JP2000133270A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JP2000133270A JP2000133270A JP10303083A JP30308398A JP2000133270A JP 2000133270 A JP2000133270 A JP 2000133270A JP 10303083 A JP10303083 A JP 10303083A JP 30308398 A JP30308398 A JP 30308398A JP 2000133270 A JP2000133270 A JP 2000133270A
- Authority
- JP
- Japan
- Prior art keywords
- hexafluoropropylene
- positive electrode
- active material
- negative electrode
- electrolyte 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.)
- Granted
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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解液あるい
は固体電解質、ゲル状電解質を用いた非水電解質電池に
関するものであり、特に、結着剤の改良に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery using a non-aqueous electrolyte, a solid electrolyte, and a gel electrolyte, and more particularly to an improvement in a binder.
【０００２】[0002]
【従来の技術】近年、カメラー体型ＶＴＲ、携帯電話、
携帯用コンピューター等のポータブル電子機器が多く登
場し、その高性能が図られている。2. Description of the Related Art In recent years, camera-type VTRs, mobile phones,
Many portable electronic devices such as portable computers have appeared and their high performance has been achieved.
【０００３】そして、これらの電子機器のポータブル電
源として、電池、特に二次電池、なかでもリチウムイオ
ン電池について多くの研究がなされている。Many studies have been made on batteries, especially secondary batteries, especially lithium ion batteries, as portable power supplies for these electronic devices.
【０００４】例えば、より高性能な機器は電池に多大な
負荷を要求するため、低負荷での使用時に比べてサイク
ル劣化が大きい。このため、より過酷な条件でもサイク
ル性能が維持できる電池が求められている。[0004] For example, a higher performance device requires a large load on a battery, and therefore, the cycle deterioration is larger than when the device is used under a low load. For this reason, a battery that can maintain cycle performance even under more severe conditions has been demanded.
【０００５】[0005]
【発明が解決しようとする課題】従来のポリビニリデン
フルオロライド単体を結着剤として用いた電池は、高負
荷でのサイクル時に電極、特に負極活物質層の集電体か
らの剥離により、容量劣化を引き起こす。The battery using the conventional polyvinylidene fluoride alone as a binder has a problem that the capacity is deteriorated due to the separation of the electrode, especially the negative electrode active material layer from the current collector during the cycle under a high load. cause.
【０００６】この活物質層の剥離は、充放電サイクルに
おける活物質の膨張、収縮によって引き起こされる。The peeling of the active material layer is caused by expansion and contraction of the active material in a charge / discharge cycle.
【０００７】本発明は、かかる従来のものの有する欠点
を解消するために提案されたものであり、負極電極や正
極電極における活物質層の剥離を防止することを目的と
し、これにより過酷な条件でも優れたサイクル性能を発
揮する非水電解質電池を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been proposed to solve the above-mentioned drawbacks of the prior art, and aims at preventing the active material layer from being peeled off from the negative electrode and the positive electrode. An object of the present invention is to provide a nonaqueous electrolyte battery exhibiting excellent cycle performance.
【０００８】[0008]
【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、本発明の非水電解質電池は、集電体と、上記集電
体上に形成され活物質と結着剤とを含有する活物質層と
からなる正極電極及び負極電極を有し、上記正極電極及
び／又は負極電極の結着剤は、ビニリデンフルオライド
とヘキサフルオロプロピレンとの共重合体及びポリビニ
リデンフルオライドを含有することを特徴とするもので
ある。In order to achieve the above-mentioned object, a non-aqueous electrolyte battery according to the present invention comprises a current collector, an active material formed on the current collector, and a binder. It has a positive electrode and a negative electrode composed of an active material layer, and the binder for the positive electrode and / or the negative electrode contains a copolymer of vinylidene fluoride and hexafluoropropylene and polyvinylidene fluoride. It is characterized by the following.
【０００９】結着剤に、ビニリデンフルオロライドとヘ
キサフルオロプロピレンの共重合体とポリビニリデンフ
ルオライドとを併用することにより、ポリビニリデンフ
ルオロライド単体を用いた場合に比べて集電体への接着
強度が高くなり、その結果、高負荷でのサイクル特性が
向上する。By using a copolymer of vinylidenefluoride and hexafluoropropylene and polyvinylidenefluoride in combination as a binder, the adhesive strength to the current collector is higher than when polyvinylidenefluoride alone is used. , And as a result, the cycle characteristics under a high load are improved.
【００１０】[0010]
【発明の実施の形態】以下、本発明の非水電解質電池の
構成について、詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The structure of the nonaqueous electrolyte battery of the present invention will be described in detail below.
【００１１】本発明の非水電解質電池は、集電体と、上
記集電体上に形成され活物質と結着剤とを含有する活物
質層とからなる正極電極及び負極電極を有してなるもの
である。The non-aqueous electrolyte battery of the present invention has a positive electrode and a negative electrode each comprising a current collector and an active material layer formed on the current collector and containing an active material and a binder. It becomes.
【００１２】そして、これら正極電極、負極電極のいず
れか一方、あるいは両方の結着剤としてビニリデンフル
オライドとヘキサフルオロプロピレンとの共重合体（コ
ポリマー）及びポリビニリデンフルオライドを用いるこ
とが大きな特徴である。A major feature is that a copolymer of vinylidene fluoride and hexafluoropropylene and polyvinylidene fluoride are used as a binder for one or both of the positive electrode and the negative electrode. is there.
