JP2003317721A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2003317721A JP2003317721A JP2002124077A JP2002124077A JP2003317721A JP 2003317721 A JP2003317721 A JP 2003317721A JP 2002124077 A JP2002124077 A JP 2002124077A JP 2002124077 A JP2002124077 A JP 2002124077A JP 2003317721 A JP2003317721 A JP 2003317721A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- binder
- acrylonitrile
- butadiene
- battery
- 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.)
- Pending
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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解質二次電
池に関する。TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術】近年、電子技術の進歩により携帯電話、
ノートパソコン、ビデオカメラ等の電子機器の高性能
化、小型化軽量化が進み、これら電子機器に使用できる
高エネルギー密度の電池を求める要求が非常に強くなっ
ている。このような要求を満たす代表的な電池は、リチ
ウムが負極活物質として用いられたリチウム二次電池で
ある。2. Description of the Related Art In recent years, due to advances in electronic technology, mobile phones,
As electronic devices such as laptop computers and video cameras have become higher in performance, smaller in size and lighter in weight, there has been a strong demand for batteries with high energy density that can be used in these electronic devices. A typical battery that meets such requirements is a lithium secondary battery in which lithium is used as a negative electrode active material.
【０００３】リチウム二次電池は、例えば、リチウムイ
オンを吸蔵放出する炭素材料が集電体に保持されてなる
負極板、リチウムコバルト複合酸化物のようなリチウム
イオンを吸蔵放出するリチウム複合酸化物が集電体に保
持されてなる正極板、非プロトン性の有機溶媒にＬｉＣ
ｌＯ４、ＬｉＰＦ６等のリチウム塩が溶解された電解液
を保持するとともに負極板と正極板との間に介在されて
両極の短絡を防止するセパレータとからなっている。Lithium secondary batteries include, for example, a negative electrode plate in which a carbon material that absorbs and releases lithium ions is held by a current collector, and a lithium composite oxide that absorbs and releases lithium ions such as a lithium cobalt composite oxide. A positive electrode plate held by a current collector, LiC in an aprotic organic solvent
It is composed of a separator that holds an electrolytic solution in which a lithium salt such as 10 4 or LiPF 6 is dissolved and that is interposed between the negative electrode plate and the positive electrode plate to prevent a short circuit between both electrodes.
【０００４】そして、これら正極板及び負極板は、薄板
状に成形され、これらがセパレータを介して順に積層又
は円筒形状などに巻回されて発電要素とされ、この発電
要素が、ステンレス、ニッケルメッキを施した鉄、又は
アルミニウム製等の金属缶または、ラミネートフィルム
からなる電池容器に収納された後、電解液が注液され、
密封されて電池とされる。The positive electrode plate and the negative electrode plate are formed into a thin plate shape, and these are sequentially laminated or wound into a cylindrical shape or the like via a separator to form a power generating element. The power generating element is plated with stainless steel or nickel. After being stored in a metal can made of iron, aluminum, or the like, or a battery container made of a laminated film, an electrolytic solution is injected,
The battery is hermetically sealed.
【０００５】正極板や負極板は、活物質粒子と結着剤と
を含んでなる塗液を集電体上に塗工することで活物質合
材層を集電体に形成することで作製される。結着剤とし
ては、種々のものを用いることが可能で、例えば、ポリ
フッ化ビニリデンや、スチレンブタジエンゴム等が知ら
れており、ポリフッ化ビニリデンが用いられることが多
い。The positive electrode plate and the negative electrode plate are produced by applying a coating liquid containing active material particles and a binder onto a current collector to form an active material mixture layer on the current collector. To be done. Various binders can be used, for example, polyvinylidene fluoride, styrene-butadiene rubber, etc. are known, and polyvinylidene fluoride is often used.
【０００６】[0006]
【発明が解決しようとする課題】最近では、このような
リチウム二次電池において、以前にも増して高容量化へ
の動きが急速に進みつつある。特に携帯電話において
は、通常の通話だけではなく画像や音楽ファイルの送受
信に対応していることなど、今までにも増して多くの電
力消費量が必要とされる。そのために内蔵されたリチウ
ム二次電池を高容量化させることがさらに重要となって
きている。Recently, in such a lithium secondary battery, the movement toward higher capacity is rapidly progressing more than ever before. In particular, mobile phones are required to consume much more power than ever, such as being able to send and receive images and music files as well as ordinary calls. Therefore, it has become more important to increase the capacity of the built-in lithium secondary battery.
【０００７】従来からのリチウムイオン電池の正極に使
用されているポリフッ化ビニリデンは、耐酸化性に優れ
ているがアルミニウム箔などの金属集電体との接着性に
乏しいために、高容量化のために結着剤量を減らすと正
極合材が集電体から剥離して、それにより電池が短絡す
るなどの不都合が生じることがあった。さらに、ポリフ
ッ化ビニリデンは比較的結晶性の高い樹脂であり硬い性
質をもつ。そのために、ポリフッ化ビニリデンを用いた
正極合材は硬くなるために、特に電極を巻回して発電要
素を作製する際には、正極板が切断したりするという不
都合を生じることがあった。Polyvinylidene fluoride used for the positive electrode of a conventional lithium ion battery is excellent in oxidation resistance but poor in adhesion to a metal current collector such as an aluminum foil, so that it has a high capacity. Therefore, when the amount of the binder is reduced, the positive electrode mixture may be separated from the current collector, which may cause inconvenience such as short circuit of the battery. Further, polyvinylidene fluoride is a resin having relatively high crystallinity and has a hard property. For this reason, the positive electrode mixture made of polyvinylidene fluoride becomes hard, which may cause a disadvantage that the positive electrode plate is cut especially when the electrode is wound to produce a power generating element.
【０００８】また、ポリフッ化ビニリデンの接着性が乏
しいという問題を改善したものに、マレイン酸などのエ
チレン性不飽和ジカルボン酸等と共重合したポリフッ化
ビニリデンなども開発されているが、コバルト酸リチウ
ムなどのアルカリ性の金属化合物などでは、アルカリ分
の影響を受けてスラリーのゲル化を引き起こすために適
用できなかった。[0008] In addition, polyvinylidene fluoride copolymerized with an ethylenically unsaturated dicarboxylic acid such as maleic acid has been developed to solve the problem of poor adhesion of polyvinylidene fluoride, but lithium cobalt oxide is also known. Alkaline metal compounds such as, for example, cannot be applied because they are affected by the alkali content and cause gelation of the slurry.
