JP3532016B2 - Organic electrolyte secondary battery - Google Patents
Organic electrolyte secondary batteryInfo
- Publication number
- JP3532016B2 JP3532016B2 JP32841395A JP32841395A JP3532016B2 JP 3532016 B2 JP3532016 B2 JP 3532016B2 JP 32841395 A JP32841395 A JP 32841395A JP 32841395 A JP32841395 A JP 32841395A JP 3532016 B2 JP3532016 B2 JP 3532016B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- secondary battery
- negative electrode
- graphitized carbon
- aspect ratio
- 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.)
- Expired - Fee Related
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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機電解液二次電
池に係わり、さらに詳しくは、その負極活物質の改良に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electrolyte secondary battery, and more particularly to improvement of a negative electrode active material thereof.
【０００２】[0002]
【従来の技術】リチウム含有遷移金属カルコゲナイドを
正極活物質とする有機電解液二次電池では、負極活物質
として一般にカーボンが用いられている。このカーボン
は層状構造をしており、その層間をリチウムがインター
カレートすることによって充電される。この層状構造に
ついては原料を熱処理することによって制御でき、たと
えばカーボン作製過程において熱処理温度が高い場合に
は、層間距離ｄ002 が狭くなり、現存する最高の結晶性
を有する天然黒鉛では層間距離ｄ002 が３．３５Å
（０．３３５ｎｍ）近くになり、ｃ軸方向の結晶子サイ
ズＬｃは大きくなり１０００Å以上にもなる。また、原
料に比較的多くのベンゼン環を含んでいる場合と、たと
えば炭素の一次結合が多い原料とでは、同じ熱処理温度
でも、異なった層間距離ｄ002 とｃ軸方向の結晶子サイ
ズＬｃを持つことになる。2. Description of the Related Art Carbon is generally used as a negative electrode active material in an organic electrolyte secondary battery using a lithium-containing transition metal chalcogenide as a positive electrode active material. This carbon has a layered structure and is charged by intercalating lithium between the layers. This layered structure can be controlled by heat-treating the raw material. For example, when the heat treatment temperature is high in the carbon production process, the interlayer distance d 002 becomes narrow, and in the existing natural graphite having the highest crystallinity, the interlayer distance d 002. Is 3.35Å
(0.335 nm), the crystallite size Lc in the c-axis direction becomes large, reaching 1000 Å or more. Further, when the raw material contains a relatively large number of benzene rings and, for example, the raw material having a large number of carbon primary bonds, different interlayer distances d 002 and crystallite sizes Lc in the c-axis direction are obtained even at the same heat treatment temperature. It will be.
【０００３】ところで、これらのカーボンを負極活物質
として用い、たとえばＬｉＮｉＯ2、ＬｉＣｏＯ2 など
のリチウム含有遷移金属カルコゲナイドを正極活物質と
して用いた有機電解液二次電池では、黒鉛化が進んだカ
ーボン、すなわち、層間距離ｄ002 が小さく、ｃ軸方向
の結晶子サイズＬｃが大きいカーボンを負極活物質とし
て用いた方が高い充放電容量を得ることができ、理論的
にはＣ6 Ｌｉ、つまり３７２ｍＡｈ／ｇの充放電容量を
得ることができることになっている。By the way, in an organic electrolyte secondary battery using these carbons as a negative electrode active material and a lithium-containing transition metal chalcogenide such as LiNiO 2 or LiCoO 2 as a positive electrode active material, carbon that has undergone graphitization That is, a higher charge / discharge capacity can be obtained by using carbon having a small interlayer distance d 002 and a large crystallite size Lc in the c-axis direction as the negative electrode active material, and theoretically C 6 Li, that is, 372 mAh / It is supposed that a charge / discharge capacity of g can be obtained.
【０００４】これらのカーボンを用いて負極を作製する
場合、通常、これらのカーボンは粉末状態にしてバイン
ダーと混合し、要すれば、スラリー状にして、塗布、乾
燥する工程を経て、それを集電体に担持させることによ
り、負極を作製している。In the case of producing a negative electrode using these carbons, usually, these carbons are made into a powder state and mixed with a binder, and if necessary, made into a slurry, coated and dried, and then collected. A negative electrode is manufactured by supporting it on an electric body.
【０００５】そして、そのカーボンを粉末化する方法と
しては、あらかじめバルク状の炭素材料を２０００℃
以上の高温に加熱して黒鉛化カーボンを作製し、後にそ
れを粉砕する方法、あらかじめ球状のピッチを用意
し、それを加熱する方法、炭素繊維を加熱する方法、
の３種類が一般に採用されており、得られるカーボン粉
末は、それぞれ鱗片状、球状、繊維状と、形状が異なっ
ている。As a method for powderizing the carbon, a bulk carbon material is previously prepared at 2000 ° C.
To produce graphitized carbon by heating to a high temperature above, a method of crushing it later, a spherical pitch prepared in advance, a method of heating it, a method of heating carbon fiber,
The following three types are generally adopted, and the obtained carbon powders have different shapes such as scaly, spherical, and fibrous.