【００１３】ここで、結着剤中のコポリマーの割合は、
３０〜９５重量％とすることが好ましい。コポリマーの
割合が少なすぎると、十分な接着強度を確保することが
できない。また、逆にコポリマーの割合が多すぎても接
着強度が低下する。これまで、コポリマーの割合が多い
ほど接着強度が上がると考えられてきたが、本発明者等
の実験によれば、電解液を含む電池内では、コポリマー
の割合が多すぎると却って接着強度が低下することがわ
かった。このような現象は、本発明者等によって初めて
明らかにされたものである。Here, the proportion of the copolymer in the binder is
It is preferably 30 to 95% by weight. If the proportion of the copolymer is too small, sufficient adhesive strength cannot be secured. Conversely, if the proportion of the copolymer is too large, the adhesive strength will decrease. Until now, it was thought that the higher the proportion of the copolymer, the higher the bonding strength.However, according to experiments by the present inventors, in a battery containing an electrolytic solution, the bonding strength was rather lowered if the proportion of the copolymer was too high. I found out. Such a phenomenon was first clarified by the present inventors.
【００１４】また、コポリマーにおけるヘキサフルオロ
プロピレンの割合は、３〜３０重量％とすることが好ま
しい。この範囲を外れると、やはり接着強度が低下す
る。The proportion of hexafluoropropylene in the copolymer is preferably 3 to 30% by weight. Outside this range, the adhesive strength also decreases.
【００１５】本発明の電池は、上記のような結着剤を使
用する以外は、従来のリチウムイオン電池と同様に構成
することができる。The battery of the present invention can be configured in the same manner as a conventional lithium ion battery except that the above-mentioned binder is used.
【００１６】すなわち、リチウムイオン電池を構成する
場合の負極材料としては、リチウムをドープ、脱ドープ
できる材料を使用することができる。このような負極の
構成材料、たとえば難黒鉛化炭素系材料や黒鉛系材料の
炭素材料を使用することができる。より具体的には、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)、黒鉛類、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、活
性炭等の炭素材料を使用することができる。このほか、
リチウムをドープ、脱ドープできる材料としては、ポリ
アセチレン、ポリピロール等の高分子やＳｎＯ2 等の酸
化物を使用することもできる。このような材料から負極
を形成するに際しては、公知の結着剤等を添加すること
ができる。That is, a material capable of doping and undoping lithium can be used as a negative electrode material for forming a lithium ion battery. A constituent material of such a negative electrode, for example, a non-graphitizable carbon-based material or a carbon material of a graphite-based material can be used. More specifically, pyrolytic carbons, cokes (pitch coke, needle coke, petroleum coke), graphites, glassy carbons, and organic polymer compound fired bodies (phenolic resin, furan resin, etc.) at an appropriate temperature Carbon materials such as fired and carbonized), carbon fiber, and activated carbon can be used. other than this,
As a material capable of doping or undoping lithium, a polymer such as polyacetylene or polypyrrole or an oxide such as SnO 2 can be used. When forming a negative electrode from such a material, a known binder or the like can be added.
【００１７】正極は、目的とする電池の種類に応じて、
金属酸化物、金属硫化物または特定の高分子を正極活物
質として用いて構成することができる。たとえばリチウ
ムイオン電池を構成する場合、正極活物質としては、Ｔ
ｉＳ2、ＭｏＳ2、ＮｂＳｅ2，Ｖ2Ｏ5等のリチウムを含
有しない金属硫化物あるいは酸化物や、ＬｉＭＯ2 （式
中Ｍは一種以上の遷移金属を表し、ｘは電池の充放電状
態によって異なり、通常０．０５以上１．１０以下であ
る。）を主体とするリチウム複合酸化物等を使用するこ
とができる。このリチウム複合酸化物を構成する遷移金
属Ｍとしては、Ｃｏ，Ｎｉ，Ｍｎ等が好ましい。このよ
うなリチウム複合酸化物の具体例としてはＬｉＣｏ
Ｏ2，ＬｉＮｉＯ2，ＬｉＮｉyＣｏ1-yＯ2(式中、０＜ｙ
＜１である。)、ＬｉＭｎ2Ｏ4等を挙げることができ
る。これらリチウム複合酸化物は、高電圧を発生でき、
エネルギー密度的に的に優れた正極活物質となる。正極
には、これらの正極活物質の複数種をあわせて使用して
もよい。また、以上のような正極活物質を使用して正極
を形成するに際して、公知の導電剤や結着剤等を添加す
ることができる。[0017] The positive electrode depends on the type of the intended battery.
A metal oxide, a metal sulfide, or a specific polymer can be used as the positive electrode active material. For example, when configuring a lithium ion battery, the positive electrode active material may be T
Lithium-free metal sulfides or oxides such as iS 2 , MoS 2 , NbSe 2 , V 2 O 5 , and LiMO 2 (where M represents one or more transition metals, and x depends on the charge / discharge state of the battery. However, it is usually 0.05 or more and 1.10 or less.). As the transition metal M constituting the lithium composite oxide, Co, Ni, Mn and the like are preferable. A specific example of such a lithium composite oxide is LiCo.
O 2 , LiNiO 2 , LiNi y Co 1-y O 2 (where 0 <y
<1. ), LiMn 2 O 4 and the like. These lithium composite oxides can generate high voltage,
It becomes a positive electrode active material excellent in energy density. A plurality of these positive electrode active materials may be used in combination for the positive electrode. When a positive electrode is formed using the above-described positive electrode active material, a known conductive agent, a binder, and the like can be added.