【０００９】以上の問題に鑑み、本発明の課題は、活物
質粒子と結着剤とを含む混合物が合材層として集電体に
形成されてなる極板を備えた、リチウム二次電池に代表
される非水電解質二次電池において、合材中の結着剤量
を減らしても活物質の脱落を抑制して、さらに低温放電
性能にもすぐれた電池を提供することを目的とする。In view of the above problems, an object of the present invention is to provide a lithium secondary battery including an electrode plate in which a mixture containing active material particles and a binder is formed as a mixture layer on a current collector. In a representative non-aqueous electrolyte secondary battery, it is an object of the present invention to provide a battery that suppresses the active material from falling off even if the amount of the binder in the mixture is reduced, and further has excellent low-temperature discharge performance.
【００１０】[0010]
【課題を解決するための手段】上記課題を解決するため
に鋭意研究を重ねた結果、結着剤としてアクリロニトリ
ル・ブタジエン系共重合体を用いることにより、従来の
結着剤とくらべて合材中の結着剤量を減らすことがで
き、電池が高容量化できることを見いだした。そして、
さらに詳細に検討した結果、前記アクリロニトリル・ブ
タジエン系共重合体の重量平均分子量が接着性および低
温放電性能や高率放電性能に影響することを突き止め
た。また、前記アクリロニトリル・ブタジエン系共重合
体の正極合剤中における含有量が接着性および低温放電
性能や高率放電性能に影響することがわかった。[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the use of an acrylonitrile-butadiene-based copolymer as a binder results in the formation of a composite material as compared with a conventional binder. It has been found that the amount of binder can be reduced and the capacity of the battery can be increased. And
As a result of further detailed investigation, it was found that the weight average molecular weight of the acrylonitrile / butadiene-based copolymer affects the adhesiveness and the low temperature discharge performance and the high rate discharge performance. It was also found that the content of the acrylonitrile / butadiene-based copolymer in the positive electrode mixture affects the adhesiveness, the low temperature discharge performance and the high rate discharge performance.
【００１１】すなわち、前記課題を解決する、本発明の
非水電解質二次電池は、リチウムイオンを吸蔵放出でき
る金属化合物を正極活物質として、該正極活物質の粒子
と導電剤と結着剤とを含む混合物が合材層として金属集
電体に形成されてなる正極を備えた非水電解質二次電池
において、上記結着剤として重量平均分子量が３０，０
００〜５００，０００であるアクリロニトリル・ブタジ
エン系共重合体が用いられていることを特徴とするもの
である。That is, the non-aqueous electrolyte secondary battery of the present invention, which solves the above problems, uses a metal compound capable of inserting and extracting lithium ions as a positive electrode active material, and particles of the positive electrode active material, a conductive agent, and a binder. In a non-aqueous electrolyte secondary battery provided with a positive electrode in which a mixture containing is formed on a metal current collector as a mixture layer, the binder has a weight average molecular weight of 30,0.
It is characterized in that an acrylonitrile-butadiene-based copolymer having a content of 00 to 500,000 is used.
【００１２】アクリロニトリル・ブタジエン系共重合体
を結着剤として正極に用いることにより、ポリフッ化ビ
ニリデンよりも接着性に優れるので、剥離を抑制でき
る。特に電極を巻回して発電要素を作製する際には、正
極板が切断するという不都合が抑制される。By using an acrylonitrile / butadiene-based copolymer as a binder in the positive electrode, the adhesive property is superior to that of polyvinylidene fluoride, and peeling can be suppressed. In particular, when the power generation element is manufactured by winding the electrode, the disadvantage that the positive electrode plate is cut is suppressed.
【００１３】前記アクリロニトリル・ブタジエン系共重
合体としては、例えば好適に用いることが出来るものと
して、アクリロニトリルとブタジエンとの共重合体、ブ
タジエンとイソプレンとアクリロニトリルとの共重合
体、アクリロニトリルとブタジエンとメタクリル酸メチ
ルとの共重合体、または、アクリル酸、イタコン酸、フ
マル酸、マレイン酸などのエチレン性不飽和ジカルボン
酸とアクリロニトリルとブタジエンおよびメタクリル酸
メチルとの共重合体などがあり、種々の共重合体を用い
ることができる。その中でも柔軟性と接着性の良好なエ
チレン性不飽和ジカルボン酸とアクリロニトリルとブタ
ジエンおよびメタクリル酸メチルとの共重合体が、電池
性能上特に好ましい。As the acrylonitrile / butadiene-based copolymer, for example, those which can be preferably used include acrylonitrile / butadiene copolymers, butadiene / isoprene / acrylonitrile copolymers, acrylonitrile / butadiene / methacrylic acid copolymers. There are various copolymers such as copolymers with methyl, or copolymers of ethylenically unsaturated dicarboxylic acids such as acrylic acid, itaconic acid, fumaric acid and maleic acid, acrylonitrile, butadiene and methyl methacrylate. Can be used. Among them, a copolymer of an ethylenically unsaturated dicarboxylic acid, acrylonitrile, butadiene and methyl methacrylate, which has good flexibility and adhesiveness, is particularly preferable in terms of battery performance.
【００１４】極板作製には、例えば、活物質、導電助剤
および結着剤となるポリマー材料、および溶剤を混ぜ合
わせてスラリー状にしたものをアルミニウム箔などの集
電体に塗工する。極板作製時のスラリーに十分な粘性を
得るため、前記アクリロニトリル・ブタジエン系共重合
体の重量平均分子量が、３０，０００以上のものを用い
ることが望ましい。また、重量平均分子量が大きいもの
では、ポリマー自体が活物質表面を覆うように接着しや
すくなるために、高率放電性能や低温放電性能に悪影響
を及ぼすことがある。そのために前記アクリロニトリル
・ブタジエン系共重合体の重量平均分子量は、５００，
０００以下にすることが望ましい。さらに、正極合材中
における前記アクリロニトリル・ブタジエン系共重合体
の含有量を０．５〜１．５重量％とすることが好まし
い。To prepare the electrode plate, for example, an active material, a polymer material serving as a conductive aid and a binder, and a solvent are mixed to form a slurry, which is applied to a collector such as an aluminum foil. In order to obtain sufficient viscosity of the slurry at the time of producing the electrode plate, it is desirable to use the acrylonitrile / butadiene-based copolymer having a weight average molecular weight of 30,000 or more. Further, when the weight average molecular weight is large, the polymer itself easily adheres to cover the surface of the active material, which may adversely affect the high rate discharge performance and the low temperature discharge performance. Therefore, the acrylonitrile-butadiene-based copolymer has a weight average molecular weight of 500,
It is desirable to set it to 000 or less. Further, it is preferable that the content of the acrylonitrile / butadiene-based copolymer in the positive electrode mixture is 0.5 to 1.5% by weight.