【０００６】これらの中で、特に鱗片状黒鉛化カーボン
は、製造工程でのエネルギー投資などの点から最も低価
格にできる。しかし、電池用の負極としての性能は単位
体積当たりの充放電容量が大きいことが要求されるの
で、単位体積当たりの充放電容量を大きくするため、上
記鱗片状黒鉛化カーボンを用いた負極を圧縮すると、他
の２種類の形状のカーボンを用いた場合に比べて、急激
に充放電容量が低下するという問題があった。[0006] Of these, the scale-like graphitized carbon can be made the lowest in price in terms of energy investment in the manufacturing process. However, since performance as a negative electrode for a battery is required to have a large charge / discharge capacity per unit volume, in order to increase the charge / discharge capacity per unit volume, a negative electrode using the above scale-like graphitized carbon is compressed. Then, there is a problem that the charge / discharge capacity is drastically reduced as compared with the case of using the other two types of carbon.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記のよう
な鱗片状黒鉛化カーボンを負極活物質として用いた場合
の問題点を解決し、鱗片状黒鉛化カーボンを負極活物質
として用いる有機電解液二次電池において充放電特性を
向上させ、充放電特性の優れた有機電解液二次電池を提
供することを目的とする。DISCLOSURE OF THE INVENTION The present invention solves the problems in the case of using scaly graphitized carbon as a negative electrode active material as described above, and organic electrolysis using scaly graphitized carbon as a negative electrode active material. An object of the present invention is to provide an organic electrolyte secondary battery having improved charge / discharge characteristics and excellent charge / discharge characteristics in a liquid secondary battery.
【０００８】[0008]
【課題を解決するための手段】本発明は、アスペクト比
が３以上の鱗片状黒鉛化カーボンとアスペクト比が１以
上２以下の球状カーボンとの混合比を負極活物質として
用いることによって、上記目的を達成したものである。Means for Solving the Problems The present invention achieves the above object by using a mixture ratio of scaly graphitized carbon having an aspect ratio of 3 or more and spherical carbon having an aspect ratio of 1 or more and 2 or less as a negative electrode active material. Has been achieved.
【０００９】以下、これを詳細に説明すると、本発明者
は、まず、鱗片状黒鉛化カーボンが圧縮されることによ
って容量が低下するのは、次の理由によるものと推定し
た。たとえば、球状カーボンを圧縮した場合も負極内で
のカーボン粒子間のすき間（以下、単に「すき間」とい
う）が減少するが、球と球とのすき間は、この球が形状
破壊を起こさない限り、小さくはならず、一定の空間が
確保される。通常、負極の厚み方向において直接負極表
面で電解液に接していない内部粒子も充放電できるの
は、負極内部の上記すき間に電解液が保持されているか
らであって、負極内部のすき間が負極の充放電特性に大
きな影響を及ぼすことは明らかである。つまり、球状の
カーボンや繊維状のカーボンでは、かなり高圧で圧縮し
ても、そのようなすき間が確保されるので急激な容量低
下が生じない。To explain this in detail below, the present inventor first estimated that the reason that the capacity of the scaly graphitized carbon is reduced by compression is as follows. For example, when spherical carbon is compressed, the gap between carbon particles in the negative electrode (hereinafter, simply referred to as "gap") is reduced, but the gap between spheres is limited as long as this sphere does not cause shape destruction. It does not become small, but a certain space is secured. Usually, the internal particles that are not in direct contact with the electrolytic solution on the surface of the negative electrode in the thickness direction of the negative electrode can also be charged and discharged because the electrolytic solution is held in the above-mentioned gap inside the negative electrode, and the gap inside the negative electrode is the negative electrode. It is obvious that the charging and discharging characteristics of the are greatly affected. That is, with spherical carbon or fibrous carbon, even if compressed at a considerably high pressure, such a gap is ensured, so that a sudden decrease in capacity does not occur.
【００１０】これに対して、鱗片状黒鉛化カーボン、特
にアスペクト比が３以上、すなわち、粒子の長軸方向の
長さと短軸方向の長さとの比が３以上の鱗片状黒鉛化カ
ーボンでは、圧縮により粒子が重なり合うようにして揃
うため、すき間がほとんどなくなったり、すき間が粒子
で密閉されてしまい、そのため、電解液がすみやかに負
極内部に浸透することができず、その結果、負極を構成
する活物質の一部しか充放電反応に寄与できず、充放電
容量が低くなる。On the other hand, in the case of scaly graphitized carbon, in particular, the scaly graphitized carbon having an aspect ratio of 3 or more, that is, a ratio of the length in the major axis direction to the length in the minor axis direction of the particles is 3 or more, Since the particles are aligned so as to overlap each other by compression, the gap is almost eliminated or the gap is sealed with the particles, and therefore the electrolytic solution cannot quickly penetrate into the negative electrode, and as a result, the negative electrode is formed. Only part of the active material can contribute to the charge / discharge reaction, and the charge / discharge capacity becomes low.
【００１１】ただし、鱗片状黒鉛化カーボンでも、多少
の充放電容量が得られるのは、充放電過程において、鱗
片状黒鉛化カーボン粒子が１０％程度の膨張、収縮を起
こすので、密閉されたすき間に電解液が徐々に浸透し、
充放電反応が生じるようになるからであるが、それでも
高々理論容量の５０％程度しか充放電できない。However, even with the scale-like graphitized carbon, some charge / discharge capacity can be obtained because the scale-like graphitized carbon particles expand and contract by about 10% during the charging / discharging process. The electrolyte gradually penetrates into the
This is because a charge / discharge reaction occurs, but even then, at most about 50% of the theoretical capacity can be charged / discharged.
