μｍ、アスペクト比が５０であ
る。Next, 98.5% by weight of the negative electrode active material sample powder was mixed with fibrous carbon (VGCF, manufactured by Showa Denko KK).
Was mixed with 1.0% by weight and 0.5% by weight of acetylene black as carbon black to prepare a negative electrode material. The above-mentioned fibrous carbon has an average fiber length of 0.2.
μm, average fiber length is 10 μm, and aspect ratio is 50.

【００６７】更に、上記負極材料を９０重量部と、結着
剤としてポリフッ化ビニリデンを１０重量部とを混合し
て負極合剤を調製した後に、Ｎ−メチルピロリドン中に
分散させて負極合剤スラリーとした。そして、この負極
合剤スラリーを、帯状の負極集電体上に均一に塗布して
乾燥させ、一定圧力で圧縮成型した後にスリットするこ
とで、帯状の負極を作製した。なお、負極集電体として
は、厚みが１０μｍである帯状の銅箔を使用した。Further, 90 parts by weight of the above negative electrode material and 10 parts by weight of polyvinylidene fluoride as a binder were mixed to prepare a negative electrode mixture, which was then dispersed in N-methylpyrrolidone to prepare a negative electrode mixture. A slurry was obtained. Then, the negative electrode mixture slurry was uniformly applied onto a band-shaped negative electrode current collector, dried, compression-molded at a constant pressure, and slit to prepare a band-shaped negative electrode. Note that a strip-shaped copper foil having a thickness of 10 μm was used as the negative electrode current collector.

【００６８】〔正極の作製〕正極活物質を、以下に示す
ようにして調製した。まず、炭酸リチウムを０．５モル
と炭酸コバルトを１モルとを混合し、空気中において温
度９００℃にて５時間焼成することで、ＬｉＣｏＯ２を
合成した。なお、得られた材料についてＸ線回折測定を
行い、ピークがＪＣＰＤＳファイルに登録されたＬｉＣ
ｏＯ２のデータと一致していることを確認した。[Preparation of Positive Electrode] A positive electrode active material was prepared as described below. First, LiCoO 2 was synthesized by mixing 0.5 mol of lithium carbonate and 1 mol of cobalt carbonate and calcining them in air at 900 ° C. for 5 hours. In addition, X-ray diffraction measurement was performed on the obtained material, and the peak was LiC registered in the JCPDS file.
It was confirmed that it matched the data of oO 2 .

【００６９】次に、ＬｉＣｏＯ２を粉砕してレーザ回折
法で得られる累積５０％粒径が１５μｍであるＬｉＣｏ
Ｏ２粉末とした後に、このＬｉＣｏＯ２粉末を９５重量
％と、炭酸リチウム粉末を５重量％とを混合して混合粉
末とした。そして、混合粉末を９１重量部と、導電剤と
して鱗片状黒鉛を６重量部と、結着剤としてポリフッ化
ビニリデンを３重量部とを混合して正極合剤を調製した
後に、Ｎ−メチルピロリドン中に分散させて正極合剤ス
ラリーとした。Next, LiCoO 2 is pulverized to obtain a LiCoO 2 having a cumulative 50% particle size of 15 μm obtained by a laser diffraction method.
After the O 2 powder, 95% by weight of the LiCoO 2 powder and 5% by weight of the lithium carbonate powder were mixed to obtain a mixed powder. Then, 91 parts by weight of the mixed powder, 6 parts by weight of flake graphite as a conductive agent, and 3 parts by weight of polyvinylidene fluoride as a binder were mixed to prepare a positive electrode mixture, and then N-methylpyrrolidone was prepared. The mixture was dispersed therein to obtain a positive electrode mixture slurry.

【００７０】そして、この正極合剤スラリーを、正極集
電体となる厚さが２０μｍである帯状のアルミニウム箔
に均一に塗布して乾燥させ、一定圧力で圧縮成型した後
にスリットすることで、帯状の正極を作製した。The positive electrode mixture slurry is uniformly applied to a 20-μm-thick strip-shaped aluminum foil serving as a positive electrode current collector, dried, compression-molded at a constant pressure, and slit to form a strip. Was produced.