【００１５】また前記課題を解決する、本発明の非水電
解質二次電池は、リチウムイオンを吸蔵放出できる金属
化合物を正極活物質として、該正極活物質の粒子と導電
剤と結着剤とを含む混合物が合材層として金属集電体に
形成されてなる正極を備えた非水電解質二次電池におい
て、上記結着剤としてアクリロニトリル・ブタジエン系
共重合体が用いられ、正極合材中の前記アクリロニトリ
ル・ブタジエン系共重合体の含有量が０．５〜１．５重
量％であることを特徴とするものである。Further, the non-aqueous electrolyte secondary battery of the present invention which solves the above-mentioned problems uses a metal compound capable of inserting and extracting lithium ions as a positive electrode active material, and particles of the positive electrode active material, a conductive agent and a binder. In a non-aqueous electrolyte secondary battery provided with a positive electrode formed by forming a mixture into a metal current collector as a mixture layer, an acrylonitrile-butadiene-based copolymer is used as the binder, The content of the acrylonitrile / butadiene-based copolymer is 0.5 to 1.5% by weight.
【００１６】前記アクリロニトリル・ブタジエン系共重
合体の正極合材中の含有量が０．５重量％未満である
と、結着力が十分でないために、例えば極板を所定の空
孔率までつぶすときの極板合材と金属集電体との間のず
りに耐えられなくなり合材が集電体から剥離してしま
う。０．５重量％以上とすることにより、極板作製時の
スラリーが保持されるための、スラリー中に粘性をもた
せるために十分なポリマー量とすることができる。ま
た、極板合材と金属集電体との接着強度を確保すること
ができる。一方、極板合材中の結着剤量が多すぎると活
物質表面を覆うように接着する傾向が大きくなり、高率
放電性能や低温放電性能に悪影響を及ぼしてしまう。そ
のために前記アクリロニトリル・ブタジエン系共重合体
の正極合材中の含有量は、１．５重量％以下にすること
が望ましい。When the content of the acrylonitrile-butadiene-based copolymer in the positive electrode mixture is less than 0.5% by weight, the binding force is insufficient. Since the electrode plate composite material and the metal current collector cannot withstand shearing, the composite material peels off from the current collector. When the amount is 0.5% by weight or more, the amount of the polymer can be sufficient to retain the slurry during the production of the electrode plate and to give the slurry viscosity. Further, it is possible to secure the adhesive strength between the electrode plate composite material and the metal current collector. On the other hand, when the amount of the binder in the electrode plate mixture is too large, the tendency to adhere to cover the surface of the active material increases, which adversely affects the high rate discharge performance and the low temperature discharge performance. Therefore, the content of the acrylonitrile / butadiene-based copolymer in the positive electrode mixture is preferably 1.5% by weight or less.
【００１７】さらに、前記アクリロニトリル・ブタジエ
ン系共重合体の重量平均分子量を３０，０００〜５０
０，０００とし、正極合材中の含有量を０．５〜１．５
重量％とするのが好ましい。前記放電性能をさらに高め
ることができるからである。Further, the weight average molecular weight of the acrylonitrile-butadiene copolymer is 30,000 to 50.
And the content in the positive electrode mixture is 0.5 to 1.5.
It is preferably set to wt%. This is because the discharge performance can be further enhanced.
【００１８】[0018]
【発明の実施の形態】以下、非水電解質リチウム二次電
池についての実施形態を示しながら、本願発明について
さらに詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to embodiments of a non-aqueous electrolyte lithium secondary battery.
【００１９】正極活物質としては、例えば、ＬｉＣｏＯ
２、ＬｉＮｉＯ２、ＬｉＣｏｘＮｉ１−ｘＯ２、ＬｉＭ
ｎ２Ｏ４、ＭｎＯ２、ＦｅＯ２、Ｖ２Ｏ５、Ｖ
６Ｏ１３、ＴｉＯ２等のトンネル構造または層状構造の
金属酸化物、オキシ水酸化ニッケル等の金属水酸化物、
ＴｉＳ等の金属硫化物、ポリアニリン等の導電性ポリマ
ー等を用いることができ、これらは混合して用いること
もできる。Examples of the positive electrode active material include LiCoO 2.
2 , LiNiO 2 , LiCoxNi1-xO 2 , LiM
n 2 O 4 , MnO 2 , FeO 2 , V 2 O 5 , V
6 O 13 , a metal oxide having a tunnel structure or a layered structure such as TiO 2 , a metal hydroxide such as nickel oxyhydroxide,
A metal sulfide such as TiS or a conductive polymer such as polyaniline can be used, and these can also be mixed and used.
【００２０】正極の結着剤としては、アクリロニトリル
とブタジエンとの共重合体、ブタジエンとイソプレンと
アクリロニトリルとの共重合体、アクリロニトリルとブ
タジエンとメタクリル酸メチルとの共重合体、または、
アクリル酸、イタコン酸、フマル酸、マレイン酸などの
エチレン性不飽和ジカルボン酸とアクリロニトリルとブ
タジエンおよびメタクリル酸メチルとの共重合体などが
あり、種々のアクリルニトリル・ブタジエン共重合体を
用いることができる。As the binder for the positive electrode, a copolymer of acrylonitrile and butadiene, a copolymer of butadiene, isoprene and acrylonitrile, a copolymer of acrylonitrile, butadiene and methyl methacrylate, or
There are copolymers of ethylenically unsaturated dicarboxylic acids such as acrylic acid, itaconic acid, fumaric acid, and maleic acid, acrylonitrile, butadiene, and methyl methacrylate, and various acrylonitrile-butadiene copolymers can be used. .
【００２１】負極活物質としては、例えば、Ａｌ、Ｓ
ｉ、Ｐｂ、Ｓｎ、Ｚｎ、Ｃｄ等とリチウムとの合金、グ
ラファイト、カーボン等の炭素質材料、ＬｉＦｅ
２Ｏ３、ＷＯ ２、ＭｏＯ２、ＳｉＯ、ＣｕＯ、ＳｎＯ等
の金属酸化物、Ｌｉ５（Ｌｉ３Ｎ）等のリチウム金属窒
化物、オキシ水酸化錫等の金属水酸化物、金属リチウム
等を用いることができ、これらは混合して用いることも
できる。Examples of the negative electrode active material include Al and S
Alloys of i, Pb, Sn, Zn, Cd, etc. with lithium,
Lafite, carbonaceous materials such as carbon, LiFe
TwoOThree, WO Two, MoOTwo, SiO, CuO, SnO, etc.