【００１２】そこで、本発明者は、そのような鱗片状黒
鉛化カーボンに球状のカーボンを混合することによっ
て、そのような電解液の通路となるすき間が密閉される
のが防止され、電解液が負極内部まですみやかに浸透し
て、負極内部のカーボン粒子まで充分に充放電に寄与で
きるようになることを見出し、本発明を完成したのであ
る。Therefore, the present inventor mixed the scaly graphitized carbon with the spherical carbon to prevent the gap serving as the passage of the electrolytic solution from being sealed, and The present invention has been completed by discovering that the carbon particles inside the negative electrode can quickly permeate into the negative electrode and can fully contribute to charging and discharging.
【００１３】すなわち、鱗片状黒鉛化カーボンだけであ
れば、圧縮によって重なるところを、その間に球状のカ
ーボン粒子が存在することによって、電解液が浸透でき
る程度のすき間を確保できるようにしたのである。That is, in the case of only the scale-like graphitized carbon, it is possible to secure a gap where the electrolytic solution can permeate by the presence of spherical carbon particles between the overlapping places by compression.
【００１４】上記の球状カーボンとしては、カーボンマ
イクロビーズを２５００℃以上で熱処理した黒鉛化カー
ボンでもよいし、また低結晶カーボンでもよい。そし
て、上記球状カーボンの粒子形状はアスペクト比が１以
上２以下のものであることが必要であり、アスペクト比
が２より大きくなると、鱗片状カーボンと同様の挙動を
示すようになるので好ましくない。なお、本発明におい
て、球状カーボンのアスペクト比を１以上としているの
は、アスペクト比が１より小さいものは存在しないから
である。The spherical carbon may be graphitized carbon obtained by heat-treating carbon microbeads at 2500 ° C. or higher, or low crystalline carbon. The particle shape of the spherical carbon is required to have an aspect ratio of 1 or more and 2 or less, and if the aspect ratio is larger than 2, the same behavior as that of scale-like carbon is exhibited, which is not preferable. In the present invention, the spherical carbon has an aspect ratio of 1 or more because there is no one having an aspect ratio smaller than 1.
【００１５】また、球状カーボンの粒子サイズは、鱗片
状黒鉛化カーボンと同程度のサイズでもよく、また１／
１０程度の小さいものでもよいが、すき間を効率よく確
保するためにはなるべく小さい方が好ましく、鱗片状黒
鉛化カーボンの粒径にもよるが、平均粒径で１〜１５μ
ｍ程度のものが好ましい。すなわち、上記範囲内では所
望とする充放電特性の充分な向上が得られるが、球状カ
ーボンの粒子サイズが大きくなると、その混合量を多く
しないと、すき間を充分に確保することがむつかしくな
り、その球状カーボンの増量によって、放電容量が小さ
くなったり、コストが高くなる場合が生じるためであ
る。The particle size of the spherical carbon may be the same as that of the scale-like graphitized carbon.
Although it may be as small as about 10, it is preferably as small as possible in order to efficiently secure a gap, and depending on the particle size of the scaly graphitized carbon, the average particle size is 1 to 15 μm.
It is preferably about m. That is, within the above range, a desired sufficient improvement in charge / discharge characteristics can be obtained, but when the particle size of the spherical carbon becomes large, it becomes difficult to secure a sufficient gap unless the mixing amount is increased, This is because the increase in the amount of spherical carbon may reduce the discharge capacity or increase the cost.
【００１６】鱗片状黒鉛化カーボンと球状カーボンとの
混合比は、特に限定されるものではなく種々の範囲を採
用することができるが、通常、７０：３０〜９５：５、
特に８５：１５〜９５：０５が好ましい。鱗片状黒鉛化
カーボンの量が上記範囲より多い場合は、球状カーボン
による効果が充分に発現しなくなって、充放電特性の充
分な向上が得られなくなるおそれがあり、また、鱗片状
黒鉛化カーボンの量が上記範囲より少ない場合は、放電
容量が低下するおそれがある。The mixing ratio of the scale-like graphitized carbon and the spherical carbon is not particularly limited and various ranges can be adopted, but usually 70:30 to 95: 5,
Particularly, 85:15 to 95:05 is preferable. If the amount of scaly graphitized carbon is more than the above range, the effect due to spherical carbon may not be sufficiently expressed, and sufficient improvement of charge / discharge characteristics may not be obtained. If the amount is less than the above range, the discharge capacity may decrease.