【００１８】電解質は、非水電解液あるいは固体電解
質、ゲル状電解質のいずれであってもよい。The electrolyte may be a non-aqueous electrolyte, a solid electrolyte, or a gel electrolyte.
【００１９】例えば固体電解質電池、またはゲル状電解
質電池を考えた場合、高分子固体電解質に使用する高分
子材料としては、シリコンゲル、アクリルゲル、アクリ
ロニトリルゲル、ポリフォスファゼン変成ポリマー、ポ
リエチレンオキサイド、ポリプロピレンオキサイド、及
びこれらの複合ポリマーや架橋ポリマー、変成ポリマー
などもしくはフッ素系ポリマーとして、たとえばポリ
（ビニリデンフルオロライド）やポリ（ビニリデンフル
オロライド-co-ヘキサフルオロプロピレン）、ポリ（ビ
ニリデンフルオロライド-co-テトラフルオロエチレ
ン）、ポリ（ビニリデンフルオロライド-co-トリフルオ
ロエチレン）などおよびこれらの混合物が各種使用でき
るが、勿論、これらに限定されるものではない。For example, when a solid electrolyte battery or a gel electrolyte battery is considered, the polymer materials used for the polymer solid electrolyte include silicon gel, acrylic gel, acrylonitrile gel, polyphosphazene modified polymer, polyethylene oxide, and polypropylene. Oxides and their composite polymers, cross-linked polymers, modified polymers, or fluorine-based polymers such as poly (vinylidene fluoride), poly (vinylidene fluoride-co-hexafluoropropylene), and poly (vinylidene fluoride-co-tetra) Fluoroethylene), poly (vinylidenefluoride-co-trifluoroethylene), and the like and various mixtures thereof can be used, but are not limited thereto.
【００２０】正極活物質層または負極活物質層に積層さ
れている固体電解質、またはゲル状電解質は、高分子化
合物と電解質塩と溶媒、（ゲル電解質の場合は、さらに
可塑剤）からなる溶液を正極活物質層または負極活物質
層に含浸させ、溶媒を除去し固体化したものである。正
極活物質層または負極活物質層に積層された固体電解
質、またはゲル状電解質は、その一部が正極活物質層ま
たは負極活物質層に含浸されて固体化されている。架橋
系の場合は、その後、光または熱で架橋して固体化され
る。The solid electrolyte or the gel electrolyte laminated on the positive electrode active material layer or the negative electrode active material layer is a solution comprising a polymer compound, an electrolyte salt and a solvent, and (in the case of a gel electrolyte, a plasticizer). It is obtained by impregnating the positive electrode active material layer or the negative electrode active material layer, removing the solvent, and solidifying. A part of the solid electrolyte or the gel electrolyte laminated on the positive electrode active material layer or the negative electrode active material layer is impregnated into the positive electrode active material layer or the negative electrode active material layer to be solidified. In the case of a crosslinked system, it is then solidified by crosslinking with light or heat.
【００２１】ゲル状電解質は、リチウム塩を含む可塑剤
と２重量％以上〜３０重量％以下のマトリクス高分子か
らなる。このとき、エステル類、エーテル類、炭酸エス
テル類などを単独または可塑剤の一成分として用いるこ
とができる。The gel electrolyte comprises a plasticizer containing a lithium salt and a matrix polymer of 2% to 30% by weight. At this time, esters, ethers, carbonates and the like can be used alone or as one component of a plasticizer.
【００２２】ゲル状電解質を調整するにあたり、このよ
うな炭酸エステル類をゲル化するマトリクス高分子とし
ては、ゲル状電解質を構成するのに使用されている種々
の高分子が利用できるが、酸化還元安定性から、たとえ
ばポリ（ビニリデンフルオロライド）やポリ（ビニリデ
ンフルオロライド-co-ヘキサフルオロプロピレン）など
のフッ素系高分子を用いることが望ましい。In preparing the gel electrolyte, various polymers used for forming the gel electrolyte can be used as the matrix polymer for gelling the carbonates. From the viewpoint of stability, it is desirable to use a fluorine-based polymer such as poly (vinylidene fluoride) or poly (vinylidene fluoride-co-hexafluoropropylene).
【００２３】高分子固体電解質は、リチウム塩とそれを
溶解する高分子化合物からなり、高分子化合物として
は、ポリ（エチレンオキサイド）や同架橋体などのエー
テル系高分子、ポリ（メタクリレート）エステル系、ア
クリレート系、ポリ（ビニリデンフルオロライド）やポ
リ（ビニリデンフルオロライド-co-ヘキサフルオロプロ
ピレン）などのフッ素系高分子などを単独、または混合
して用いることができるが、酸化還元安定性から、たと
えばポリ（ビニリデンフルオロライド）やポリ（ビニリ
デンフルオロライド-co-ヘキサフルオロプロピレン）な
どのフッ素系高分子を用いることが望ましい。The solid polymer electrolyte is composed of a lithium salt and a polymer compound that dissolves the lithium salt. Examples of the polymer compound include ether polymers such as poly (ethylene oxide) and the same crosslinked product, and poly (methacrylate) ester polymers. , Acrylate polymers, fluorine polymers such as poly (vinylidenefluoride) and poly (vinylidenefluoride-co-hexafluoropropylene) can be used alone or as a mixture. It is desirable to use a fluorinated polymer such as poly (vinylidene fluoride) or poly (vinylidene fluoride-co-hexafluoropropylene).