Metal oxides of Li5(LiThreeN) and other lithium metal nitrides
Compounds, metal hydroxides such as tin oxyhydroxide, metal lithium
Etc. can be used, and these can be mixed and used.
it can.
【００２２】負極の結着剤としては、ポリフッ化ビニリ
デンやフッ化ビニリデン系の共重合体、マレイン酸など
の不飽和カルボン酸エステル等と共重合したポリフッ化
ビニリデンやフッ化ビニリデン系の共重合体、スチレン
・ブタジエン共重合体、スチレン・ブタジエン・エチレ
ン・スチレン共重合体、アクリロニトリル・ブタジエン
共重合体やこれらのカルボキシ変性の共重合体、カルボ
キシメチルセルロース、あるいは、メチルセルロース、
ヒドロキシエチルセルロースなどのセルロース類、ポリ
アクリル酸などが挙げられ、これらの複合体を用いるこ
ともできる。As the binder for the negative electrode, polyvinylidene fluoride or vinylidene fluoride copolymer, polyvinylidene fluoride copolymerized with unsaturated carboxylic acid ester such as maleic acid, or vinylidene fluoride copolymer , Styrene / butadiene copolymers, styrene / butadiene / ethylene / styrene copolymers, acrylonitrile / butadiene copolymers and their carboxy-modified copolymers, carboxymethyl cellulose, or methyl cellulose,
Examples thereof include celluloses such as hydroxyethyl cellulose, polyacrylic acid, and the like, and a complex thereof can also be used.
【００２３】非水電解質としては、電解液または無機固
体電解質、ポリマー固体電解質等の固体電解質を使用す
ることができ、電解液を用いる場合には、電解液溶媒と
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、ジエチルカーボネート、γ
−ブチロラクトン、スルホラン、ジメチルスルホキシ
ド、アセトニトリル、ジメチルホルムアミド、ジメチル
アセトアミド、１，２−ジメトキシエタン、１，２−ジ
エトキシエタン、テトラヒドロフラン、２−メチルテト
ラヒドロフラン、ジオキソラン、メチルアセテート等の
極性溶媒、もしくはこれらの混合物を使用することがで
きる。As the non-aqueous electrolyte, an electrolyte solution or a solid electrolyte such as an inorganic solid electrolyte or a polymer solid electrolyte can be used. When an electrolyte solution is used, the electrolyte solution solvent is ethylene carbonate, propylene carbonate, Dimethyl carbonate, diethyl carbonate, γ
-A polar solvent such as butyrolactone, sulfolane, dimethyl sulfoxide, acetonitrile, dimethylformamide, dimethylacetamide, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, methylacetate, or the like. Mixtures can be used.
【００２４】また、溶媒に溶解させるリチウム塩として
は、ＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＢＦ４、ＬｉＡｓＦ
６、ＬｉＣＦ３ＣＯ２、 ＬｉＣＦ３（ＣＦ３）３、Ｌ
ｉＣＦ３（Ｃ２Ｆ５）３、ＬｉＣＦ３ＳＯ３、ＬｉＮ
（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２ＣＦ２Ｃ
Ｆ３）２、ＬｉＮ（ＣＯＣＦ３）２およびＬｉＮ（ＣＯ
ＣＦ２ＣＦ３）２などの塩もしくはこれらの混合物を用
いることが出来る。The lithium salt to be dissolved in the solvent includes LiPF 6 , LiClO 4 , LiBF 4 , LiAsF.
6 , LiCF 3 CO 2 , LiCF 3 (CF 3 ) 3 , L
iCF 3 (C 2 F 5) 3, LiCF 3 SO 3, LiN
(SO 2 CF 3 ) 2 , LiN (SO 2 CF 2 C
F 3 ) 2 , LiN (COCF 3 ) 2 and LiN (CO
A salt such as CF 2 CF 3 ) 2 or a mixture thereof can be used.
【００２５】セパレータとしては、織布、不織布、合成
樹脂微多孔膜等を用いることが出来、特に、合成樹脂微
多孔膜を好適に用いることができる。中でもポリエチレ
ン及びポリプロピレン製微多孔膜、またはこれらを複合
した微多孔膜等のポリオレフィン系微多孔膜が、厚さ、
膜強度、膜抵抗等の面で好適に用いられる。As the separator, a woven cloth, a non-woven cloth, a synthetic resin microporous membrane or the like can be used, and particularly, a synthetic resin microporous membrane can be preferably used. Among them, polyethylene and polypropylene microporous film, or a polyolefin-based microporous film such as a composite microporous film, thickness,
It is preferably used in terms of film strength, film resistance and the like.
【００２６】また、高分子固体電解質等の固体電解質を
用いることで、セパレータを兼ねさせることも可能で、
この場合、高分子固体電解質として有孔性高分子固体電
解質膜を使用する等して高分子固体電解質にさらに電解
液を含有させても良い。この場合、ゲル状の高分子固体
電解質を用いる場合には、ゲルを構成する電解液と、細
孔中等に含有されている電解液とは異なっていてもよ
い。また、合成樹脂微多孔膜と高分子固体電解質等を組
み合わせて使用してもよい。Further, by using a solid electrolyte such as a polymer solid electrolyte, it is possible to serve also as a separator.
In this case, the solid polymer electrolyte may further contain an electrolytic solution, for example, by using a porous solid polymer electrolyte membrane as the solid polymer electrolyte. In this case, when a gel-like polymer solid electrolyte is used, the electrolytic solution forming the gel may be different from the electrolytic solution contained in the pores or the like. Further, a synthetic resin microporous membrane and a polymer solid electrolyte may be used in combination.
【００２７】また、電池の形状は特に限定されるもので
はなく、本発明は、角形、楕円形、コイン形、ボタン
形、シート形電池等の様々な形状の非水電解質二次電池
に適用可能である。The shape of the battery is not particularly limited, and the present invention can be applied to various shapes of non-aqueous electrolyte secondary batteries such as prismatic, elliptical, coin-shaped, button-shaped and sheet-shaped batteries. Is.