【００７１】〔電池の作製〕上述のようにして作製した
帯状の負極と帯状の正極とを、厚さが２５μｍであり微
孔性ポリエチレンフィルムからなるセパレータ４を介し
て、負極、セパレータ４、正極、セパレータ４の順に積
層した後に多数回巻き回すことで、外径１８ｍｍである
渦巻型の電極体を作製した。[Preparation of Battery] A negative electrode, a separator 4 and a positive electrode were formed by interposing a strip-shaped negative electrode and a strip-shaped positive electrode prepared as described above via a separator 4 having a thickness of 25 μm and made of a microporous polyethylene film. Then, by laminating the separator 4 in this order and winding it many times, a spiral electrode body having an outer diameter of 18 mm was produced.

【００７２】次に、この電極体を、ニッケルメッキを施
した鉄製の電池缶に収納した。そして、電極体上下両面
に絶縁板を配設し、アルミニウム製の正極リードを正極
集電体から導出して電池蓋に溶接し、ニッケル製の負極
リードを負極集電体から導出して電池缶に溶接した。Next, the electrode body was housed in a nickel-plated iron battery can. Then, insulating plates are provided on the upper and lower surfaces of the electrode body, the aluminum positive electrode lead is led out of the positive electrode current collector and welded to the battery lid, and the nickel negative electrode lead is drawn out of the negative electrode current collector and the battery can Welded.

【００７３】そして、電池缶の中に、エチレンカーボネ
ートとジメチルカーボネートとを１対１で混合した溶液
にＬｉＢＦ４を１ｍｏｌ／ｌとなるように溶解した電解
液を注入した。次いで、アスファルトで表面を塗布した
絶縁封口ガスケットを介して電池缶をかしめることによ
り、電流遮断機構を有する安全弁装置、ＰＴＣ素子並び
に電池蓋を固定し、電池内の気密性を保持させた。Then, an electrolyte obtained by dissolving LiBF 4 at a concentration of 1 mol / l in a solution obtained by mixing ethylene carbonate and dimethyl carbonate at a ratio of 1: 1 was injected into the battery can. Next, the battery can was caulked through an insulating sealing gasket whose surface was coated with asphalt, thereby fixing the safety valve device having the current cutoff mechanism, the PTC element, and the battery lid, thereby maintaining the airtightness in the battery.

【００７４】以上のようにして、直径が１８ｍｍ、高さ
が６５ｍｍである円筒型の非水電解液二次電池を作製し
た。As described above, a cylindrical non-aqueous electrolyte secondary battery having a diameter of 18 mm and a height of 65 mm was produced.

【００７５】比較例１ 負極活物質のみからなる負極材料を用いること以外は、
実施例１と同様にして非水電解液二次電池を作製した。 Comparative Example 1 Except for using the negative electrode material consisting of only the negative electrode active material,
A non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 1.

【００７６】比較例２ 負極活物質を９９．５重量％と、カーボンブラックを
０．５重量％とを混合してなる負極材料を用いること以
外は、実施例１と同様にして非水電解液二次電池を作製
した。 Comparative Example 2 A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that a negative electrode material obtained by mixing 99.5% by weight of the negative electrode active material and 0.5% by weight of carbon black was used. A secondary battery was manufactured.

【００７７】比較例３ 負極活物質を９９．０重量％と、繊維状炭素を１．０重
量％とを混合してなる負極材料を用いること以外は、実
施例１と同様にして非水電解液二次電池を作製した。 Comparative Example 3 Non-aqueous electrolysis was performed in the same manner as in Example 1, except that a negative electrode material obtained by mixing 99.0% by weight of the negative electrode active material and 1.0% by weight of fibrous carbon was used. A liquid secondary battery was manufactured.

【００７８】以上のようにして作製された実施例１及び
比較例１〜比較例３の非水電解液二次電池に対して、先
ず、２３℃環境下において、充電電流を０．５Ａとして
終止電圧が４．２Ｖまで４時間の定電流充電を行った。
そして、２３℃環境下において、放電電流を０．５Ａと
して終止電圧が２．７５Ｖまでの定電流放電を行い、初
期電池容量を測定した。The non-aqueous electrolyte secondary batteries of Example 1 and Comparative Examples 1 to 3 manufactured as described above were terminated at a charging current of 0.5 A under a 23 ° C. environment. The constant current charging was performed for 4 hours until the voltage reached 4.2 V.
Then, in a 23 ° C. environment, a constant current discharge was performed until the final voltage was 2.75 V with a discharge current of 0.5 A, and the initial battery capacity was measured.