【００２４】このようなゲル状電解質または高分子固体
電解質に含有させるリチウム塩として通常の電池電解液
に用いられるリチウム塩を使用することができ、リチウ
ム化合物（塩）としては、例えば以下のものが挙げられ
るが、これらに限定されるものではない。As the lithium salt contained in such a gel electrolyte or a solid polymer electrolyte, a lithium salt used in a usual battery electrolyte can be used. Examples of the lithium compound (salt) include the following. But are not limited to these.
【００２５】たとえば、塩化リチウム臭化リチウム、ヨ
ウ化リチウム、塩素酸リチウム、過塩素酸リチウム、臭
素酸リチウム、ヨウ素酸リチウム、硝酸リチウム、テト
ラフルオロほう酸リチウム、ヘキサフルオロリン酸リチ
ウム、酢酸リチウム、ビス（トリフルオロメタンスルフ
ォニル）イミドリチウム、ＬｉＡｓＦ6、ＬｉＣＦ3ＳＯ
3、ＬｉＣ（ＳＯ2ＣＦ3）3、ＬｉＡｌＣｌ4、ＬｉＳｉ
Ｆ6等を挙げることができる。For example, lithium chloride, lithium bromide, lithium iodide, lithium chlorate, lithium perchlorate, lithium bromate, lithium iodate, lithium nitrate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium acetate, bismuth Lithium (trifluoromethanesulfonyl) imide, LiAsF 6 , LiCF 3 SO
3 , LiC (SO 2 CF 3 ) 3 , LiAlCl 4 , LiSi
F 6 and the like can be given.
【００２６】これらリチウム化合物は単独で用いても複
数を混合して用いても良いが、これらの中でＬｉＰ
Ｆ6、ＬｉＢＦ4が酸化安定性の点から望ましい。These lithium compounds may be used alone or in combination of two or more.
F 6 and LiBF 4 are desirable from the viewpoint of oxidation stability.
【００２７】リチウム塩を溶解する濃度として、ゲル状
電解質なら、可塑剤中に０．１〜３．０モルで実施でき
るが、好ましくは０．５から２．０モル／リットルで用
いることができる。As a concentration for dissolving the lithium salt, a gel electrolyte can be used in a plasticizer at a concentration of 0.1 to 3.0 mol, preferably 0.5 to 2.0 mol / l. .
【００２８】上記構成の非水電解質電池においては、電
池形状についても特に限定されることはない。例えば、
円筒型、角型、コイン型、ボタン型等、任意の形状とす
ることができ、薄型、大型等、サイズも任意に設定すれ
ばよい。In the nonaqueous electrolyte battery having the above structure, the shape of the battery is not particularly limited. For example,
Any shape such as a cylindrical shape, a square shape, a coin shape, and a button shape can be used, and the size may be arbitrarily set, such as a thin shape and a large size.
【００２９】[0029]
【実施例】次に、本発明を適用した具体的な実施例及び
比較例について、実験結果に基づいて説明する。Next, specific examples and comparative examples to which the present invention is applied will be described based on experimental results.
【００３０】実施例１ 先ず、負極を次のように作製した。 Example 1 First, a negative electrode was manufactured as follows.
【００３１】粉砕した黒鉛粉末９０重量部と、結着剤と
してポリ（ビニリデンフルオロライド-co-ヘキサフルオ
ロプロピレン）（ヘキサフルオロプロピレンの含有量：
７重量％）１０重量部とを混合して負極合剤を調製し、
さらにこれをＮ−メチル−２−ピロリドンに分散させス
ラリー状とした。そして、このスラリーを負極集電体で
ある厚さ１０μｍの帯状銅箔の片面に均一に塗布し、乾
燥後、ロールプレス機で圧縮成形し、負極を作製した。90 parts by weight of the pulverized graphite powder and poly (vinylidene fluoride-co-hexafluoropropylene) (hexafluoropropylene content:
7% by weight) and 10 parts by weight to prepare a negative electrode mixture,
This was further dispersed in N-methyl-2-pyrrolidone to form a slurry. Then, this slurry was uniformly applied to one surface of a 10 μm-thick strip-shaped copper foil as a negative electrode current collector, dried, and then compression-molded with a roll press to produce a negative electrode.
【００３２】一方、正極を次のように作製した。On the other hand, a positive electrode was produced as follows.
【００３３】正極活物質（ＬｉＣｏＯ2）を得るため
に、炭酸リチウムと炭酸コバルトを０．５モル対１モル
の比率で混合し、空気中、９００℃で５時間焼成した。
次に、得られたＬｉＣｏＯ2 ８５重量部、導電剤として
黒鉛５重量部、結着剤としてポリビニリデンフルオロラ
イド１０重量部とを混合して正極合剤を調製し、さらに
これをＮ−メチル−２−ピロリドンに分散させスラリー
状とした。そして、このスラリーを正極集電体である厚
さ２０μｍの帯状アルミニウム箔の片面に均一に塗布
し、乾燥した後、ロールプレス機で圧縮成形し、正極を
作製した。In order to obtain a positive electrode active material (LiCoO 2 ), lithium carbonate and cobalt carbonate were mixed at a ratio of 0.5 mol to 1 mol, and fired in air at 900 ° C. for 5 hours.