【００１７】ここで、本発明において用いる鱗片状黒鉛
化カーボンについても詳しく説明すると、この鱗片状黒
鉛化カーボンはアスペクト比が３以上のものである。つ
まり、アスペクト比が３以上の鱗片状黒鉛化カーボンで
あれば、低価格のカーボンを得る可能性があるが、アス
ペクト比が３より小さい場合は、価格面で有利性を持つ
カーボンが得られにくくなるおそれがあるからである。The scaly graphitized carbon used in the present invention will now be described in detail. The scaly graphitized carbon has an aspect ratio of 3 or more. In other words, if the scale-like graphitized carbon has an aspect ratio of 3 or more, it is possible to obtain low-priced carbon, but if the aspect ratio is smaller than 3, it is difficult to obtain carbon having a price advantage. This is because there is a risk that
【００１８】また、本発明において用いる鱗片状黒鉛化
カーボンは、層間距離ｄ002 が３．３７Å以上で、ｃ軸
方向の結晶子サイズＬｃが４００Å以上のものであるこ
とが好ましい。すなわち、カーボンの層間距離ｄ002 が
３．３７Å以上になると、結晶性の向上が顕著になり、
それによって、カーボンの層間へのリチウムイオンのイ
ンターカレーション量が増加し、理想的なＣ6 Ｌｉの状
態に近付くことができ、充放電容量が大きくなる可能性
が生じ、また、カーボンのｃ軸方向の結晶子サイズＬｃ
が４００Å以上になると、カーボンの層間へのリチウム
のインターカレーション量の増加が助長されて、充放電
容量が大きくなる可能性が生じる。そして、層間距離に
関しては、自然界の限界の層間距離ｄ002 が３．３５Å
のものまで使用可能であり、また、ｃ軸方向の結晶子サ
イズＬｃに関し２０００Å程度のものまで好適に使用す
ることができる。The scale-like graphitized carbon used in the present invention preferably has an interlayer distance d 002 of 3.37 Å or more and a crystallite size Lc in the c-axis direction of 400 Å or more. That is, when the carbon interlayer distance d 002 is 3.37 Å or more, the crystallinity is remarkably improved,
As a result, the amount of intercalation of lithium ions between the layers of carbon is increased, and it is possible to approach the ideal C 6 Li state, which may lead to an increase in charge and discharge capacity. Direction crystallite size Lc
Is more than 400 Å, the increase in the amount of lithium intercalation between carbon layers is promoted, and the charge / discharge capacity may increase. Regarding the interlayer distance, the limit interlayer distance d 002 in nature is 3.35Å
Those having a crystallite size Lc in the c-axis direction of about 2000 Å can be suitably used.
【００１９】本発明において、正極活物質としては、た
とえばリチウムニッケル酸化物、リチウムマンガン酸化
物、リチウムコバルト酸化物（これらは、通常、それぞ
れ、ＬｉＮｉＯ2 、ＬｉＭｎＯ2 、ＬｉＣｏＯ2 などで
表すが、これらのＬｉとＮｉの比、ＬｉとＭｎの比、Ｌ
ｉとＣｏの比は化学量論組成からずれている場合が多
い）などのリチウム含有遷移金属カルコゲナイドが単独
でまたは２種以上の混合物として用いられる。ただし、
正極活物質が上記化合物として存在するのは、電池が放
電状態にある時であり、電池が充放電状態にある時はリ
チウムを放出した状態で存在する。In the present invention, examples of the positive electrode active material include lithium nickel oxide, lithium manganese oxide and lithium cobalt oxide (these are usually represented by LiNiO 2 , LiMnO 2 and LiCoO 2 , respectively. Ratio of Li to Ni, ratio of Li to Mn, L
The ratio of i to Co is often deviated from the stoichiometric composition), and a lithium-containing transition metal chalcogenide is used alone or as a mixture of two or more kinds. However,
The positive electrode active material exists as the above compound when the battery is in a discharged state, and when the battery is in a charged and discharged state, it exists in a state in which lithium is released.
【００２０】そして、正極は、上記正極活物質に、必要
に応じて、たとえばりん（鱗）状黒鉛、アセチレンブラ
ック、カーボンブラックなどの導電助剤と、たとえばポ
リフッ化ビニリデン、ポリテトラフルオロエチレン、エ
チレンプロピレンジエンターポリマーなどのバインダー
を加えて調製した正極合剤を加圧成形するか、あるいは
さらに溶媒を加えてペースト状にし、それをたとえば金
属箔（たとえば、アルミニウム箔、チタン箔、白金箔な
ど）などからなる集電体上に塗布、乾燥する工程を経て
作製される。ただし、正極の作製方法は上記例示のもの
に限定されることはない。The positive electrode may be made by adding the conductive material such as phosphorus (scaly) graphite, acetylene black or carbon black to the positive electrode active material, if necessary, and polyvinylidene fluoride, polytetrafluoroethylene or ethylene. A positive electrode mixture prepared by adding a binder such as propylene diene terpolymer is pressure-molded, or a solvent is further added to form a paste, which is made of, for example, metal foil (eg, aluminum foil, titanium foil, platinum foil, etc.). It is manufactured through a process of coating and drying on a current collector made of, for example. However, the method for producing the positive electrode is not limited to the above-exemplified one.
【００２１】負極は、上記特定のカーボンの混合物から
なる負極活物質（ただし、負極活物質がカーボンそのも
のとして存在するのは、電池が放電状態にある時であ
り、電池が充電状態にある時にはカーボンの層間にリチ
ウムイオンがインターカレートした状態になる）に、必
要に応じて、たとえばポリフッ化ビニリデン、ポリテト
ラフルオロエチレン、エチレンプロピレンジエンターポ
リマーなどのバインダーを適宜加え、混合して調製した
負極合剤を加圧成形するか、あるいは、さらに溶媒を加
えてペースト状にし、そのペーストをたとえば金属箔
（たとえば、銅箔、ニッケル箔など）などからなる集電
体上に塗布、乾燥する工程を経て作製される。ただし、
負極の作製方法も上記例示のものに限定されることはな
い。The negative electrode is a negative electrode active material composed of a mixture of the above-mentioned specific carbons (however, the negative electrode active material exists as carbon itself when the battery is in a discharged state and when the battery is in a charged state. In the state where lithium ions are intercalated between the layers), a binder such as polyvinylidene fluoride, polytetrafluoroethylene, or ethylene propylene diene terpolymer is appropriately added to the negative electrode mixture prepared as necessary. After pressure-molding the agent, or adding a solvent to form a paste, the paste is applied onto a current collector made of, for example, a metal foil (eg, copper foil, nickel foil, etc.), and dried. It is made. However,
The method for producing the negative electrode is not limited to the above-exemplified one.