【００７９】次に、２３℃環境下において、充電電流を
１．０Ａとして終止電圧が４．２Ｖまで２．５時間の定
電流充電を行った。その後、−１０℃環境下において、
放電電流を１．０Ａとして終止電圧が２．７５Ｖまでの
定電流放電を行い、−１０℃環境下での電池容量を測定
した。そして、初期電池容量に対する−１０℃環境下で
の電池容量の割合を求め、その比率を−１０℃環境下で
の電池容量維持率とした。Next, under a 23 ° C. environment, constant current charging was performed for 2.5 hours until the final voltage was 4.2 V, with the charging current being 1.0 A. Then, under -10 ° C environment,
At a discharge current of 1.0 A, a constant current discharge was performed to a final voltage of 2.75 V, and the battery capacity under a -10 ° C environment was measured. Then, the ratio of the battery capacity under the -10 ° C environment to the initial battery capacity was determined, and the ratio was defined as the battery capacity retention rate under the -10 ° C environment.

【００８０】以上の測定結果と、負極材料中における繊
維状炭素及びカーボンブラックの含有量とを合わせて表
１に示す。なお、表１において、繊維状炭素の含有量を
ａ重量％とし、カーボンブラックの含有量をｂ重量％と
して、繊維状炭素とカーボンブラックとの重量比をａ／
ｂで表す。Table 1 shows the results of the above measurements together with the contents of fibrous carbon and carbon black in the negative electrode material. In Table 1, the content of fibrous carbon is a weight%, the content of carbon black is b weight%, and the weight ratio of fibrous carbon to carbon black is a /%.
Expressed as b.

【００８１】[0081]

【表１】 [Table 1]

【００８２】表１から、実施例１の非水電解液二次電池
では、初期電池容量が高く、−１０℃環境下における電
池容量維持率が高いことがわかる。Table 1 shows that the non-aqueous electrolyte secondary battery of Example 1 has a high initial battery capacity and a high battery capacity retention rate in an environment of -10 ° C.

【００８３】これに対し、比較例１の非水電解質二次電
池は、初期電池容量が低く、−１０℃環境下における電
池容量維持率も低いことがわかる。また、比較例２の非
水電解液二次電池は、−１０℃環境下における電池容量
が改善されているが、初期電池容量が低いことがわか
る。また、比較例３の非水電解液二次電池は、初期電池
容量が高いが、−１０℃環境下における電池容量維持率
が低いことがわかる。On the other hand, it can be seen that the nonaqueous electrolyte secondary battery of Comparative Example 1 has a low initial battery capacity and a low battery capacity retention rate in an environment of −10 ° C. The non-aqueous electrolyte secondary battery of Comparative Example 2 has an improved battery capacity under a -10 ° C environment, but has a low initial battery capacity. In addition, it can be seen that the nonaqueous electrolyte secondary battery of Comparative Example 3 has a high initial battery capacity, but has a low battery capacity retention rate in a -10 ° C environment.

【００８４】従って、非水電解液二次電池は、負極活物
質、繊維状炭素およびカーボンブラックとからなる負極
材料を含有する負極を備えることにより、低温環境下で
充放電する場合であっても、充放電特性に優れ、高い電
池容量を有することがわかる。Therefore, the non-aqueous electrolyte secondary battery is provided with the negative electrode containing the negative electrode material composed of the negative electrode active material, fibrous carbon and carbon black, so that it can be charged and discharged even in a low-temperature environment. It can be seen that the battery has excellent charge-discharge characteristics and high battery capacity.

【００８５】＜実験２＞実験２では、負極材料中に含有
させるカーボンブラックの含有量を一定とし、繊維状炭
素の含有量を変化させた場合の電池特性を評価した。<Experiment 2> In Experiment 2, the battery characteristics when the content of fibrous carbon was changed while the content of carbon black contained in the negative electrode material was kept constant were evaluated.

【００８６】実施例２〜実施例９ カーボンブラックの含有量を０．５重量％とし、負極活
物質および繊維状炭素の含有量を表２に示すようにして
調製した負極材料を用いること以外は実施例１と同様に
して非水電解液二次電池を作製した。 Examples 2 to 9 Except that the content of carbon black was 0.5% by weight, and that the negative electrode materials prepared as shown in Table 2 were used for the negative electrode active material and fibrous carbon, respectively, were used. A non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 1.