【００２８】[0028]
【実施例】以下、本発明を適用した具体的な実施例につ
いて説明するが、本発明は本実施例により何ら限定され
るものではなく、その主旨を変更しない範囲において適
宜変更して実施することが可能である。EXAMPLES Hereinafter, specific examples to which the present invention is applied will be described. However, the present invention is not limited to the examples, and various modifications may be made without departing from the scope of the invention. Is possible.
【００２９】［実施例１］本発明に用いた角形非水電解
質二次電池の概略断面図を図1に示す。図1において非水
電解質二次電池１はアルミ集電体に正極活物質を塗布し
てなる正極３と、銅集電体に負極活物質を塗布してなる
負極４と非水電解液を注入したセパレータ５を介して巻
回した巻回型電極群２を電池ケース６に収納してなるも
のである。電池ケース６に安全弁８を設けた電池蓋７を
レーザー溶接することによって取り付けられ、正極端子
９は正極リード１０を介して正極３と接続され、負極４
は電池ケース６の内壁と接触により接続されている。[Example 1] Fig. 1 is a schematic sectional view of a prismatic non-aqueous electrolyte secondary battery used in the present invention. In FIG. 1, a non-aqueous electrolyte secondary battery 1 has a positive electrode 3 formed by coating a positive electrode active material on an aluminum current collector, a negative electrode 4 formed by coating a negative electrode active material on a copper current collector, and a non-aqueous electrolyte solution. The wound type electrode group 2 wound via the separator 5 is housed in a battery case 6. The battery cover 7 provided with the safety valve 8 is attached to the battery case 6 by laser welding, the positive electrode terminal 9 is connected to the positive electrode 3 through the positive electrode lead 10, and the negative electrode 4 is attached.
Are connected by contact with the inner wall of the battery case 6.
【００３０】正極は、活物質のＬｉＣｏＯ２、導電材の
アセチレンブラックと、結着剤として重量平均分子量が
１２０，０００のイタコン酸とアクリロニトリルとブタ
ジエンおよびメタクリル酸メチルとの共重合体を重量比
で９５．８：３：１．２の割合となるように混合して正
極合材とし、Ｎ−メチル−２−ピロリドンに分散させる
ことによりスラリーを調製した。このスラリーを厚さ２
０μmのアルミ集電体に均一に塗布して、乾燥させた後
に合材層の空孔率が両面とも２５％となるように、ロー
ルプレスで圧縮成型することにより正極３を作製した。The positive electrode comprises LiCoO 2 as an active material, acetylene black as a conductive material, and a copolymer of itaconic acid having a weight average molecular weight of 120,000, acrylonitrile, butadiene, and methyl methacrylate in a weight ratio as a binder. A slurry was prepared by mixing so as to have a ratio of 95.8: 3: 1.2 to obtain a positive electrode mixture and dispersing the mixture in N-methyl-2-pyrrolidone. This slurry has a thickness of 2
A positive electrode 3 was produced by uniformly applying it to a 0 μm aluminum current collector, drying it, and then compression molding with a roll press so that the porosity of the composite material layer was 25% on both sides.
【００３１】負極板は、グラファイト（黒鉛）９０重量
％と結着剤としてのポリフッ化ビニリデン１０重量％と
を混合してなる混合物に、Ｎ−メチルピロリドンを加え
てペースト状に調製した後、これを厚さ１５μｍの銅箔
集電体両面に塗布、乾燥した後に、ロールプレスで１８
０μｍになるように圧縮成型することにより負極４を作
製した。セパレータ５には、厚さ２５μｍ程度の微多孔
性ポリエチレンフィルム５を用いた。The negative electrode plate was prepared by adding N-methylpyrrolidone to a mixture prepared by mixing 90% by weight of graphite and 10% by weight of polyvinylidene fluoride as a binder, and preparing a paste. Is applied to both sides of a copper foil current collector having a thickness of 15 μm, dried, and then rolled to 18
The negative electrode 4 was produced by compression molding so that the thickness was 0 μm. As the separator 5, a microporous polyethylene film 5 having a thickness of about 25 μm was used.
【００３２】電解液は、１ＭのＬｉＰＦ６をエチレンカ
ーボネート及びエチルメチルカーボネートの混合溶媒
（容積比１：２）に溶解した電解液を含浸させ、上述の
構成要素および手順により、電池を作製した。The electrolytic solution was impregnated with an electrolytic solution in which 1M LiPF 6 was dissolved in a mixed solvent of ethylene carbonate and ethylmethyl carbonate (volume ratio 1: 2), and a battery was produced by the above-mentioned components and procedures.
【００３３】［実施例２］正極の結着剤として重量平均
分子量が２００，０００のアクリロニトリルとブタジエ
ンおよびメタクリル酸メチルとの共重合体を用いること
以外は、実施例１と同様な手順で電池を作製した。Example 2 A battery was prepared in the same procedure as in Example 1 except that a copolymer of acrylonitrile having a weight average molecular weight of 200,000, butadiene and methyl methacrylate was used as the binder for the positive electrode. It was made.
【００３４】［実施例３］正極の結着剤として重量平均
分子量が３５０，０００のアクリロニトリルとブタジエ
ンの共重合体を用いること以外は、実施例１と同様な手
順で電池を作製した。Example 3 A battery was produced in the same procedure as in Example 1 except that a copolymer of acrylonitrile and butadiene having a weight average molecular weight of 350,000 was used as the binder for the positive electrode.
【００３５】［実施例４］正極の結着剤として重量平均
分子量が３５０，０００のイタコン酸とアクリロニトリ
ルとブタジエンとの共重合体を用いること以外は、実施
例１と同様な手順で電池を作製した。Example 4 A battery was prepared in the same procedure as in Example 1 except that a copolymer of itaconic acid, acrylonitrile and butadiene having a weight average molecular weight of 350,000 was used as the binder for the positive electrode. did.
【００３６】［実施例５］正極の結着剤として、重量平
均分子量が７０，０００のイタコン酸とアクリロニトリ
ルとブタジエンおよびメタクリル酸メチルとの共重合体
を用いること以外は、実施例１と同様な手順で電池を作
製した。Example 5 The same as Example 1 except that a copolymer of itaconic acid having a weight average molecular weight of 70,000, acrylonitrile, butadiene and methyl methacrylate was used as the binder for the positive electrode. A battery was produced by the procedure.
【００３７】［実施例６］正極の結着剤として、重量平
均分子量が３０，０００のイタコン酸とアクリロニトリ
ルとブタジエンおよびメタクリル酸メチルとの共重合体
を用いること以外は、実施例１と同様な手順で電池を作
製した。Example 6 The same as Example 1 except that a copolymer of itaconic acid having a weight average molecular weight of 30,000, acrylonitrile, butadiene and methyl methacrylate was used as the binder for the positive electrode. A battery was produced by the procedure.
【００３８】［比較例１］正極の結着剤として重量平均
分子量が１５，０００のイタコン酸とアクリロニトリル
とブタジエンおよびメタクリル酸メチルとの共重合体を
用いること以外は、実施例１と同様な手順で電池を作製
した。[Comparative Example 1] The same procedure as in Example 1 except that a copolymer of itaconic acid, acrylonitrile, butadiene and methyl methacrylate having a weight average molecular weight of 15,000 was used as the binder for the positive electrode. Then, a battery was manufactured.
【００３９】［実施例７］正極の結着剤として、重量平
均分子量が４００，０００のイタコン酸とアクリロニト
リルとブタジエンおよびメタクリル酸メチルとの共重合
体を用いること以外は、実施例１と同様な手順で電池を
作製した。Example 7 The same as Example 1 except that a copolymer of itaconic acid, acrylonitrile, butadiene and methyl methacrylate having a weight average molecular weight of 400,000 was used as the binder for the positive electrode. A battery was produced by the procedure.
【００４０】［実施例８］正極の結着剤として、重量平
均分子量が５００，０００のイタコン酸とアクリロニト
リルとブタジエンおよびメタクリル酸メチルとの共重合
体を用いること以外は、実施例１と同様な手順で電池を
作製した。[Example 8] The same as Example 1 except that a copolymer of itaconic acid, acrylonitrile, butadiene and methyl methacrylate having a weight average molecular weight of 500,000 was used as the binder for the positive electrode. A battery was produced by the procedure.
【００４１】［比較例２］正極の結着剤として重量平均
分子量が６００，０００のイタコン酸とアクリロニトリ
ルとブタジエンおよびメタクリル酸メチルとの共重合体
を用いること以外は、実施例１と同様な手順で電池を作
製した。Comparative Example 2 Procedure similar to that of Example 1 except that a copolymer of itaconic acid having a weight average molecular weight of 600,000, acrylonitrile, butadiene and methyl methacrylate was used as the binder for the positive electrode. Then, a battery was manufactured.
【００４２】［実施例９］活物質のＬｉＣｏＯ２、導電
材のアセチレンブラックと、結着剤として重量平均分子
量が１２０，０００のイタコン酸とアクリロニトリルと
ブタジエンおよびメタクリル酸メチルとの共重合体を重
量比で９６．１：３：０．９の割合となるように混合し
たこと以外は、実施例１と同様な手順で電池を作製し
た。[Example 9] LiCoO 2 as an active material, acetylene black as a conductive material, and a copolymer of itaconic acid having a weight average molecular weight of 120,000, acrylonitrile, butadiene, and methyl methacrylate as a binder were weighted. A battery was produced in the same procedure as in Example 1 except that the mixture was mixed at a ratio of 96.1: 3: 0.9.
【００４３】［実施例１０］活物質のＬｉＣｏＯ２、導
電材のアセチレンブラックと、結着剤として重量平均分
子量が１２０，０００のイタコン酸とアクリロニトリル
とブタジエンおよびメタクリル酸メチルとの共重合体を
重量比で９６．５：３：０．５の割合となるように混合
したこと以外は、実施例１と同様な手順で電池を作製し
た。[Example 10] LiCoO 2 as an active material, acetylene black as a conductive material, and a copolymer of itaconic acid having a weight average molecular weight of 120,000, acrylonitrile, butadiene, and methyl methacrylate as a binder were weighted. A battery was produced in the same procedure as in Example 1 except that the mixture was mixed at a ratio of 96.5: 3: 0.5.
【００４４】［比較例３］活物質のＬｉＣｏＯ２、導電
材のアセチレンブラックと、結着剤として重量平均分子
量が１２０，０００のイタコン酸とアクリロニトリルと
ブタジエンおよびメタクリル酸メチルとの共重合体を重
量比で９６．７：３：０．３の割合となるように混合し
たこと以外は、実施例１と同様な手順で電池を作製し
た。COMPARATIVE EXAMPLE 3 LiCoO 2 as an active material, acetylene black as a conductive material, and a copolymer of itaconic acid having a weight average molecular weight of 120,000, acrylonitrile, butadiene, and methyl methacrylate as a binder were weighted. A battery was made in the same procedure as in Example 1 except that the mixture was carried out at a ratio of 96.7: 3: 0.3.
【００４５】［実施例１１］活物質のＬｉＣｏＯ２、導
電材のアセチレンブラックと、結着剤として重量平均分
子量が１２０，０００のイタコン酸とアクリロニトリル
とブタジエンおよびメタクリル酸メチルとの共重合体を
重量比で９５．５：３：１．５の割合となるように混合
したこと以外は、実施例１と同様な手順で電池を作製し
た。Example 11 LiCoO 2 as an active material, acetylene black as a conductive material, and a copolymer of itaconic acid having a weight average molecular weight of 120,000, acrylonitrile, butadiene, and methyl methacrylate as a binder were weighted. A battery was produced in the same procedure as in Example 1 except that the components were mixed at a ratio of 95.5: 3: 1.5.
【００４６】［比較例４］活物質のＬｉＣｏＯ２、導電
材のアセチレンブラックと、結着剤として重量平均分子
量が１２０，０００のイタコン酸とアクリロニトリルと
ブタジエンおよびメタクリル酸メチルとの共重合体を重
量比で９５．２：３：１．８の割合となるように混合し
たこと以外は、実施例１と同様な手順で電池を作製し
た。Comparative Example 4 LiCoO 2 as an active material, acetylene black as a conductive material, and a copolymer of itaconic acid having a weight average molecular weight of 120,000, acrylonitrile, butadiene, and methyl methacrylate as a binder were weighted. A battery was made in the same procedure as in Example 1 except that the components were mixed at a ratio of 95.2: 3: 1.8.
【００４７】［比較例５］ＬｉＣｏＯ２、アセチレンブ
ラック、および結着剤としてポリフッ化ビニリデンを重
量比で９５：３：２の割合となるように混合した以外
は、実施例１と同様の手順で作製した。Comparative Example 5 The same procedure as in Example 1 was repeated except that LiCoO 2 , acetylene black, and polyvinylidene fluoride as a binder were mixed in a weight ratio of 95: 3: 2. It was made.
【００４８】［比較例６］ＬｉＣｏＯ２、アセチレンブ
ラック、および結着剤としてポリフッ化ビニリデンを重
量比で９５．８：３：１．２の割合となるように混合し
たこと以外は、実施例１と同様な手順で作製した。Comparative Example 6 Example 1 was repeated except that LiCoO 2 , acetylene black, and polyvinylidene fluoride as a binder were mixed in a weight ratio of 95.8: 3: 1.2. It was prepared by the same procedure.
【００４９】（電池の評価）これらの実施例及び比較例
の角形非水電解質二次電池について、初期容量と、低温
時での放電容量を測定した。なお、初期容量は室温下に
おいて、充電電流６００ｍＡ、充電電圧４．２０Ｖの定
電流低電圧充電で２．５時間充電した後、放電電流６０
０ｍＡ、終止電圧２．７５Ｖの条件で放電を行ったとき
の放電容量を示す。(Evaluation of Battery) Regarding the prismatic nonaqueous electrolyte secondary batteries of these Examples and Comparative Examples, the initial capacity and the discharge capacity at low temperature were measured. The initial capacity was room temperature, the charging current was 600 mA, the charging voltage was 4.20 V, and the constant current low voltage charging was 2.5 hours.
The discharge capacity when discharging under the conditions of 0 mA and a final voltage of 2.75 V is shown.
【００５０】低温時における放電容量は、初期容量の調
査を終わった電池を、充電電流６００ｍＡ、充電電圧
４．２０Ｖの定電流低電圧充電で２．５時間室温下にお
いて充電した後、０℃にて３時間放置した後に、０℃に
おいて放電電流６００ｍＡ、終止電圧２．７５Ｖの条件
で放電を行ったときの放電容量を示す。さらに、室温に
おいて放電したときと放電容量比（０℃での放電容量÷
室温での放電容量）を算出して、低温放電特性を評価す
ることとした。The discharge capacity at low temperature was set to 0 ° C. after charging the battery whose initial capacity had been examined by constant current low voltage charging with a charging current of 600 mA and a charging voltage of 4.20 V at room temperature for 2.5 hours. After being left for 3 hours, the discharge capacity when discharged at 0 ° C. under the conditions of a discharge current of 600 mA and a final voltage of 2.75 V is shown. Furthermore, the discharge capacity ratio at the time of discharge at room temperature (discharge capacity at 0 ° C ÷
The discharge capacity at room temperature) was calculated to evaluate the low temperature discharge characteristics.
【００５１】実施例１〜１１及び比較例１〜６における
初期容量及び０℃放電容量の結果を表１に示す。Table 1 shows the results of the initial capacity and 0 ° C. discharge capacity in Examples 1 to 11 and Comparative Examples 1 to 6.
【００５２】[0052]
【表１】 [Table 1]
【００５３】実施例１〜１１の電池は、従来の電池に比
べ、結着剤がかなり少ない含有量で、正極合材のアルミ
ニウム集電体への塗工が良好に行え、さらに極板を巻回
した際に前記合材の剥離のない良好な電極を作製するこ
とができた。初期放電容量、低温放電性能ともに良好で
あった。また、高率放電性能についても検討した結果、
良好な特性を示した。The batteries of Examples 1 to 11 contained the binder in a considerably smaller amount than the conventional batteries, and were able to coat the positive electrode mixture material on the aluminum current collector satisfactorily. It was possible to produce a good electrode without peeling of the mixture when it was turned. Both the initial discharge capacity and the low temperature discharge performance were good. In addition, as a result of examining the high rate discharge performance,
It showed good characteristics.
【００５４】比較例１の電池は、正極作製時のスラリー
の粘性が悪く、極板作製が困難であった。また、実施例
の各電池とくらべて初期放電容量が小さかった。In the battery of Comparative Example 1, the viscosity of the slurry during the production of the positive electrode was poor and it was difficult to produce the electrode plate. Also, the initial discharge capacity was smaller than that of each battery of the example.
【００５５】比較例２の電池は、０℃放電容量が低く、
低温放電性能がかなり低いものとなった。これはポリマ
ー自体が活物質表面を覆うように接着しやすくなるた
め、放電性能を低下させたものと考えられる。The battery of Comparative Example 2 had a low discharge capacity at 0 ° C.,
The low temperature discharge performance was considerably low. It is considered that this is because the polymer itself easily adhered so as to cover the surface of the active material, and thus the discharge performance was deteriorated.
【００５６】比較例３の電池は、実施例の各電池と比べ
て初期放電容量が小さかった。また、電池を解体する
と、正極板の極板合材と集電体とが剥離している部分が
みられた。特に最内周からはじめの正極板の曲率部で顕
著に認められた。このことから、放電容量が小さくなっ
たものと考えられる。The battery of Comparative Example 3 had a smaller initial discharge capacity than the batteries of Examples. Further, when the battery was disassembled, a portion where the electrode plate mixture of the positive electrode plate and the current collector were separated was observed. Especially, it was noticeable in the curvature portion of the positive electrode plate from the innermost circumference. From this, it is considered that the discharge capacity has decreased.
【００５７】比較例４の電池は、実施例の各電池と比べ
て初期放電容量が小さかった。さらに０℃放電容量はか
なり低いものとなり、低温放電性能の低下は著しかっ
た。極板合材中の結着剤量が所定の値を超えて大きくな
ると、活物質表面を覆うように接着する傾向が強く現
れ、放電性能を低下させたものと考えられる。The battery of Comparative Example 4 had a smaller initial discharge capacity than the batteries of Examples. Furthermore, the 0 ° C. discharge capacity was considerably low, and the low-temperature discharge performance was significantly deteriorated. It is considered that when the amount of the binder in the electrode plate composite material exceeds a predetermined value and becomes large, there is a strong tendency to adhere so as to cover the surface of the active material, which deteriorates the discharge performance.
【００５８】比較例５の電池は、実施例の各電池とくら
べて初期放電容量が小さかった。比較例５の電池を解体
すると、巻回して発電要素を作製したときに、正極板の
極板合材と集電体とが剥離している部分がみられた。特
に最内周からはじめの正極板の曲率部が切断しているこ
とがわかった。剥離した部分や切断した部分は充放電に
関与することがないことから、その分だけ放電容量が低
下したものと考えられる。The battery of Comparative Example 5 had a smaller initial discharge capacity than the batteries of Examples. When the battery of Comparative Example 5 was disassembled, a part where the electrode plate composite material of the positive electrode plate and the current collector were separated was observed when the battery was wound to form a power generation element. In particular, it was found that the first curved portion of the positive electrode plate was cut from the innermost circumference. Since the peeled portion and the cut portion do not participate in charging / discharging, it is considered that the discharge capacity is reduced accordingly.
【００５９】比較例６の電池は、比較例５とくらべても
初期放電容量がさらに小さかった。比較例６の電池を解
体すると、比較例５の電池と同様に、最内周からはじめ
の正極板の曲率部が切断していること、また、結着剤量
がすくないために極板合材と集電体とが剥離している部
分がみられた。これらのことから、放電容量が小さくな
ったものと考えられる。The battery of Comparative Example 6 had a smaller initial discharge capacity than that of Comparative Example 5. When the battery of Comparative Example 6 was disassembled, like the battery of Comparative Example 5, the curvature part of the positive electrode plate was cut off from the innermost circumference, and the amount of the binder was small, so that the electrode plate mixture material was used. There was a part where the current collector and the current collector were separated. From these things, it is considered that the discharge capacity became smaller.
【００６０】[0060]
【発明の効果】以上より、本願発明である非水電解質二
次電池において、結着剤としてアクリロニトリル・ブタ
ジエン系共重合体を用いて合材中の結着材量を減らすこ
とにより、電池を高容量化できる。そして、結着剤とし
てアクリロニトリル・ブタジエン系共重合体を用い、前
記共重合体の重量平均分子量を３０，０００〜５００，
０００とすることにより、電池製造時における正極板の
作製を容易にし、しかも高率放電性能および低温放電性
能を向上させることができる。また、前記共重合体の正
極合材中における含有量を０．５〜１．５重量％とする
ことにより、正極合材の剥離を抑制し、しかも高率放電
性能および低温放電性能を向上させることができる。As described above, in the non-aqueous electrolyte secondary battery of the present invention, by using an acrylonitrile-butadiene-based copolymer as a binder to reduce the amount of the binder in the mixture, the battery can be improved. Capacity can be increased. Then, an acrylonitrile-butadiene-based copolymer is used as a binder, and the weight average molecular weight of the copolymer is 30,000 to 500,
When it is 000, the production of the positive electrode plate at the time of battery production can be facilitated, and the high rate discharge performance and the low temperature discharge performance can be improved. Further, by controlling the content of the above-mentioned copolymer in the positive electrode mixture to be 0.5 to 1.5% by weight, peeling of the positive electrode mixture is suppressed, and further, high rate discharge performance and low temperature discharge performance are improved. be able to.
【図１】本発明にかかる角形非水電解質二次電池の縦断
面略図。FIG. 1 is a schematic vertical cross-sectional view of a prismatic non-aqueous electrolyte secondary battery according to the present invention.
【符号の説明】 １ 非水電解質二次電池 ２ 発電要素 ３ 正極板 ４ 負極板 ５ セパレータ ６ 電池ケース ７ 蓋 ８ 安全弁 ９ 正極端子 １０ 正極リード[Explanation of symbols] 1 Non-aqueous electrolyte secondary battery 2 power generation elements 3 Positive plate 4 Negative plate 5 separator 6 battery case 7 lid 8 safety valve 9 Positive terminal 10 Positive electrode lead
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H029 AJ02 AK02 AK03 AK05 AK16 AL02 AL03 AL06 AL12 AM03 AM04 AM05 AM07 BJ02 BJ14 DJ08 EJ12 HJ02 HJ11 5H050 AA06 BA17 CA02 CA07 CA11 CA20 CB02 CB03 CB07 CB12 DA02 DA11 EA28 FA05 HA02 HA11 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 5H029 AJ02 AK02 AK03 AK05 AK16 AL02 AL03 AL06 AL12 AM03 AM04 AM05 AM07 BJ02 BJ14 DJ08 EJ12 HJ02 HJ11 5H050 AA06 BA17 CA02 CA07 CA11 CA20 CB02 CB03 CB07 CB12 DA02 DA11 EA28 FA05 HA02 HA11
Claims (2)
物を正極活物質として、該正極活物質の粒子と導電剤と
結着剤とを含む混合物が合材層として金属集電体に形成
されてなる正極を備えた非水電解質二次電池において、
上記結着剤として重量平均分子量が３０，０００〜５０
０，０００であるアクリロニトリル・ブタジエン系共重
合体が用いられていることを特徴とする非水電解質二次
電池。1. A metal current collector comprising a metal compound capable of occluding and releasing lithium ions as a positive electrode active material, and a mixture containing particles of the positive electrode active material, a conductive agent and a binder as a mixture layer formed on a metal current collector. In a non-aqueous electrolyte secondary battery provided with a positive electrode,
The binder has a weight average molecular weight of 30,000 to 50.
A non-aqueous electrolyte secondary battery characterized in that an acrylonitrile-butadiene-based copolymer of 20,000 is used.
物を正極活物質として、該正極活物質の粒子と導電剤と
結着剤とを含む混合物が合材層として金属集電体に形成
されてなる正極を備えた非水電解質二次電池において、
上記結着剤としてアクリロニトリル・ブタジエン系共重
合体が用いられ、正極合材中の前記アクリロニトリル・
ブタジエン系共重合体の含有量が０．５〜１．５重量％
であることを特徴とする非水電解質二次電池。2. A metal current collector comprising a metal compound capable of occluding and releasing lithium ions as a positive electrode active material, and a mixture containing particles of the positive electrode active material, a conductive agent and a binder as a composite material layer formed on a metal current collector. In a non-aqueous electrolyte secondary battery provided with a positive electrode,
An acrylonitrile-butadiene-based copolymer is used as the binder, and the acrylonitrile-
Content of butadiene-based copolymer is 0.5 to 1.5% by weight
A non-aqueous electrolyte secondary battery characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002124077A JP2003317721A (en) | 2002-04-25 | 2002-04-25 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002124077A JP2003317721A (en) | 2002-04-25 | 2002-04-25 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003317721A true JP2003317721A (en) | 2003-11-07 |
Family
ID=29539191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002124077A Pending JP2003317721A (en) | 2002-04-25 | 2002-04-25 | Nonaqueous electrolyte secondary battery |
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| Country | Link |
|---|---|
| JP (1) | JP2003317721A (en) |
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