【００２２】有機電解液（以下、電池を表す場合を除
き、簡略化して「電解液」という）としては、たとえば
１，２−ジメトキシエタン、１，２−ジエトキシエタ
ン、プロピレンカーボネート、エチレンカーボネート、
γ−ブチロラクトン、テトラヒドロフラン、１，３−ジ
オキソラン、ジエチレンカーボネート、ジメチルカーボ
ネート、エチルメチルカーボネートなどの単独または２
種以上の混合溶媒に、たとえばＬｉＣＦ3 ＳＯ3 、Ｌｉ
Ｃ4 Ｆ9 ＳＯ3 、ＬｉＣｌＯ4 、ＬｉＰＦ6 、ＬｉＢＦ
4 などの電解質を単独でまたは２種以上を溶解させたも
のが用いられる。Examples of the organic electrolytic solution (hereinafter, simply referred to as “electrolytic solution” unless otherwise indicated as a battery) include 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene carbonate, ethylene carbonate,
γ-butyrolactone, tetrahydrofuran, 1,3-dioxolane, diethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, etc. alone or 2
In a mixed solvent of one or more kinds, for example, LiCF 3 SO 3 , Li
C 4 F 9 SO 3 , LiClO 4 , LiPF 6 , LiBF
Electrolyte such as 4 is used alone or in which two or more kinds are dissolved.
【００２３】[0023]
【発明の実施の形態】つぎに、実施例を挙げて本発明を
より具体的に説明する。ただし、本発明はそれらの実施
例のみに限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to only those examples.
【００２４】実施例１
鱗片状黒鉛化カーボンとして、コークスを３０００℃で
熱処理して得たバルクカーボンを粉砕して、平均粒径が
１０μｍで、アスペクト比が６の鱗片状粉末を得た。こ
の鱗片状黒鉛化カーボンは、層間距離ｄ002 が３．３６
Åで、ｃ軸方向の結晶子サイズＬｃが８５３Åであっ
た。また、球状カーボンとしては、カーボンマイクロビ
ーズを３０００℃で熱処理して得た平均粒径１０μｍ
で、アスペクト比１．１の黒鉛化カーボンを用意した。Example 1 As scale-like graphitized carbon, bulk carbon obtained by heat-treating coke at 3000 ° C. was pulverized to obtain scale-like powder having an average particle size of 10 μm and an aspect ratio of 6. This scale-like graphitized carbon has an interlayer distance d 002 of 3.36.
And the crystallite size Lc in the c-axis direction was 853Å. The spherical carbon has an average particle size of 10 μm obtained by heat-treating carbon microbeads at 3000 ° C.
Then, graphitized carbon having an aspect ratio of 1.1 was prepared.
【００２５】これらの鱗片状黒鉛化カーボンと球状カー
ボンとを重量比６０：４０で混合し、得られたカーボン
混合物９０重量部に対して、バインダーとしてポリフッ
化ビニリデン１０重量部、溶媒としてＮ−メチル−２−
ピロリドン１５０重量部を配合して、カーボンペースト
を調製し、そのカーボンペーストを集電体としての厚さ
２０μｍの銅箔上に塗布し、乾燥した後、カレンダーロ
ールでプレスして、負極として用いるカーボン電極を作
製した。なお、上記カーボンペーストの調製にあたって
は、あらかじめポリフッ化ビニリデンをＮ−メチル−２
−ピロリドンに溶解させておいた。また、上記のように
して得られた合剤層（集電体としての銅箔上に形成され
たカーボンとバインダーとの合剤の層）との密度は１．
６４ｇ／ｃｃであった。These scale-like graphitized carbons and spherical carbons were mixed at a weight ratio of 60:40, and to 90 parts by weight of the obtained carbon mixture, 10 parts by weight of polyvinylidene fluoride as a binder and N-methyl as a solvent were mixed. -2-
A carbon paste was prepared by mixing 150 parts by weight of pyrrolidone, and the carbon paste was applied onto a copper foil having a thickness of 20 μm as a current collector, dried, and then pressed with a calendar roll to be used as a negative electrode. An electrode was prepared. In preparing the carbon paste, polyvinylidene fluoride was previously added to N-methyl-2.
-Dissolved in pyrrolidone. The density of the mixture layer obtained as described above (the layer of the mixture of carbon and binder formed on the copper foil as the current collector) was 1.
It was 64 g / cc.
【００２６】一方、正極は次のようにして作製した。す
なわち、正極活物質としては、リチウムニッケル酸化物
（通常、ＬｉＮｉＯ2 として表すが、ＬｉとＮｉの比は
化学量論組成から若干ずれている）を用い、このリチウ
ムニッケル酸化物とりん状黒鉛とポリフッ化ビニリデン
とを下記の割合で含む正極形成用の活物質含有ペースト
を調製した。On the other hand, the positive electrode was manufactured as follows. That is, as the positive electrode active material, lithium nickel oxide (usually expressed as LiNiO 2 , but the ratio of Li and Ni is slightly deviated from the stoichiometric composition) was used, and this lithium nickel oxide and phosphorous graphite were used. An active material-containing paste for forming a positive electrode containing polyvinylidene fluoride in the following ratio was prepared.