Next, 85 parts by weight of the obtained LiCoO 2 , 5 parts by weight of graphite as a conductive agent, and 10 parts by weight of polyvinylidene fluoride as a binder were mixed to prepare a positive electrode mixture. It was dispersed in 2-pyrrolidone to form a slurry. Then, this slurry was uniformly applied to one surface of a 20 μm-thick strip-shaped aluminum foil as a positive electrode current collector, dried, and then compression-molded with a roll press to produce a positive electrode.
【００３４】以上のようにして得られた正極、負極を厚
さ２５μｍの微孔性ポリボロピレンフィルムからなるセ
パレーターを介して密着させ、炭酸プロピレン５０容量
％、ジメトキシエタン５０容量％を混合した混合溶媒中
に、６フッ化リン酸リチウムを１ｍｏｌ／ｌの割合で溶
解させた電解液を注入し、サンプル電池を作製した。The positive electrode and the negative electrode obtained as described above are brought into close contact with each other via a separator made of a microporous polyboropyrene film having a thickness of 25 μm, and mixed by mixing 50% by volume of propylene carbonate and 50% by volume of dimethoxyethane. An electrolyte in which lithium hexafluorophosphate was dissolved at a rate of 1 mol / l was injected into the solvent to prepare a sample battery.
【００３５】実施例２〜２４ 負極中、正極中の結着剤を表１のようにして作製した以
外は、実施例１と同様に電池を作製した。 Examples 2 to 24 A battery was prepared in the same manner as in Example 1, except that the binder in the positive electrode was prepared as shown in Table 1 in the negative electrode.
【００３６】実施例２５ 先ず、負極を次のように作製した。 Example 25 First, a negative electrode was produced as follows.
【００３７】粉砕した黒鉛粉末９０重量部と、結着剤と
してポリ（ビニリデンフルオロライド-co-ヘキサフルオ
ロプロピレン）（ヘキサフルオロプロピレンの含有量：
７重量％）１０重量部とを混合して負極合剤を調製し、
さらにこれをＮ−メチル−２−ピロリドンに分散させス
ラリー状とした。そして、このスラリーを負極集電体で
ある厚さ１０μｍの帯状銅箔の片面に均一に塗布し、乾
燥後、ロールプレス機で圧縮成形し、負極を作製した。90 parts by weight of the pulverized graphite powder and poly (vinylidenefluoride-co-hexafluoropropylene) (hexafluoropropylene content as a binder)
7% by weight) and 10 parts by weight to prepare a negative electrode mixture,
This was further dispersed in N-methyl-2-pyrrolidone to form a slurry. Then, this slurry was uniformly applied to one surface of a 10 μm-thick strip-shaped copper foil as a negative electrode current collector, dried, and then compression-molded with a roll press to produce a negative electrode.
【００３８】一方、正極を次のように作製した。On the other hand, a positive electrode was produced as follows.
【００３９】正極活物質（ＬｉＣｏＯ2）を得るため
に、炭酸リチウムと炭酸コバルトを０．５モル対１モル
の比率で混合し、空気中、９００℃で５時間焼成した。
次に、得られたＬｉＣｏＯ2 ８５重量部、導電剤として
黒鉛５重量部、結着剤としてポリビニリデンフルオロラ
イド１０重量部とを混合して正極合剤を調製し、さらに
これをＮ−メチル−２−ピロリドンに分散させスラリー
状とした。そして、このスラリーを正極集電体である厚
さ２０μｍの帯状アルミニウム箔の片面に均一に塗布
し、乾燥した後、ロールプレス機で圧縮成形し、正極を
作製した。In order to obtain a positive electrode active material (LiCoO 2 ), lithium carbonate and cobalt carbonate were mixed at a ratio of 0.5 mol to 1 mol, and calcined in air at 900 ° C. for 5 hours.
Next, 85 parts by weight of the obtained LiCoO 2 , 5 parts by weight of graphite as a conductive agent, and 10 parts by weight of polyvinylidene fluoride as a binder were mixed to prepare a positive electrode mixture. It was dispersed in 2-pyrrolidone to form a slurry. Then, this slurry was uniformly applied to one surface of a 20 μm-thick strip-shaped aluminum foil as a positive electrode current collector, dried, and then compression-molded with a roll press to produce a positive electrode.
【００４０】さらに、ゲル状電解質を次のようにして得
た。Further, a gel electrolyte was obtained as follows.
【００４１】負極、正極上に炭酸エチレン（ＥＣ）４
２．５重量部、炭酸プロピレン（ＰＣ）４２．５重量
部、ＬｉＰＦ6 １５重量部からなる可塑剤３０重量部
に、ポリ（ビニリデンフルオロライド-co-ヘキサフルオ
ロプロピレン）（ヘキサフルオロプロピレンの含有量：
７重量％）１０重量部、そして炭酸ジエチル６０重量部
を混合溶解させた溶液を均一に塗布し、含浸させ、常温
で８時間放置し、炭酸ジメチルを気化、除去しゲル状電
解質を得た。Ethylene carbonate (EC) 4 on the negative and positive electrodes
2.5 parts by weight, 30 parts by weight of a plasticizer composed of 42.5 parts by weight of propylene carbonate (PC) and 15 parts by weight of LiPF 6 are mixed with poly (vinylidene fluoride-co-hexafluoropropylene) (content of hexafluoropropylene). :
A solution prepared by mixing and dissolving 10 parts by weight (7% by weight) and 60 parts by weight of diethyl carbonate was uniformly applied, impregnated, and allowed to stand at room temperature for 8 hours to evaporate and remove dimethyl carbonate to obtain a gel electrolyte.