【００８７】以上のようにして作製した実施例２から実
施例９の非水電解液二次電池について、初期電池容量お
よび−１０℃環境下における電池容量維持率を、上述し
た方法と同様にして測定した。For the non-aqueous electrolyte secondary batteries of Examples 2 to 9 manufactured as described above, the initial battery capacity and the battery capacity retention rate in an environment of −10 ° C. were determined in the same manner as in the above-described method. It was measured.

【００８８】以上の測定結果を、負極材料中における繊
維状炭素及びカーボンブラックの含有量、ａ／ｂと合わ
せて表２に示す。The above measurement results are shown in Table 2 together with the contents of fibrous carbon and carbon black in the negative electrode material and a / b.

【００８９】[0089]

【表２】 [Table 2]

【００９０】表２より、負極材料中に繊維状炭素が０．
１重量％含有されている実施例２の非水電解液二次電池
は、負極材料中に繊維状炭素が含有されていない比較例
２（表１）の非水電解液二次電池と比較すると、初期電
池容量が高く、−１０℃環境下における電池容量維持率
も向上していることがわかる。From Table 2, it can be seen that the amount of fibrous carbon in the negative electrode material was 0.1%.
The non-aqueous electrolyte secondary battery of Example 2 containing 1% by weight was compared with the non-aqueous electrolyte secondary battery of Comparative Example 2 (Table 1) in which fibrous carbon was not contained in the negative electrode material. It can be seen that the initial battery capacity is high and the battery capacity retention rate in a -10 ° C environment is also improved.

【００９１】また、負極材料中に繊維状炭素が１０重量
％含有されている実施例８の非水電解液二次電池は、負
極材料中に繊維状炭素が２０重量％含有されている実施
例９の非水電解液二次電池と比較すると、初期電池容量
がより高く、−１０℃環境下における電池容量がより高
いことがわかる。Further, in the nonaqueous electrolyte secondary battery of Example 8 in which fibrous carbon was contained in the negative electrode material at 10% by weight, the non-aqueous electrolyte secondary battery of Example 8 contained 20% by weight of fibrous carbon in the negative electrode material. As compared with the nonaqueous electrolyte secondary battery of No. 9, the initial battery capacity is higher, and the battery capacity under a -10 ° C environment is higher.

【００９２】従って、非水電解液二次電池では、繊維状
炭素が負極材料中に０．１重量％以上、１０重量％以下
の範囲で含有されるていると、負極では本来の容量を十
分に引き出すことができ、高い電池容量が実現されるこ
とがわかる。Therefore, in the non-aqueous electrolyte secondary battery, if the fibrous carbon is contained in the range of 0.1% by weight or more and 10% by weight or less in the negative electrode material, the negative electrode will have a sufficient capacity. It can be seen that high battery capacity is realized.

【００９３】＜実験３＞実験３では、負極材料中に含有
させる繊維状炭素の含有量を一定とし、カーボンブラッ
クの含有量を変化させた場合の電池特性を評価した。<Experiment 3> In Experiment 3, the battery characteristics when the content of fibrous carbon contained in the negative electrode material was fixed and the content of carbon black was changed were evaluated.

【００９４】実施例１０〜実施例１７ 繊維状炭素の含有量を１．０重量％とし、負極活物質お
よびカーボンブラックの含有量を表３に示すようにして
調製した負極材料を用いること以外は実施例１と同様に
して非水電解液二次電池を作製した。 Examples 10 to 17 Except that the content of fibrous carbon was set to 1.0% by weight and the negative electrode materials prepared as shown in Table 3 were used for the negative electrode active material and the carbon black, respectively, were used. A non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 1.

【００９５】以上のようにして作製した実施例１０から
実施例１７の非水電解液二次電池について、初期電池容
量および−１０℃環境下における電池容量維持率を、上
述した方法と同様にして測定した。For the non-aqueous electrolyte secondary batteries of Examples 10 to 17 manufactured as described above, the initial battery capacity and the battery capacity retention rate in an environment of −10 ° C. were determined in the same manner as in the above-described method. It was measured.

【００９６】以上の測定結果を、負極材料中における繊
維状炭素及びカーボンブラックの含有量、ａ／ｂと合わ
せて表３に示す。Table 3 shows the above measurement results together with the contents of fibrous carbon and carbon black in the negative electrode material and a / b.