【００２７】 リチウムニッケル酸化物 ９１重量部 りん状黒鉛 ６重量部 ポリフッ化ビニリデン ３重量部[0027] Lithium nickel oxide 91 parts by weight Phosphorous graphite 6 parts by weight Polyvinylidene fluoride 3 parts by weight
【００２８】上記の正極形成用の活物質含有ペーストの
調製は、ポリフッ化ビニリデンをＮ−メチル−２−メチ
ルピロリドンにあらかじめ溶解し、それにリチウムニッ
ケル酸化物とりん状黒鉛を加えて混合し、さらにＮ−メ
チルピロリドンを加えて混合することによって行った。To prepare the above-mentioned paste containing the active material for forming the positive electrode, polyvinylidene fluoride was previously dissolved in N-methyl-2-methylpyrrolidone, and lithium nickel oxide and phosphorous graphite were added thereto and mixed, and This was done by adding N-methylpyrrolidone and mixing.
【００２９】得られた正極形成用の活物質含有ペースト
を厚さ２０μｍのアルミニウム箔上にアプリケーターを
用いて塗布し、その後、乾燥した後、カレンダーロール
でプレスして、正極を作製した。The obtained active material-containing paste for forming a positive electrode was applied onto an aluminum foil having a thickness of 20 μm using an applicator, dried and then pressed with a calendar roll to produce a positive electrode.
【００３０】そして、電解液としては、エチレンカーボ
ネートと１，２−ジメトキシエタンとの体積比１：１の
混合溶媒にＬｉＰＦ6 を１モル／リットル溶解させたも
のを用い、図１に示す構造で、外径２０ｍｍ、高さ５ｍ
ｍのボタン形有機電解液二次電池を作製した。As the electrolytic solution, a solution obtained by dissolving 1 mol / liter of LiPF 6 in a mixed solvent of ethylene carbonate and 1,2-dimethoxyethane in a volume ratio of 1: 1 was used. , Outer diameter 20mm, height 5m
A m-type button-type organic electrolyte secondary battery was produced.
【００３１】図１において、１は上記の正極であり、２
は上記の負極である。３は微孔性ポリプロピレンフィル
ムからなるセパレータで、４はポリプロピレン不織布か
らなる電解液吸収体である。５はステンレス鋼製の正極
缶であり、６はアルミニウム箔からなる正極集電体で、
７はステンレス鋼製で表面にニッケルメッキを施した負
極缶である。８は銅箔からなる負極集電体であり、９は
ポリプロピレン製の環状ガスケットであって、この電池
にはエチレンカーボネートとメチルエチルカーボネート
との体積比１：１の混合溶媒にＬｉＰＦ6 を１モル／リ
ットル溶解した電解液が注入されている。In FIG. 1, 1 is the above positive electrode, and 2
Is the above-mentioned negative electrode. Reference numeral 3 is a separator made of a microporous polypropylene film, and 4 is an electrolytic solution absorber made of a polypropylene nonwoven fabric. 5 is a stainless steel positive electrode can, 6 is a positive electrode current collector made of aluminum foil,
Reference numeral 7 is a negative electrode can made of stainless steel and having a surface plated with nickel. 8 is a negative electrode current collector made of copper foil, 9 is a polypropylene annular gasket, and 1 mol of LiPF 6 is mixed in a mixed solvent of ethylene carbonate and methyl ethyl carbonate at a volume ratio of 1: 1. / Liter Dissolved electrolyte is injected.
【００３２】実施例２
鱗片状黒鉛化カーボンとしては実施例１と同様のものを
用い、球状カーボンとしては、カーボンマイクロビーズ
を３０００℃で熱処理して得た平均粒径２μｍで、アス
ペクト比１．１の黒鉛化カーボンを用い、かつ鱗片状黒
鉛化カーボンと球状カーボンとの混合比を重量比で９
０：１０にした以外は、実施例１と同様にしてボタン形
有機電解液二次電池を作製した。Example 2 As the scale-like graphitized carbon, the same one as in Example 1 was used, and as the spherical carbon, an average particle diameter of 2 μm obtained by heat-treating carbon microbeads at 3000 ° C. and an aspect ratio of 1. 1 is used, and the mixing ratio of the scale-like graphitized carbon and the spherical carbon is 9 by weight.
A button type organic electrolyte secondary battery was produced in the same manner as in Example 1 except that the time was set to 0:10.
【００３３】実施例３
鱗片状黒鉛化カーボンとしては実施例１と同様のものを
用い、球状カーボンとしては、コークスを１０００℃で
熱処理して得た平均粒径１０μｍで、アスペクト比１．
１の黒鉛化カーボンを用い、かつ鱗片状黒鉛化カーボン
と球状カーボンとの混合比を重量比で７０：３０とした
以外は、実施例１と同様にしてボタン形有機電解液二次
電池を作製した。Example 3 As the scale-like graphitized carbon, the same one as in Example 1 was used, and as the spherical carbon, the average particle size obtained by heat treatment of coke at 1000 ° C. was 10 μm, and the aspect ratio was 1.
A button type organic electrolyte secondary battery was produced in the same manner as in Example 1 except that the graphitized carbon of No. 1 was used and the mixing ratio of the scaly graphitized carbon and the spherical carbon was 70:30 by weight. did.
【００３４】実施例４
鱗片状黒鉛化カーボンとしては、コークスを２５００℃
で熱処理したものを粉砕して、平均粒径１２μｍで、ア
スペクト比が３の鱗片状粉末を得た。この鱗片状黒鉛化
カーボンは、層間距離ｄ002 が３．３８Åで、ｃ軸方向
の結晶子サイズＬｃが５３０Åであった。球状カーボン
としては、コークスを１０００℃で熱処理して得た平均
粒径１μｍで、アスペクト比１．１の低結晶カーボンを
用意した。これらの鱗片状黒鉛化カーボンと球状カーボ
ンを用いたことと、両者の混合比を重量比で９０：１０
にした以外は、実施例１と同様にしてボタン形有機電解
液二次電池を作製した。Example 4 As scale-like graphitized carbon, coke was 2,500 ° C.
The powder heat-treated in (1) was pulverized to obtain a scaly powder having an average particle diameter of 12 μm and an aspect ratio of 3. This scale-like graphitized carbon had an interlayer distance d 002 of 3.38Å and a crystallite size Lc in the c-axis direction of 530Å. As the spherical carbon, low crystalline carbon having an average particle size of 1 μm and an aspect ratio of 1.1, which was obtained by heat-treating coke at 1000 ° C., was prepared. These scale-like graphitized carbon and spherical carbon were used, and the mixing ratio of both was 90:10 by weight.
A button type organic electrolyte secondary battery was produced in the same manner as in Example 1 except that the above was used.
【００３５】実施例５
鱗片状黒鉛化カーボンとしては実施例１と同様のものを
用い、球状カーボンとしては、コークスを１８００℃で
熱処理して得た平均粒径３μｍで、アスペクト比１．９
の乱層カーボンを用い、かつ鱗片状黒鉛化カーボンと球
状カーボンとの混合比を重量比で８０：２０にした以外
は、実施例１と同様にしてボタン形有機電解液二次電池
を作製した。Example 5 As the scale-like graphitized carbon, the same one as in Example 1 was used, and as the spherical carbon, the average particle size obtained by heat treatment of coke at 1800 ° C. was 3 μm, and the aspect ratio was 1.9.
A button type organic electrolyte secondary battery was produced in the same manner as in Example 1 except that the turbostratic carbon of No. 1 was used and the mixing ratio of the scale-like graphitized carbon and the spherical carbon was 80:20 by weight. .
【００３６】実施例６
鱗片状黒鉛化カーボンとしては実施例１と同様のものを
用い、球状カーボンとしては、フェノール樹脂を１２０
０℃で熱処理して得た平均粒径７μｍで、アスペクト比
１．５の低結晶カーボンを用い、かつ鱗片状黒鉛化カー
ボンと球状カーボンとの混合比を重量比で９０：１０と
した以外は、実施例１と同様にしてボタン形有機電解液
二次電池を作製した。Example 6 As the scale-like graphitized carbon, the same one as in Example 1 was used, and as the spherical carbon, 120 phenol resin was used.
Except that low crystalline carbon having an average particle size of 7 μm and an aspect ratio of 1.5 obtained by heat treatment at 0 ° C. was used, and the mixing ratio of scaly graphitized carbon and spherical carbon was 90:10 by weight. A button type organic electrolyte secondary battery was prepared in the same manner as in Example 1.
【００３７】比較例１
球状カーボンを用いず、そのぶん鱗片状黒鉛化カーボン
を増量した以外は、実施例１と同様にしてボタン形有機
電解液二次電池を作製した。Comparative Example 1 A button type organic electrolyte secondary battery was prepared in the same manner as in Example 1 except that spherical carbon was not used and the scale-like graphitized carbon was increased.
【００３８】比較例２
球状カーボンとして、コークスを２６００℃で熱処理し
て得た平均粒径２μｍで、アスペクト比２．７の黒鉛化
カーボンを用い、かつ鱗片状黒鉛化カーボンと球状カー
ボンとの混合比を重量比９０：１０にした以外は、実施
例１と同様にしてボタン形有機電解液二次電池を作製し
た。Comparative Example 2 As the spherical carbon, a graphitized carbon having an average particle size of 2 μm obtained by heat treatment of coke at 2600 ° C. and an aspect ratio of 2.7 was used, and the flaky graphitized carbon and the spherical carbon were mixed. A button type organic electrolyte secondary battery was produced in the same manner as in Example 1 except that the weight ratio was 90:10.
【００３９】上記のようにして作製した実施例１〜６お
よび比較例１〜２の電池について、２０℃、０．５ｍＡ
／ｃｍ2 で充放電させた場合の最高放電容量、上記最高
放電容量に達するまでに必要なサイクル数、２ｍＡ／ｃ
ｍ2 で充電し、０．５ｍＡ／ｃｍ2 で放電させた場合の
放電容量の最高放電容量に対する比率、０．５ｍＡ／ｃ
ｍ2 で充電し、２ｍＡ／ｃｍ2 で放電させた場合の放電
容量の最高放電容量に対する比率を調べた。その結果を
表１に示す。Regarding the batteries of Examples 1 to 6 and Comparative Examples 1 and 2 produced as described above, 20 ° C., 0.5 mA
Discharge capacity when charging / discharging at 1 / cm 2 , the number of cycles required to reach the above maximum discharge capacity, 2 mA / c
Ratio of discharge capacity to maximum discharge capacity when charged at m 2 and discharged at 0.5 mA / cm 2 , 0.5 mA / c
The ratio of the discharge capacity to the maximum discharge capacity when charged at m 2 and discharged at 2 mA / cm 2 was examined. The results are shown in Table 1.