【００４２】ゲル状電解質を塗布した負極、及び正極を
ゲル状電解質側をあわせ、圧着することで平板型ゲル状
電解質電池を作製した。The negative electrode coated with the gel electrolyte and the positive electrode were brought into contact with the gel electrolyte and pressed together to produce a flat gel electrolyte battery.
【００４３】実施例２６〜４８ 負極中、正極中の結着剤を表２のようにして作製した以
外は、実施例２５と同様に電池を作製した。 Examples 26 to 48 Batteries were produced in the same manner as in Example 25 except that the binder in the positive electrode was prepared as shown in Table 2 among the negative electrodes.
【００４４】比較例１〜９ 負極中、正極中の結着剤を表１のようにして作製した以
外は、実施例１と同様に電池を作製した。 Comparative Examples 1 to 9 A battery was prepared in the same manner as in Example 1 except that the binder in the negative electrode and the positive electrode was prepared as shown in Table 1.
【００４５】比較例１０〜１８ 負極中、正極中の結着剤を表２のようにして作製した以
外は、実施例２５と同様に電池を作製した。 Comparative Examples 10 to 18 Batteries were produced in the same manner as in Example 25 except that the binder in the positive electrode was prepared as shown in Table 2 in the negative electrode.
【００４６】評価 各実施例、比較例で用いた正極、負極の活物質層の集電
体への接着強度測定を行い、次のように評価した。 Evaluation The adhesive strength of the active material layers of the positive electrode and the negative electrode used in each of the examples and comparative examples to the current collector was measured and evaluated as follows.
【００４７】短冊状に切り取った電極に粘着テープを貼
り、集電体と活物質層を一部剥離させ、引っ張り試験機
で１８０°に引っ張り、そのときの応力から接着強度を
算出した。An adhesive tape was applied to the electrode cut in a strip shape, the current collector and the active material layer were partially peeled off, pulled at 180 ° by a tensile tester, and the adhesive strength was calculated from the stress at that time.
【００４８】また、実施例１〜４８及び比較例１〜１８
の電池について、理論容量の１時間率充放電（１Ｃ）を
行い、次のように評価した。Examples 1 to 48 and Comparative Examples 1 to 18
The battery was charged / discharged (1C) at a theoretical capacity of 1 hour, and evaluated as follows.
【００４９】各電池に対して、２３℃、５時間率（Ｏ．
２Ｃ）の定電流定電圧充電を上限４．２Ｖまで１５時間
行い、次にＯ．２Ｃの定電流放電を終止電圧２．５Ｖ間
で行なった。放電容量はこのように決定し、これを１０
０％としたときの１時間率充放電（１Ｃ）５００サイク
ル後の容量維持率を計算した。For each battery, at 23 ° C. for 5 hours (O.
2C) is performed for 15 hours up to an upper limit of 4.2 V for 15 hours. A constant current discharge of 2C was performed at a final voltage of 2.5V. The discharge capacity was determined in this way, and
The capacity retention rate after 500 cycles of 1 hour rate charging / discharging (1C) was calculated assuming 0%.
【００５０】これらの測定結果を表１、表２及び図１、
図２に示す。Tables 1 and 2 and FIGS.
As shown in FIG.
【００５１】[0051]
【表１】 [Table 1]
【００５２】[0052]
【表２】 [Table 2]
【００５３】図１、図２から明らかなように、ポリ（ビ
ニリデンフルオロライド−ｃｏ−ヘキサフルオロプロピ
レン）を単独、または混合した電極の集電体への接着強
度は向上しているのがわかった。As is clear from FIG. 1 and FIG. 2, it was found that the adhesive strength to the current collector of an electrode containing poly (vinylidenefluoride-co-hexafluoropropylene) alone or mixed was improved. .
【００５４】その効果がポリ（ビニリデンフルオロライ
ド−ｃｏ−ヘキサフルオロプロピレン）中のヘキサフル
オロプロピレンが３重量％から３０重量％のとき、顕著
な効果を示した。The effect was remarkable when the content of hexafluoropropylene in the poly (vinylidenefluoride-co-hexafluoropropylene) was 3% by weight to 30% by weight.
【００５５】ポリ（ビニリデンフルオロライド−ｃｏ−
ヘキサフルオロプロピレン）とポリビニリデンフルオロ
ライドを混合する場合、ポリ（ビニリデンフルオロライ
ド−ｃｏ−ヘキサフルオロプロピレン）が３０重量％以
上で顕著な効果が見られ、それは９５重量％まで持続し
た。Poly (vinylidene fluoride) -co-
When hexafluoropropylene) and polyvinylidenefluoride were mixed, a remarkable effect was observed at 30% by weight or more of poly (vinylidenefluoride-co-hexafluoropropylene), and it was maintained up to 95% by weight.