【００９７】[0097]

【表３】 [Table 3]

【００９８】表３より、負極材料中にカーボンブラック
が０．０２重量％含有されている実施例１１の非水電解
液二次電池は、負極材料中にカーボンブラックが０．０
１重量％含有されている実施例１０の非水電解液二次電
池と比較すると、同程度に良好な初期電池容量を有して
いるとともに、−１０℃環境下における電池容量維持率
がより向上していることがわかる。From Table 3, it can be seen that the nonaqueous electrolyte secondary battery of Example 11 in which the negative electrode material contained 0.02% by weight of carbon black contained 0.06% by weight of carbon black in the negative electrode material.
Compared to the non-aqueous electrolyte secondary battery of Example 10 containing 1% by weight, the battery has the same good initial battery capacity and the battery capacity retention rate in a -10 ° C environment is further improved. You can see that it is doing.

【００９９】また、負極材料中にカーボンブラックが
２．０重量％含有されている実施例１６の非水電解液二
次電池は、負極材料中にカーボンブラックが３．０重量
％含有されている実施例１７の非水電解液二次電池と比
較すると、同程度に良好な−１０℃環境下における電池
容量維持率を有しているとともに、初期電池容量がより
高いことがわかる。Further, in the nonaqueous electrolyte secondary battery of Example 16 in which carbon black was contained in the negative electrode material in an amount of 2.0% by weight, carbon black was contained in the negative electrode material in an amount of 3.0% by weight. As compared with the non-aqueous electrolyte secondary battery of Example 17, it is understood that the battery has the same good battery capacity retention rate in the -10 ° C. environment and has a higher initial battery capacity.

【０１００】従って、非水電解液二次電池は、カーボン
ブラックが負極材料中に０．０２重量％以上、２重量％
以下の範囲で含有されるていると、例えば−１０℃とい
う低温環境下で充放電された場合であっても、良好な充
放電特性を有し、高い電池容量を有することがわかる。Therefore, in the non-aqueous electrolyte secondary battery, carbon black is contained in the negative electrode material in an amount of 0.02% by weight or more and 2% by weight or less.
When contained in the following range, for example, even when charged and discharged in a low-temperature environment of -10 ° C, the battery has good charge / discharge characteristics and a high battery capacity.

【０１０１】ここで、繊維状炭素とカーボンブラックと
の重量比、すなわちａ／ｂについて考察する。ａ／ｂが
２０である実施例８を、ａ／ｂが３０である実施例９お
よびａ／ｂが１００である実施例１０と比較すると、実
施例８は−１０℃環境下における容量維持率がより高い
ことがわかる。Here, the weight ratio between fibrous carbon and carbon black, that is, a / b will be considered. When Example 8 in which a / b is 20 is compared with Example 9 in which a / b is 30 and Example 10 in which a / b is 100, Example 8 has a capacity retention ratio in an environment of −10 ° C. Is higher.

【０１０２】また、ａ／ｂが０．５である実施例１６
を、ａ／ｂが０．４である実施例２およびａ／ｂが０．
３３である実施例１７と比較すると実施例１６は初期電
池容量がより高いことがわかる。Embodiment 16 in which a / b is 0.5
In Example 2 in which a / b is 0.4 and 0 in a / b.
It can be seen that Example 16 has a higher initial battery capacity as compared to Example 17, which is 33.

【０１０３】したがって、繊維状炭素とカーボンブラッ
クとの重量比を０．５以上、２０以下の範囲とすること
により、負極活物質粒界の導電性を高める作用と、負極
に電解液を保持する作用とを両立して得ることができ、
極めて電池特性に優れる非水電解液二次電池を得られる
ことがわかる。Therefore, by setting the weight ratio of fibrous carbon to carbon black to be in the range of 0.5 or more and 20 or less, the effect of increasing the conductivity of the negative electrode active material grain boundary and maintaining the electrolyte in the negative electrode are provided. Can achieve both the effect and
It can be seen that a nonaqueous electrolyte secondary battery having extremely excellent battery characteristics can be obtained.

【０１０４】[0104]

【発明の効果】以上の説明からも明らかなように、本発
明に係る非水電解質電池は、正極と、負極活物質と繊維
状炭素とカーボンブラックとからなる負極材料を有する
負極と、電解質とを備えているので、低温環境下で充放
電をされた場合でも、良好な充放電特性を有し、高容量
である。As is apparent from the above description, the nonaqueous electrolyte battery according to the present invention comprises a positive electrode, a negative electrode having a negative electrode material comprising a negative electrode active material, fibrous carbon and carbon black, and an electrolyte. Therefore, even when charged and discharged in a low-temperature environment, it has good charge / discharge characteristics and high capacity.

【図面の簡単な説明】[Brief description of the drawings]

【図１】円筒型の非水電解液二次電池の一構成例を示す
断面図である。FIG. 1 is a cross-sectional view illustrating a configuration example of a cylindrical nonaqueous electrolyte secondary battery.

【符号の説明】[Explanation of symbols]

１ 非水電解液二次電池、２ 負極、３ 正極、４ セ
パレータ、５ 電池缶、６ 負極集電体、７ 正極集電
体、８ 絶縁板、９ 負極リード、１０ 正極リード、
１１ 電池蓋、１２ 絶縁封口ガスケット、１３ 安全
弁装置、１４ＰＴＣ素子1 Non-aqueous electrolyte secondary battery, 2 Negative electrode, 3 Positive electrode, 4 Separator, 5 Battery can, 6 Negative current collector, 7 Positive current collector, 8 Insulating plate, 9 Negative lead, 10 Positive lead,
11 Battery cover, 12 Insulation sealing gasket, 13 Safety valve device, 14 PTC element

フロントページの続き (72)発明者 小丸 篤雄 福島県安達郡本宮町字樋ノ口２番地 ソニ ー福島株式会社内 (72)発明者 井本 浩 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 AJ06 AK03 AL06 AL07 AM02 AM03 AM04 AM05 AM07 BJ02 DJ08 DJ15 EJ04 HJ01 5H050 AA06 AA08 AA12 BA17 CB07 CB08 DA10 EA08 EA10 FA16 HA01 Continuing on the front page (72) Inventor Atsushi Komaru 2 Hinoguchi, Motomiya-cho, Adachi-gun, Fukushima Prefecture Inside Sony Fukushima Co., Ltd. (72) Inventor Hiroshi Imoto 6-7-35 Kita Shinagawa, Shinagawa-ku, Tokyo Sony Corporation F term (reference) 5H029 AJ03 AJ06 AK03 AL06 AL07 AM02 AM03 AM04 AM05 AM07 BJ02 DJ08 DJ15 EJ04 HJ01 5H050 AA06 AA08 AA12 BA17 CB07 CB08 DA10 EA08 EA10 FA16 HA01

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 リチウムをドープ／脱ドープ可能な正極
活物質を含有する正極と、 リチウムをドープ／脱ドープ可能な負極活物質、繊維状
炭素およびカーボンブラックからなる負極材料を含有す
る負極と、 非水電解質とを備えることを特徴とする非水電解質電
池。1. A positive electrode containing a lithium-doped / dedopable positive electrode active material; a lithium-doped / dedopable negative electrode active material; a negative electrode containing a negative electrode material comprising fibrous carbon and carbon black; A nonaqueous electrolyte battery comprising: a nonaqueous electrolyte. 【請求項２】 上記繊維状炭素が、負極材料中に０．１
重量％以上、１０重量％以下の範囲で含有されることを
特徴とする請求項１記載の非水電解質電池。2. The method according to claim 1, wherein the fibrous carbon is 0.1% in the negative electrode material.
2. The non-aqueous electrolyte battery according to claim 1, wherein the non-aqueous electrolyte battery is contained in an amount of not less than 10% by weight and not more than 10% by weight. 【請求項３】 上記カーボンブラックが、負極材料中に
０．０２重量％以上、２重量％以下の範囲で含有される
ことを特徴とする請求項１記載の非水電解質電池。3. The non-aqueous electrolyte battery according to claim 1, wherein the carbon black is contained in the negative electrode material in a range of 0.02% by weight or more and 2% by weight or less. 【請求項４】 上記繊維状炭素と上記カーボンブラック
との重量比が、０．５以上、２０以下の範囲であること
を特徴とする請求項１記載の非水電解質電池。4. The non-aqueous electrolyte battery according to claim 1, wherein a weight ratio of the fibrous carbon to the carbon black is in a range of 0.5 or more and 20 or less. 【請求項５】 上記非水電解質は、非水電解液であるこ
とを特徴とする請求項１記載の非水電解質電池。5. The non-aqueous electrolyte battery according to claim 1, wherein the non-aqueous electrolyte is a non-aqueous electrolyte.
JP2000360256A 2000-11-27 2000-11-27 Non-aqueous electrolyte battery Expired - Lifetime JP4734707B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2000360256A JP4734707B2 (en) 2000-11-27 2000-11-27 Non-aqueous electrolyte battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2000360256A JP4734707B2 (en) 2000-11-27 2000-11-27 Non-aqueous electrolyte battery

Publications (2)

Publication Number Publication Date
JP2002164052A true JP2002164052A (en) 2002-06-07
JP4734707B2 JP4734707B2 (en) 2011-07-27

Family

ID=18831885

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2000360256A Expired - Lifetime JP4734707B2 (en) 2000-11-27 2000-11-27 Non-aqueous electrolyte battery

Country Status (1)

Country Link
JP (1) JP4734707B2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007004728A1 (en) * 2005-07-04 2007-01-11 Showa Denko K.K. Method for producing anode for lithium secondary battery and anode composition, and lithium secondary battery
JP2009059713A (en) * 2008-11-11 2009-03-19 Mitsubishi Materials Corp Negative electrode material, negative electrode using the same, and lithium ion battery and lithium polymer battery using the negative electrode
CN105226291A (en) * 2015-10-27 2016-01-06 苏州宽温电子科技有限公司 A kind of environment-friendly water-based binding agent and preparation method thereof
KR20190096649A (en) * 2018-02-09 2019-08-20 삼성에스디아이 주식회사 Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same
US10923705B2 (en) 2017-05-26 2021-02-16 Toyota Jidosha Kabushiki Kaisha Method of producing negative electrode for nonaqueous electrolyte secondary battery and method of producing nonaqueous electrolyte secondary battery

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1079252A (en) * 1996-09-04 1998-03-24 Toray Ind Inc Battery electrode and non-aqueous solvent-based secondary battery using thereof
JPH113710A (en) * 1997-06-10 1999-01-06 Hitachi Maxell Ltd Lithium secondary battery
JPH1125954A (en) * 1997-07-02 1999-01-29 Toray Ind Inc Secondary battery
JPH1173996A (en) * 1997-08-28 1999-03-16 Toray Ind Inc Nonaqueous secondary battery
JPH1173997A (en) * 1997-08-28 1999-03-16 Toray Ind Inc Nonaqueous secondary battery
JPH11144714A (en) * 1997-11-07 1999-05-28 Toray Ind Inc Manufacture of slurry for electrode
JPH11204107A (en) * 1998-01-13 1999-07-30 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary battery
JP2000133267A (en) * 1998-10-28 2000-05-12 Toyota Central Res & Dev Lab Inc Negative active material for lithium secondary battery and lithium secondary battery using this
JP2000294283A (en) * 1999-04-02 2000-10-20 Toshiba Battery Co Ltd Polymer lithium secondary battery

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1079252A (en) * 1996-09-04 1998-03-24 Toray Ind Inc Battery electrode and non-aqueous solvent-based secondary battery using thereof
JPH113710A (en) * 1997-06-10 1999-01-06 Hitachi Maxell Ltd Lithium secondary battery
JPH1125954A (en) * 1997-07-02 1999-01-29 Toray Ind Inc Secondary battery
JPH1173996A (en) * 1997-08-28 1999-03-16 Toray Ind Inc Nonaqueous secondary battery
JPH1173997A (en) * 1997-08-28 1999-03-16 Toray Ind Inc Nonaqueous secondary battery
JPH11144714A (en) * 1997-11-07 1999-05-28 Toray Ind Inc Manufacture of slurry for electrode
JPH11204107A (en) * 1998-01-13 1999-07-30 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary battery
JP2000133267A (en) * 1998-10-28 2000-05-12 Toyota Central Res & Dev Lab Inc Negative active material for lithium secondary battery and lithium secondary battery using this
JP2000294283A (en) * 1999-04-02 2000-10-20 Toshiba Battery Co Ltd Polymer lithium secondary battery

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007004728A1 (en) * 2005-07-04 2007-01-11 Showa Denko K.K. Method for producing anode for lithium secondary battery and anode composition, and lithium secondary battery
US8003257B2 (en) 2005-07-04 2011-08-23 Showa Denko K.K. Method for producing anode for lithium secondary battery and anode composition, and lithium secondary battery
US8685362B2 (en) 2005-07-04 2014-04-01 Showa Denko K.K. Method for producing anode for lithium secondary battery and anode composition, and lithium secondary battery
US9276257B2 (en) 2005-07-04 2016-03-01 Showa Denko K.K. Method for producing anode for lithium secondary battery and anode composition, and lithium secondary battery
JP2009059713A (en) * 2008-11-11 2009-03-19 Mitsubishi Materials Corp Negative electrode material, negative electrode using the same, and lithium ion battery and lithium polymer battery using the negative electrode
CN105226291A (en) * 2015-10-27 2016-01-06 苏州宽温电子科技有限公司 A kind of environment-friendly water-based binding agent and preparation method thereof
US10923705B2 (en) 2017-05-26 2021-02-16 Toyota Jidosha Kabushiki Kaisha Method of producing negative electrode for nonaqueous electrolyte secondary battery and method of producing nonaqueous electrolyte secondary battery
KR20190096649A (en) * 2018-02-09 2019-08-20 삼성에스디아이 주식회사 Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same
KR102343706B1 (en) 2018-02-09 2021-12-24 삼성에스디아이 주식회사 Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same

Also Published As

Publication number Publication date
JP4734707B2 (en) 2011-07-27

Similar Documents

Publication Publication Date Title
JP4147442B2 (en) Non-aqueous electrolyte type secondary battery
JP4228593B2 (en) Nonaqueous electrolyte secondary battery
JP4161376B2 (en) Non-aqueous electrolyte secondary battery
JP3436033B2 (en) Non-aqueous electrolyte secondary battery
JP2007048717A (en) Battery
JP3709628B2 (en) Non-aqueous electrolyte secondary battery
JPH07192724A (en) Nonaqueous electrolyte secondary battery
JPH11233140A (en) Nonaqueous electrolyte secondary battery
JPH0927344A (en) Nonaqueous electrolyte secondary battery
JP2003346804A (en) Negative electrode material, non-aqueous electrolyte battery, and method for manufacturing the negative electrode material
JP3552377B2 (en) Rechargeable battery
JP2001196052A (en) Negative electrode and nonaqueous electrolyte battery
JP4192574B2 (en) Non-aqueous electrolyte secondary battery electrode and non-aqueous electrolyte secondary battery
JP4395925B2 (en) Non-aqueous electrolyte battery
JP4734707B2 (en) Non-aqueous electrolyte battery
JP2002198036A (en) Negative electrode, nonaqueous electrolyte cell and their manufacturing method
JPH07335262A (en) Nonaqueous electrolyte secondary battery
JPH0613109A (en) Nonaqueous electrolyte secondary battery
JP3863514B2 (en) Lithium secondary battery
JP2001148241A (en) Non-aqueous electrolyte battery
JP3787943B2 (en) Non-aqueous electrolyte secondary battery
JP2000251885A (en) Negative electrode material for nonaqueous electrolyte secondary battery, and secondary battery using the material
JP2007280836A (en) Negative electrode mixture for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
JP2000348719A (en) Nonaqueous electrolyte secondary battery
JP2001216970A (en) Nonaqueous electrolyte battery

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20070130

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20100114

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20100119

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20100315

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110111

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110304

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20110329

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20110411

R151 Written notification of patent or utility model registration

Ref document number: 4734707

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R151

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140513

Year of fee payment: 3

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313113

Free format text: JAPANESE INTERMEDIATE CODE: R313111

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R360 Written notification for declining of transfer of rights

Free format text: JAPANESE INTERMEDIATE CODE: R360

R371 Transfer withdrawn

Free format text: JAPANESE INTERMEDIATE CODE: R371

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313113

R360 Written notification for declining of transfer of rights

Free format text: JAPANESE INTERMEDIATE CODE: R360

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R360 Written notification for declining of transfer of rights

Free format text: JAPANESE INTERMEDIATE CODE: R360

R371 Transfer withdrawn

Free format text: JAPANESE INTERMEDIATE CODE: R371

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313113

R360 Written notification for declining of transfer of rights

Free format text: JAPANESE INTERMEDIATE CODE: R360

R360 Written notification for declining of transfer of rights

Free format text: JAPANESE INTERMEDIATE CODE: R360

R371 Transfer withdrawn

Free format text: JAPANESE INTERMEDIATE CODE: R371

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313113

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

EXPY Cancellation because of completion of term