【００４０】[0040]
【表１】 [Table 1]
【００４１】表１に示すように、実施例１〜６は、比較
例１〜２に比べて、放電容量が高く、また、高電流密度
での充放電での放電容量も高く、最高放電容量にも少な
いサイクル数で到達することができた。すなわち、本発
明の実施例１〜６の電池は、高電流密度での充放電にお
いても充放電特性が優れており、また、その結果から、
負荷特性も優れていることが明らかにされていた。As shown in Table 1, Examples 1 to 6 have higher discharge capacities and higher discharge capacities in charging and discharging at a high current density as compared with Comparative Examples 1 and 2, and thus have the highest discharge capacities. I was able to reach it with a small number of cycles. That is, the batteries of Examples 1 to 6 of the present invention have excellent charge / discharge characteristics even in charge / discharge at high current density, and from the results,
It has been revealed that the load characteristics are also excellent.
【００４２】[0042]
【発明の効果】以上説明したように、本発明では、鱗片
状黒鉛化カーボンに球状カーボンを混合して負極活物質
として用いることにより、高電流密度での充放電におい
ても、充放電特性が優れていて、負荷特性においても優
れた有機電解液二次電池を提供することができた。As described above, according to the present invention, the scaly graphitized carbon is mixed with the spherical carbon to be used as the negative electrode active material, so that the charge and discharge characteristics are excellent even in the charge and discharge at high current density. Therefore, it was possible to provide an organic electrolyte secondary battery having excellent load characteristics.
【図１】本発明に係る有機電解液二次電池の一例を示す
断面図である。FIG. 1 is a cross-sectional view showing an example of an organic electrolyte secondary battery according to the present invention.
１ 正極 ２ 負極 ３ セパレータ ４ 電解液吸収体 1 positive electrode 2 Negative electrode 3 separator 4 Electrolyte solution absorber
Claims (3)
正極活物質とする正極、負極および有機電解液を有する
有機電解液二次電池において、負極活物質が、アスペク
ト比が３以上の鱗片状黒鉛化カーボンとアスペクト比が
１以上２以下の球状カーボンとの混合物からなることを
特徴とする有機電解液二次電池。1. In an organic electrolyte secondary battery having a positive electrode, a negative electrode, and an organic electrolytic solution using a lithium-containing transition metal chalcogenide as a positive electrode active material, the negative electrode active material is scaly graphitized carbon having an aspect ratio of 3 or more. An organic electrolyte secondary battery comprising a mixture of spherical carbon having an aspect ratio of 1 or more and 2 or less.
ーボンとアスペクト比が１以上２以下の球状カーボンと
の混合比が重量比で７０：３０〜９５：５であることを
特徴とする請求項１記載の有機電解液二次電池。2. The weight ratio of the scaly graphitized carbon having an aspect ratio of 3 or more and the spherical carbon having an aspect ratio of 1 or more and 2 or less is 70:30 to 95: 5. Item 2. The organic electrolyte secondary battery according to item 1.
が３．３８Å以下で、ｃ軸方向の結晶子サイズＬｃが４
００Å以上であることを特徴とする請求項１または２記
載の有機電解液二次電池。3. An interlayer distance d 002 of scale-like graphitized carbon
Is 3.38Å or less, and the crystallite size Lc in the c-axis direction is 4
The organic electrolytic solution secondary battery according to claim 1 or 2, wherein the organic electrolytic solution secondary battery is 00 Å or more.
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|---|---|---|---|
| JP32841395A JP3532016B2 (en) | 1995-11-22 | 1995-11-22 | Organic electrolyte secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32841395A JP3532016B2 (en) | 1995-11-22 | 1995-11-22 | Organic electrolyte secondary battery |
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| Publication Number | Publication Date |
|---|---|
| JPH09147862A JPH09147862A (en) | 1997-06-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3783706A4 (en) * | 2019-01-03 | 2021-09-01 | Lg Chem, Ltd. | Anode active material for secondary battery, electrode comprising same, and method for manufacturing same |
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|---|---|---|---|---|
| US6337156B1 (en) * | 1997-12-23 | 2002-01-08 | Sri International | Ion battery using high aspect ratio electrodes |
| JP2002008655A (en) * | 2000-06-20 | 2002-01-11 | Sony Corp | Negative electrode and non-aqueous electrolyte cell |
| JP5430063B2 (en) * | 2000-09-26 | 2014-02-26 | 三菱化学株式会社 | Lithium secondary battery and negative electrode |
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1995
- 1995-11-22 JP JP32841395A patent/JP3532016B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
| EP3783706A4 (en) * | 2019-01-03 | 2021-09-01 | Lg Chem, Ltd. | Anode active material for secondary battery, electrode comprising same, and method for manufacturing same |
| US11799072B2 (en) | 2019-01-03 | 2023-10-24 | Lg Energy Solution, Ltd. | Anode active material for secondary battery, electrode comprising same, and method for manufacturing same |
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| Publication number | Publication date |
|---|---|
| JPH09147862A (en) | 1997-06-06 |
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