【００５６】また、表１、表２から明らかなように、負
極または正極にポリ（ビニリデンフルオロライド−ｃｏ
−ヘキサフルオロプロピレン）とポリビニリデンフルオ
ロライドとを混合した結着剤を用いた場合、ポリビニリ
デンフルオロライドのみのものに比べて、明らかに５０
０サイクル後の維持率が良かった。その効果は負極に用
いたときに大きかった。また、ポリ（ビニリデンフルオ
ロライド−ｃｏ−ヘキサフルオロプロピレン）中のヘキ
サフルオロプロピレンが３重量％から３０重量％のと
き、顕著な効果を示し、接着強度と相関性があった。As is clear from Tables 1 and 2, poly (vinylidenefluoride-co
-Hexafluoropropylene) and polyvinylidenefluoride in the case of using a binder mixed with the polyvinylidenefluoride alone, it is clearly 50
The maintenance rate after 0 cycles was good. The effect was great when used for a negative electrode. Further, when the content of hexafluoropropylene in the poly (vinylidenefluoride-co-hexafluoropropylene) was 3% by weight to 30% by weight, a remarkable effect was exhibited, and there was a correlation with the adhesive strength.
【００５７】ポリ（ビニリデンフルオロライド−ｃｏ−
ヘキサフルオロプロピレン）とポリビニリデンフルオロ
ライドを混合する場合、ポリ（ビニリデンフルオロライ
ド−ｃｏ−ヘキサフルオロプロピレン）が３０重量％以
上で顕著な効果が見られ、それは９５重量％まで持続
し、やはり接着強度と相関性があった。Poly (vinylidene fluoride) -co-
When mixing hexafluoropropylene) and polyvinylidene fluoride, poly (vinylidene fluoride-co-hexafluoropropylene) has a remarkable effect at 30% by weight or more, which lasts up to 95% by weight. And correlated.
【００５８】なお、非水電解液電池、ゲル状電解質電池
共に同様の傾向が得られた。The same tendency was obtained for both the non-aqueous electrolyte battery and the gel electrolyte battery.
【００５９】[0059]
【発明の効果】以上の説明からも明らかなように、本発
明によれば、負極電極や正極電極における活物質層の剥
離を防止することができ、過酷な条件でも優れたサイク
ル性能を発揮する非水電解質電池を提供することができ
る。As is apparent from the above description, according to the present invention, the active material layer on the negative electrode and the positive electrode can be prevented from peeling, and excellent cycle performance can be exhibited even under severe conditions. A non-aqueous electrolyte battery can be provided.
【図１】ヘキサフルオロプロピレンの含有率と接着強度
の関係を示す特性図である。FIG. 1 is a characteristic diagram showing a relationship between a hexafluoropropylene content and an adhesive strength.
【図２】コポリマーの含有率と接着強度の関係を示す特
性図である。FIG. 2 is a characteristic diagram showing a relationship between a copolymer content and an adhesive strength.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 畠沢 剛信 東京都品川区北品川６丁目７番35号 ソニ ー株式会社内 (72)発明者 渋谷 真志夫 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） 5H003 AA04 AA06 BB02 BB04 BB05 BB11 BB38 BB48 BD04 5H029 AJ05 AJ11 AK03 AL06 AL07 AM01 AM02 AM03 AM04 AM07 AM11 AM16 BJ02 BJ03 BJ04 DJ08 EJ12 EJ14 HJ01 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takenobu Hatakezawa 6-7-35 Kita Shinagawa, Shinagawa-ku, Tokyo Inside Sony Corporation (72) Inventor Masashi Shibuya 6-7 Kita-Shinagawa, Shinagawa-ku, Tokyo No. 35 Sony Corporation F term (reference) 5H003 AA04 AA06 BB02 BB04 BB05 BB11 BB38 BB48 BD04 5H029 AJ05 AJ11 AK03 AL06 AL07 AM01 AM02 AM03 AM04 AM07 AM11 AM16 BJ02 BJ03 BJ04 DJ08 EJ12 EJ14 HJ01
Claims (7)
質と結着剤とを含有する活物質層とからなる正極電極及
び負極電極を有し、 上記正極電極及び／又は負極電極の結着剤は、ビニリデ
ンフルオライドとヘキサフルオロプロピレンとの共重合
体及びポリビニリデンフルオライドを含有することを特
徴とする非水電解質電池。1. A positive electrode and a negative electrode each comprising a current collector and an active material layer formed on the current collector and containing an active material and a binder, wherein the positive electrode and / or the negative electrode A non-aqueous electrolyte battery, wherein the binder of the electrode contains a copolymer of vinylidene fluoride and hexafluoropropylene and polyvinylidene fluoride.
ルオロプロピレンとの共重合体の結着剤中に占める割合
が３０〜９５重量％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。2. The nonaqueous electrolyte battery according to claim 1, wherein the proportion of the copolymer of vinylidene fluoride and hexafluoropropylene in the binder is 30 to 95% by weight.
ルオロプロピレンとの共重合体において、ヘキサフルオ
ロプロピレンの割合が３〜３０重量％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。3. The non-aqueous electrolyte battery according to claim 1, wherein the proportion of hexafluoropropylene in the copolymer of vinylidene fluoride and hexafluoropropylene is 3 to 30% by weight.
をドープ、脱ドープし得る材料を含むことを特徴とする
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 the active material of the negative electrode includes a material capable of doping and undoping lithium.
材料が炭素材料であることを特徴とする請求項４記載の
非水電解質電池。5. The non-aqueous electrolyte battery according to claim 4, wherein the material capable of doping and undoping lithium is a carbon material.
と遷移金属の複合酸化物を含むことを特徴とする請求項
１記載の非水電解質電池。6. The non-aqueous electrolyte battery according to claim 1, wherein the active material of the positive electrode includes a composite oxide of lithium and a transition metal.
ウム塩を含むゲル電解質又は固体電解質を用いたことを
特徴とする請求項１記載の非水電解質電池。7. The non-aqueous electrolyte battery according to claim 1, wherein a gel electrolyte or a solid electrolyte containing a matrix polymer and a lithium salt is used as the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30308398A JP4613370B2 (en) | 1998-10-23 | 1998-10-23 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30308398A JP4613370B2 (en) | 1998-10-23 | 1998-10-23 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000133270A true JP2000133270A (en) | 2000-05-12 |
| JP4613370B2 JP4613370B2 (en) | 2011-01-19 |
Family
ID=17916694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30308398A Expired - Fee Related JP4613370B2 (en) | 1998-10-23 | 1998-10-23 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4613370B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008021586A (en) * | 2006-07-14 | 2008-01-31 | Nec Tokin Corp | Nonaqueous secondary battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0997611A (en) * | 1995-09-29 | 1997-04-08 | Toray Ind Inc | Electrode for battery, and secondary battery |
| JPH09199130A (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem Japan Kk | Electrode and secondary battery using it |
| JPH09199134A (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem Japan Kk | Electrode and secondary battery using it |
| JPH09199133A (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem Japan Kk | Electrode and secondary battery using it |
| JPH09259890A (en) * | 1996-03-21 | 1997-10-03 | Dainippon Printing Co Ltd | Electrode applying solution and electrode plate for nonaqueous electrolyte secondary battery |
| JPH09293535A (en) * | 1996-04-25 | 1997-11-11 | Sumitomo Chem Co Ltd | Nonaqueous secondary battery |
| JPH10112321A (en) * | 1996-10-07 | 1998-04-28 | Sony Corp | Nonaqueous electrolyte secondary battery and its manufacture |
| JPH10189053A (en) * | 1996-12-24 | 1998-07-21 | Toshiba Battery Co Ltd | Manufacture of polyelectrolyte battery |
-
1998
- 1998-10-23 JP JP30308398A patent/JP4613370B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0997611A (en) * | 1995-09-29 | 1997-04-08 | Toray Ind Inc | Electrode for battery, and secondary battery |
| JPH09199130A (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem Japan Kk | Electrode and secondary battery using it |
| JPH09199134A (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem Japan Kk | Electrode and secondary battery using it |
| JPH09199133A (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem Japan Kk | Electrode and secondary battery using it |
| JPH09259890A (en) * | 1996-03-21 | 1997-10-03 | Dainippon Printing Co Ltd | Electrode applying solution and electrode plate for nonaqueous electrolyte secondary battery |
| JPH09293535A (en) * | 1996-04-25 | 1997-11-11 | Sumitomo Chem Co Ltd | Nonaqueous secondary battery |
| JPH10112321A (en) * | 1996-10-07 | 1998-04-28 | Sony Corp | Nonaqueous electrolyte secondary battery and its manufacture |
| JPH10189053A (en) * | 1996-12-24 | 1998-07-21 | Toshiba Battery Co Ltd | Manufacture of polyelectrolyte battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008021586A (en) * | 2006-07-14 | 2008-01-31 | Nec Tokin Corp | Nonaqueous secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4613370B2 (en) | 2011-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4714072B2 (en) | Anode for lithium secondary battery and lithium secondary battery including the same | |
| JP2001291517A (en) | Positive active material and nonaqueous electrolyte secondary battery | |
| JP2001023687A (en) | Nonaqueous electrolyte battery | |
| JP2000164254A (en) | Gel electrolyte and gel electrolyte battery | |
| JP5163065B2 (en) | Non-aqueous electrolyte secondary battery and non-aqueous electrolyte composition | |
| JP4310646B2 (en) | Negative electrode and battery using the same | |
| WO2018181243A1 (en) | Lithium ion secondary battery | |
| KR20150060513A (en) | Negative electrode active material layer for rechargeable lithium battery, preparing the same, and rechargeable lithium battery | |
| JP4355970B2 (en) | Solid electrolyte battery and manufacturing method thereof | |
| JP2003331825A (en) | Nonaqueous secondary battery | |
| JP4655118B2 (en) | Non-aqueous electrolyte battery and non-aqueous electrolyte composition | |
| JP2009302022A (en) | Nonaqueous electrolyte secondary battery | |
| JP2001015156A (en) | Nonaqueous electrolyte battery | |
| KR101472848B1 (en) | Non-crosslinked-crosslinked polymer hybrid binder, preparation method thereof, and anode active material composition for a lithium ion battery comprising same | |
| JP2007134244A (en) | Battery | |
| JP2007134245A (en) | Electrolyte solution and battery | |
| JPH11185773A (en) | Gelled electrolyte cell | |
| JP2000195518A (en) | Nonaqueous electrolyte secondary battery | |
| KR20200065625A (en) | Lithium secondary battery, and method for preparing the same | |
| JP2002015726A (en) | Gel electrolyte secondary battery | |
| JP4085481B2 (en) | battery | |
| JP2009211941A (en) | Nonaqueous electrolyte secondary battery | |
| JP4613370B2 (en) | Non-aqueous electrolyte battery | |
| JPH10270079A (en) | Nonaqueous electrolyte battery | |
| JP4080110B2 (en) | Non-aqueous electrolyte battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050713 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080910 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080924 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081125 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100323 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100623 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20100723 |
|
| 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: 20100921 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101004 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131029 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |