JP2001167763A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP2001167763A JP2001167763A JP34978299A JP34978299A JP2001167763A JP 2001167763 A JP2001167763 A JP 2001167763A JP 34978299 A JP34978299 A JP 34978299A JP 34978299 A JP34978299 A JP 34978299A JP 2001167763 A JP2001167763 A JP 2001167763A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium secondary
- secondary battery
- conductive material
- based oxide
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム二次電池
に係わり、特に、エネルギー密度が高く、サイクル特性
に優れたリチウム二次電池に関する。The present invention relates to a lithium secondary battery, and more particularly to a lithium secondary battery having a high energy density and excellent cycle characteristics.
【０００２】[0002]
【従来の技術】正極にリチウム（Ｌｉ）およびコバルト
（Ｃｏ）を含有するＣｏ系酸化物を活物質として用いる
リチウム二次電池は、高電圧、高容量であるためその需
要がますます増えている。2. Description of the Related Art Lithium secondary batteries using a Co-based oxide containing lithium (Li) and cobalt (Co) for the positive electrode as an active material are in high demand because of their high voltage and high capacity. .
【０００３】従来のＣｏ系酸化物を用いるリチウム二次
電池の構成は、コバルト酸リチウム（ＬｉＣｏＯ2）が
正極活物質に用いられ、負極にはＬｉを挿入する黒鉛等
の炭素材料を含み、正極と負極を隔てるポリエチレン等
の高分子多孔質フィルムにリチウム塩を有機溶媒に溶解
した有機電解液が含浸されている。A conventional lithium secondary battery using a Co-based oxide has a structure in which lithium cobalt oxide (LiCoO 2 ) is used as a positive electrode active material, a negative electrode contains a carbon material such as graphite into which Li is inserted, and a positive electrode has a positive electrode. An organic electrolytic solution obtained by dissolving a lithium salt in an organic solvent is impregnated in a polymer porous film of polyethylene or the like separating the anode and the negative electrode.
【０００４】特に、ＬｉＣｌＯ4やＬｉＰＦ6等のリチウ
ム塩をエチレンカーボネート（以下ＥＣと云う）やジメ
チルカーボネート（以下ＤＭＣと云う）等の炭酸エステ
ル類の混合溶媒に溶解した有機電解液が、高容量のもの
が得られるとして広く用いられている。In particular, an organic electrolyte in which a lithium salt such as LiClO 4 or LiPF 6 is dissolved in a mixed solvent of carbonates such as ethylene carbonate (hereinafter referred to as EC) or dimethyl carbonate (hereinafter referred to as DMC) has a high capacity. Is widely used as a product.
【０００５】また、Ｃｏ系酸化物を正極活物質に用いる
場合、正極の電気抵抗を減らす目的で導電材が正極に加
えられるが、従来は化学的安定性や電気電導性の点か
ら、黒鉛等の結晶性の高い炭素材料が用いられてきた。When a Co-based oxide is used as a positive electrode active material, a conductive material is added to the positive electrode in order to reduce the electric resistance of the positive electrode. However, conventionally, from the viewpoint of chemical stability and electric conductivity, graphite or the like is used. Has been used.
【０００６】しかしながら、このようなＬｉＣｏＯ2を
正極活物質として使用した従来のリチウム二次電池で
は、充電時の正極の最高電位が、金属Ｌｉ基準で４.３
Ｖ程度に規定され、電池内でのＬｉＣｏＯ2の放電容量
は１６０ｍＡｈ／ｇ以下に制限されてきた。However, in a conventional lithium secondary battery using such LiCoO 2 as a positive electrode active material, the maximum potential of the positive electrode at the time of charging is 4.3 based on metallic Li.
V, and the discharge capacity of LiCoO 2 in the battery has been limited to 160 mAh / g or less.
【０００７】理論的には、金属Ｌｉ基準で約４.８Ｖま
で充電することにより、ＬｉＣｏＯ2の全てのＬｉが放
出され、理論容量は約２７４ｍＡｈ／ｇに達するが、こ
のような、エネルギー密度を高めるため充電電位を引き
上げることは、充放電サイクルの進行により充放電の可
逆性が著しく劣化する、いわゆるサイクル劣化の問題が
あった。[0007] Theoretically, by charging to about 4.8 V on the basis of metallic Li, all Li of LiCoO 2 is released and the theoretical capacity reaches about 274 mAh / g. Increasing the charging potential to increase the charge / discharge reversibility of the charge / discharge remarkably deteriorates with the progress of the charge / discharge cycle.
【０００８】このサイクル劣化の要因として、正極の電
位が金属Ｌｉ基準で４.３Ｖを超えると、ＬｉＣｏＯ2の
結晶構造の菱面体晶から単斜晶への相転移が進行し、Ｌ
ｉイオンの挿入と放出の可逆性が損なわれることが挙げ
られる。As a cause of this cycle deterioration, when the potential of the positive electrode exceeds 4.3 V on the basis of metal Li, the phase transition of the crystal structure of LiCoO 2 from rhombohedral to monoclinic proceeds, and L
The reversibility of i-ion insertion and release is impaired.
【０００９】さらにまた、別の要因として、充電により
高電位となった正極導電材である結晶性の高い炭素材表
面で、有機電解液を構成する有機溶媒や、リチウム塩の
酸化分解が進行することが挙げられる。この影響は、従
来のリチウム二次電池の金属Ｌｉ基準で４.３Ｖの充電
電位では実用上支障はないが、充電電位を引き上げるに
つれて充放電効率の低下が著しくなる。Further, as another factor, the oxidative decomposition of the organic solvent and the lithium salt constituting the organic electrolytic solution proceeds on the surface of the highly conductive carbon material, which is the positive electrode conductive material which has been raised to a high potential by charging. It is mentioned. This effect does not hinder practical use at a charge potential of 4.3 V based on metal Li of a conventional lithium secondary battery, but the charge / discharge efficiency is significantly reduced as the charge potential is increased.
【００１０】[0010]
【発明が解決しようとする課題】正極に用いるＣｏ系酸
化物のサイクル特性を改善するため、各種の元素を添加
することが提案（例えば、特開平８−３１４０８号公
報、特開平６−４４９７３号公報）されているが、有機
電解液の分解を引き起こす充電電位の引き上げに対して
は十分ではない。In order to improve the cycle characteristics of the Co-based oxide used for the positive electrode, it is proposed to add various elements (for example, JP-A-8-31408 and JP-A-6-44973). However, it is not enough to raise the charging potential that causes the decomposition of the organic electrolyte.
【００１１】また、高電位での有機電解液の分解の問題
を解決するため、有機電解液の代わりに硫化物系のリチ
ウムイオン伝導性固体電解質を用いることが提案（特開
平１１−２１８０３号公報）されているが、充放電サイ
クルの進行による劣化を検討するまでには至っていな
い。Further, in order to solve the problem of decomposition of the organic electrolyte at a high potential, it has been proposed to use a sulfide-based lithium ion conductive solid electrolyte instead of the organic electrolyte (Japanese Patent Laid-Open No. 11-21803). ), But it has not reached the point of studying the deterioration due to the progress of the charge / discharge cycle.
【００１２】本発明の目的は、上記の問題を解決するた
め、正極活物質として用いるＣｏ系酸化物と、正極中の
導電材を規定して、エネルギー密度が高く、かつ、サイ
クル特性の優れたリチウム二次電池を提供することにあ
る。[0012] An object of the present invention is to solve the above problems by defining a Co-based oxide used as a positive electrode active material and a conductive material in the positive electrode to provide a high energy density and excellent cycle characteristics. An object of the present invention is to provide a lithium secondary battery.
【００１３】[0013]
【課題を解決するための手段】上記の目的を達成する本
発明の要旨は、正極活物質としてＬｉおよびＣｏを含有
するＣｏ系酸化物と、主成分が炭素である導電材とを含
む正極と、負極と、有機電解液を有するリチウム二次電
池において、前記Ｃｏ系酸化物がＭｇ、Ａｌ、Ｍｎ、Ｔ
ｉおよびＳｒから選ばれる少なくとも１種を含有し、か
つ、前記導電材の少なくともその表層に非晶質炭素質を
有することを特徴とするリチウム二次電池にある。The gist of the present invention to achieve the above object is to provide a positive electrode containing a Co-based oxide containing Li and Co as a positive electrode active material and a conductive material whose main component is carbon. , A negative electrode, and an organic electrolytic solution, wherein the Co-based oxide is Mg, Al, Mn, T
A lithium secondary battery containing at least one selected from i and Sr, and having an amorphous carbonaceous material in at least a surface layer of the conductive material.
【００１４】このような電池の構成により、充電時にお
ける正極の最高電位を、金属Ｌｉ基準で４.４Ｖ〜４.８
Ｖとすることができると同時に、充放電サイクルの進行
による充放電の可逆性の劣化を抑制することができる。[0014] With such a battery configuration, the maximum potential of the positive electrode during charging is 4.4 V to 4.8 on the basis of metal Li.
V, and at the same time, deterioration of the reversibility of charge / discharge due to the progress of the charge / discharge cycle can be suppressed.
【００１５】即ち、充電時における正極の最高電位を、
金属Ｌｉ基準で４.４Ｖ以上とすることで、正極活物質
の放電容量を向上させることができる。これにより、電
池内の正極活物質量を低減することができ、負極活物質
量を増やすことができる。従って、限られた電池容積に
おいて、より高エネルギー密度のリチウム二次電池が得
られる。That is, the maximum potential of the positive electrode during charging is
By setting the voltage to 4.4 V or more based on the metal Li, the discharge capacity of the positive electrode active material can be improved. Thereby, the amount of the positive electrode active material in the battery can be reduced, and the amount of the negative electrode active material can be increased. Therefore, a lithium secondary battery having a higher energy density can be obtained in a limited battery capacity.
【００１６】なお、このエネルギー密度は、正極の充電
電位を高めるほど大きくなり、理論的には４.８Ｖまで
可能であるが、サイクル劣化の点から、本発明における
正極の最高電位の上限は、金属Ｌｉ基準で４.６Ｖ以下
がより望ましい。この正極電位の規定は、正極活物質で
あるＣｏ系酸化物の物性に基因するものであるから、電
池内の負極の種類によらず決められるものである。The energy density increases as the charge potential of the positive electrode increases, and can theoretically be up to 4.8 V. However, from the viewpoint of cycle deterioration, the upper limit of the maximum potential of the positive electrode in the present invention is: 4.6V or less is more desirable based on metal Li. Since the definition of the positive electrode potential is based on the physical properties of the Co-based oxide as the positive electrode active material, it is determined regardless of the type of the negative electrode in the battery.
【００１７】なお、前記の充電時における正極の最高電
位とは、通常二次電池を満充電状態とするのに必要な定
電圧充電もしくは定電流充電における電位が相当する。
しかし、充電中の電池の電圧は、充電器により制御され
るものであるから、本発明で規定するところの充電時に
おける正極の最高電位とは、充電器の充電設定電圧に基
づくものであってもよい。The maximum potential of the positive electrode during the charging corresponds to a potential in a constant voltage charge or a constant current charge that is necessary to bring the secondary battery into a fully charged state.
However, since the voltage of the battery during charging is controlled by the charger, the maximum potential of the positive electrode during charging as defined in the present invention is based on the charging set voltage of the charger. Is also good.
【００１８】[0018]
【発明の実施の形態】本発明におけるＣｏ系酸化物は、
Ｍｇ、Ａｌ、Ｍｎ、ＴｉおよびＳｒから選ばれる少なく
とも１種を含有するもので、充放電サイクルの進行によ
るＣｏ系酸化物の、相転移に伴う充放電の可逆性の劣化
を抑制する効果がある。BEST MODE FOR CARRYING OUT THE INVENTION The Co-based oxide in the present invention comprises:
It contains at least one selected from Mg, Al, Mn, Ti and Sr, and has an effect of suppressing deterioration of reversibility of charge / discharge due to phase transition of a Co-based oxide due to progress of a charge / discharge cycle. .
【００１９】これは、上記の添加元素がＣｏやＬｉと置
換もしくはＣｏ系酸化物の結晶構造中に固溶することに
より、菱面体晶ＬｉＣｏＯ2の理想的な層状結晶構造が
若干歪み、さらにこれらの添加元素が相転移の阻害点と
して作用することによるものと考えられる。添加する元
素の種類は必ずしも１種である必要はなく、複数種の元
素を添加してもよい。This is because the ideal layered crystal structure of rhombohedral LiCoO 2 is slightly distorted because the above-mentioned additive element is substituted with Co or Li or forms a solid solution in the crystal structure of a Co-based oxide. It is considered that this is because the added element of acts as an inhibition point of the phase transition. The kind of element to be added is not necessarily one kind, and a plurality of kinds of elements may be added.
【００２０】本発明における正極活物質であるＣｏ系酸
化物は、一般式、ＬｉxＣｏyＡzＯ2（但し、ＡはＭｇ、
Ａｌ、Ｍｎ、ＴｉおよびＳｒから選ばれる少なくとも１
種であり、ｘ、ｙ、ｚはそれぞれ０.９≦ｘ≦１.１、
０.９７≦ｙ≦１.００、０.０１≦ｚ≦０.０３）で表す
ことができる。The Co-based oxide as the positive electrode active material in the present invention is represented by the general formula: Li x Co y Az O 2 (where A is Mg,
At least one selected from Al, Mn, Ti and Sr
X, y, and z are respectively 0.9 ≦ x ≦ 1.1,
0.97 ≦ y ≦ 1.00, 0.01 ≦ z ≦ 0.03).
【００２１】ｘの値は、Ｃｏ系酸化物の作製段階におけ
る化学量論組成からのずれを示すもので、通常０.９≦
ｘ≦１.１の範囲のものがよい。The value of x indicates a deviation from the stoichiometric composition at the stage of preparing the Co-based oxide, and is usually 0.9 ≦≦
Those in the range of x ≦ 1.1 are preferred.
【００２２】ｙの値は、従来のＬｉＣｏＯ2ではｙ＝１
である。ｙの値は特に限定されないが、ｙ＝１に近いほ
ど高い放電容量が得られ、その望ましい値は０.９７≦
ｙ≦１.００である。The value of y is y = 1 in the conventional LiCoO 2.
It is. Although the value of y is not particularly limited, a higher discharge capacity is obtained as y = 1, and the desirable value is 0.97 ≦
y ≦ 1.00.
【００２３】またＡで示す添加元素は、必ずしも１種で
はなく、複数種の元素であってもよく、また、ｚの値は
０.０１≦ｚ≦０.０３が望ましい。これは０.０１≦ｚ
であると、Ｌｉイオンの挿入と放出の可逆性に対する添
加元素の効果がより十分に得られ、また、ｚ≦０.０３
であるとより高い放電容量が得られる。The additive element represented by A is not necessarily one kind, but may be a plurality of kinds of elements. The value of z is preferably 0.01 ≦ z ≦ 0.03. This is 0.01 ≦ z
In this case, the effect of the added element on the reversibility of insertion and release of Li ions is more sufficiently obtained, and z ≦ 0.03.
, A higher discharge capacity can be obtained.
【００２４】本発明において正極に用いる導電材は、非
晶質炭素もしくは少なくとも表層に非晶質炭素質を有し
主成分が炭素である導電材を用いる。これにより、高い
充電電位においても有機電解液の酸化分解を抑制するこ
とができる。In the present invention, as the conductive material used for the positive electrode, use is made of amorphous carbon or a conductive material having amorphous carbonaceous material at least in its surface layer and whose main component is carbon. This makes it possible to suppress oxidative decomposition of the organic electrolyte even at a high charging potential.
【００２５】導電材の構造としては、導電材全てが非晶
質炭素で形成されてもよいが、導電性の点から、電気伝
導率の高い黒鉛等の高結晶性の炭素材表面に、非晶質炭
素層を有することがより望ましい。特に、好ましい導電
材の形態としては、ラマンスペクトルにおいて、１５４
０ｃｍ~1〜１６００ｃｍ~1の範囲に存在するピークの半
値幅が１００ｃｍ~1以上のものであり、非晶質炭素質が
高結晶性の炭素材表面を十分に覆っているものである。As for the structure of the conductive material, the entire conductive material may be formed of amorphous carbon. However, from the viewpoint of conductivity, the surface of a highly crystalline carbon material such as graphite having a high electrical conductivity is formed on a non-crystalline surface. It is more desirable to have a crystalline carbon layer. In particular, a preferred form of the conductive material is 154 in the Raman spectrum.
0 cm ~ is 1 shall ～1600Cm ~ half width of peaks present in the first range of 100 cm ~ 1 or more, in which amorphous carbonaceous is adequately covered carbon material surface of high crystallinity.
【００２６】なお、本発明におけるラマンスペクトルの
ピークの半値幅は、図１に示すよう１８００ｃｍ~1と１
０００ｃｍ~1の信号強度を結ぶ直線をベースラインと
し、このベースラインを基準としたピーク高さの１／２
の点におけるピークの幅として規定される。It should be noted that the half-value width of the peak of the Raman spectrum in the present invention ranges from 1800 cm to 1 as shown in FIG.
A straight line connecting the signal intensities of 000 cm to 1 is defined as a baseline, and １ ／ of the peak height based on this baseline.
Is defined as the width of the peak at the point.
【００２７】本発明における表面に非晶質炭素質層を有
する炭素導電材の作製法としては、例えば、液状の樹
脂、ピッチやタール等に、人造黒鉛等の炭素材を浸漬後
焼成することで得られる。また気相法として、プロパン
やアセチレン等の炭化水素ガスを熱分解により炭素化
し、これを炭素材表面に堆積させることでも作製でき
る。The method for producing a carbon conductive material having an amorphous carbonaceous layer on its surface according to the present invention is, for example, a method in which a carbon material such as artificial graphite is immersed in a liquid resin, pitch or tar, and then fired. can get. Further, as a gas phase method, it can also be produced by carbonizing a hydrocarbon gas such as propane or acetylene by thermal decomposition and depositing it on the surface of a carbon material.
【００２８】さらに、本発明におけるリチウム二次電池
の特徴として、Ｍｇ、Ａｌ、Ｍｎ、ＴｉおよびＳｒから
選ばれる少なくとも１種を含有するＣｏ系酸化物を正極
活物質として使用し、かつ、少なくともその表層に非晶
質炭素質を有する炭素導電材を使用し、充電時における
正極の最高電位を金属Ｌｉ基準で４.４Ｖ〜４.８Ｖ、望
ましくは４.４Ｖ〜４.６Ｖとすることで、電池内の正極
活物質の初期放電容量が１６０ｍＡｈ／ｇ以上で、か
つ、規定の充放電を１０回繰り返した際の電池の容量維
持率８０％以上のものである。Further, as a feature of the lithium secondary battery of the present invention, a Co-based oxide containing at least one selected from Mg, Al, Mn, Ti and Sr is used as a positive electrode active material, and By using a carbon conductive material having amorphous carbonaceous material for the surface layer, and setting the maximum potential of the positive electrode during charging to 4.4 V to 4.8 V, preferably 4.4 V to 4.6 V, based on metal Li, The initial discharge capacity of the positive electrode active material in the battery is 160 mAh / g or more, and the capacity retention rate of the battery is 80% or more when specified charge / discharge is repeated 10 times.
【００２９】本発明の電池に用いる正極には、Ｃｏ系酸
化物と導電材をポリフッ化ビニリデンなどの結着剤を適
宜添加した合剤を基に作成される。例えば、アルミ箔な
どの集電材料を芯材とし成形体に仕上げたものが用いら
れる。The positive electrode used in the battery of the present invention is prepared based on a mixture obtained by appropriately adding a Co-based oxide and a conductive material to a binder such as polyvinylidene fluoride. For example, a molded product using a current collector material such as an aluminum foil as a core material and used as a core is used.
【００３０】また、本発明の電池に用いる負極として
は、炭素材料またはＬｉ挿入もしくは化合物の形成が可
能な材料を用いて、これに結着剤などを適宜添加した合
剤をもとに作成される。例えば、合剤を溶媒に分散さ
せ、銅箔などの集電材料に塗布乾燥後、成形体に仕上げ
たものを用いる。The negative electrode used in the battery of the present invention is made of a carbon material or a material capable of inserting Li or forming a compound, and is prepared based on a mixture obtained by appropriately adding a binder and the like thereto. You. For example, a mixture obtained by dispersing a mixture in a solvent, coating and drying a current collecting material such as a copper foil, and then forming a molded product is used.
【００３１】炭素材料は、例えば、天然黒鉛、人造黒
鉛、あるいは、重質油、コールタール、ピッチ系繊維な
どを加熱処理して炭化し、粉砕することによって得られ
る炭素材料を用いる。また、Ｌｉ挿入もしくは化合物の
形成が可能な材料としては、アルミニウムなどの金属、
シリコンなどを含む金属酸化物、および、炭素材料を含
めたこれらの材料の複合材が挙げられる。As the carbon material, for example, natural graphite, artificial graphite, or a carbon material obtained by heat-treating heavy oil, coal tar, pitch-based fiber, or the like, and carbonizing and pulverizing the material is used. Materials capable of forming Li or forming a compound include metals such as aluminum,
Examples include metal oxides containing silicon and the like, and composites of these materials including carbon materials.
【００３２】上記の正極と負極とを隔て、絶縁を目的と
するためにポリエチレン、ポリプロピレン等の有機高分
子材料で形成される多孔質フィルムや、ゲル状の有機高
分子化合物等を挟み込み、これに電池内に注液した有機
電解液を含浸する。For the purpose of insulation, a porous film formed of an organic polymer material such as polyethylene or polypropylene, a gel-like organic polymer compound, or the like is sandwiched between the positive electrode and the negative electrode. The organic electrolyte injected into the battery is impregnated.
【００３３】上記の有機電解液としては、従来と同様の
もの、例えばリチウム塩を有機溶媒に溶解して使用する
ことができる。該有機溶媒として、エチレンカーボネー
ト（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレ
ンカーボネート（ＢＣ）、ジメチルカーボネート（ＤＭ
Ｃ）、メチルエチルカーボネート（ＭＥＣ）、ジエチル
カーボネート（ＤＥＣ）などの炭酸エステル類や、γ―
ブチロラクトン（γ―ＢＬ）、酢酸メチル（ＥＡ）など
のエステル類、１,３−ジオキソラン、１,２−ジメトキ
シエタンなどのエーテル類が挙げられる。As the above-mentioned organic electrolyte, the same one as in the prior art, for example, a lithium salt dissolved in an organic solvent can be used. As the organic solvent, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DM
C), carbonates such as methyl ethyl carbonate (MEC) and diethyl carbonate (DEC), and γ-
Esters such as butyrolactone (γ-BL) and methyl acetate (EA); and ethers such as 1,3-dioxolan and 1,2-dimethoxyethane.
【００３４】その他に、スルホランなどの硫黄化合物、
含窒素化合物、含珪素化合物、含フッ素化合物、含リン
化合物などの有機溶媒が挙げられ、これらは単独あるい
は混合して用いることができる。In addition, sulfur compounds such as sulfolane,
Organic solvents such as a nitrogen-containing compound, a silicon-containing compound, a fluorine-containing compound, and a phosphorus-containing compound can be used, and these can be used alone or as a mixture.
【００３５】有機溶媒に溶解させるリチウム塩にはＬｉ
ＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＰＦ6、ＬｉＢＦ4、Ｌ
ｉＡｓＦ6などがあり、上記溶媒に０.１〜２モル／リッ
トル溶解させる。次に、本発明を実施例により具体的に
説明する。Lithium salts dissolved in organic solvents include Li
ClO 4 , LiCF 3 SO 3 , LiPF 6 , LiBF 4 , L
IAsF 6 include, be 0.1 to 2 mol / l dissolved in the solvent. Next, the present invention will be specifically described with reference to examples.
【００３６】〔実施例 １〕本発明の電池形態には、筒
型、ボタン型、コイン型、角型などの各種の形態がある
が、本実施例ではボタン型電池を例に説明する。[Embodiment 1] The battery form of the present invention includes various forms such as a tubular type, a button type, a coin type, and a square type. In this example, a button type battery will be described as an example.
【００３７】まず、ＥＣとＭＥＣの混合溶媒（ＥＣ／Ｍ
ＥＣ＝１／２）にＬｉＰＦ6を１.４モル／リットル相当
加えて、混合することにより有機電解液を調製した。First, a mixed solvent of EC and MEC (EC / M
EC = 1/2), and an organic electrolyte solution was prepared by adding LiPF 6 corresponding to 1.4 mol / liter and mixing.
【００３８】導電材として、平均粒径５μｍの内部が黒
鉛で表面に非晶質炭素質層を有する塊状の炭素材（Ａ）
を用いた。この導電材のラマンスペクトルを測定したと
ころ１５８５ｃｍ~1のピークの半値幅は１０４ｃｍ~1で
あった。As a conductive material, a massive carbon material (A) having an average particle size of 5 μm and having graphite inside and an amorphous carbonaceous layer on the surface (A)
Was used. FWHM of 1585 cm ~ 1 peak was measured Raman spectrum of the conductive material was 104cm ~ 1.
【００３９】次に、平均粒径７μｍのＡｌ添加Ｃｏ系酸
化物（ＬｉＣｏ0.97Ａｌ0.03Ｏ2）を正極活物質とし、
この活物質９１.５重量％に、導電材として炭素材
（Ａ）を４.５重量％加えて混合し、結着剤として予め
４重量％のポリフッ化ビニリデンをＮ−メチルピロリド
ンに溶解させた溶液に分散させてスラリーにした。Next, an Al-added Co-based oxide (LiCo 0.97 Al 0.03 O 2 ) having an average particle size of 7 μm was used as a positive electrode active material.
To 91.5% by weight of this active material, 4.5% by weight of a carbon material (A) was added as a conductive material and mixed, and 4% by weight of polyvinylidene fluoride was previously dissolved in N-methylpyrrolidone as a binder. The slurry was dispersed in the solution.
【００４０】この正極合剤スラリーを、正極集電体であ
るアルミニウム箔（厚さ２０μｍ）の片面に塗布量が２
４.０ｍｇ／ｃｍ2となるよう均一に塗布し、乾燥後ロー
ラープレス機により正極合剤密度が３.２ｇ／ｃｍ3にな
るよう圧縮成形し、所定の大きさに打ち抜き、円板状の
正極を作製した。The positive electrode mixture slurry was coated on one side of an aluminum foil (thickness: 20 μm) as a positive electrode current collector with a coating amount of 2 μm.
After coating uniformly to 4.0 mg / cm 2 , drying and compression molding with a roller press so that the density of the positive electrode mixture becomes 3.2 g / cm 3 , punching out to a predetermined size, and disc-shaped positive electrode Was prepared.
【００４１】これとは別に、平均粒径２０μｍの燐片状
黒鉛９２重量％を、結着剤として予め８重量部のポリフ
ッ化ビニリデンを、Ｎ−メチルピロリドンに溶解させた
溶液に分散させてスラリーにした。この負極合剤スラリ
ーを、負極集電体として銅箔（厚さ１５μｍ）の片面
に、塗布量が１６.５ｍｇ／ｃｍ2となるよう塗布し、乾
燥後ローラープレス機により負極合剤密度が１.５ｇ／
ｃｍ3となるよう圧縮成形し、所定の大きさに打ち抜
き、円板状の負極を作製した。Separately, a slurry was prepared by dispersing 92% by weight of flaky graphite having an average particle diameter of 20 μm in a solution in which 8 parts by weight of polyvinylidene fluoride was dissolved in N-methylpyrrolidone in advance as a binder. I made it. This negative electrode mixture slurry was applied to one surface of a copper foil (thickness: 15 μm) as a negative electrode current collector so as to have an application amount of 16.5 mg / cm 2. After drying, the negative electrode mixture density was 1% by a roller press. .5g /
It was compression-molded to a size of cm 3 and punched out into a predetermined size to produce a disk-shaped negative electrode.
【００４２】次に、上記の正極１，負極２，セパレータ
３の順に電池ケース５に収容した。なお、このセパレー
タは厚さ２５μｍで気孔率３８％の微多孔性ポリエチレ
ンフィルムを用いた。Next, the positive electrode 1, the negative electrode 2, and the separator 3 were accommodated in the battery case 5 in this order. The separator used was a microporous polyethylene film having a thickness of 25 μm and a porosity of 38%.
【００４３】また、電池ケース５の内面にはＡｌ箔シー
ト１４を配置してある。さらに、上記の有機電解液４を
注液し、ポリプロピレン製のパッキング７を介して封口
し、図２に示すボタン型のリチウム二次電池を作製し
た。An Al foil sheet 14 is arranged on the inner surface of the battery case 5. Further, the above-mentioned organic electrolytic solution 4 was injected and sealed via a polypropylene packing 7, thereby producing a button-type lithium secondary battery shown in FIG.
【００４４】図３は、上記正極１の断面をＳＥＭで観察
した場合の拡大模式断面図である。正極集電体８に、Ｃ
ｏ系酸化物９と、表面に非晶質炭素層１２を有する導電
材１０が、結着剤１３により固着されている。電池内に
注液した有機電解液はこれらの隙間に浸透する。FIG. 3 is an enlarged schematic cross-sectional view when the cross section of the positive electrode 1 is observed by SEM. C for the positive electrode current collector 8
An o-based oxide 9 and a conductive material 10 having an amorphous carbon layer 12 on the surface are fixed by a binder 13. The organic electrolyte injected into the battery penetrates these gaps.
【００４５】〔実施例 ２〕実施例１とはＡｌの添加量
が異なるＣｏ系酸化物（ＬｉＣｏ0.99Ａｌ0.01Ｏ2）を
正極活物質とした以外は、実施例１と同様にしてボタン
型のリチウム二次電池を作製した。Example 2 A button-type electrode was prepared in the same manner as in Example 1 except that a Co-based oxide (LiCo 0.99 Al 0.01 O 2 ) having a different amount of Al added was used as the positive electrode active material. A lithium secondary battery was manufactured.
【００４６】〔実施例 ３〜８〕正極活物質として、Ｍ
ｇ添加Ｃｏ系酸化物（ＬｉＣｏＭｇ0.03Ｏ2）、Ｍｎ添
加Ｃｏ系酸化物（ＬｉＣｏ0.97Ｍｎ0.03Ｏ2）、Ｓｒ添
加Ｃｏ系酸化物（ＬｉＣｏ0.99Ｓｒ0.01Ｏ2）、Ａｌと
Ｍｎ添加Ｃｏ系酸化物（ＬｉＣｏ0.97Ａｌ0.02Ｍｎ0.01
Ｏ2）、ＴｉとＭｇ添加Ｃｏ系酸化物（ＬｉＣｏ0.98Ｔ
ｉ0.02Ｍｇ0.01Ｏ2）、およびＡｌとＴｉとＭｎ添加Ｃ
ｏ系酸化物（ＬｉＣｏ0.97Ａｌ0.01Ｔｉ0.01Ｍｎ0.01Ｏ
2）を用い、実施例１と同様にして、それぞれボタン型
のリチウム二次電池を作製した。[Examples 3 to 8] As the positive electrode active material, M
g-added Co-based oxide (LiCoMg 0.03 O 2 ), Mn-added Co-based oxide (LiCo 0.97 Mn 0.03 O 2 ), Sr-added Co-based oxide (LiCo 0.99 Sr 0.01 O 2 ), Al and Mn-added Co-based oxide (LiCo 0.97 Al 0.02 Mn 0.01
O 2 ), Ti and Mg-added Co-based oxides (LiCo 0.98 T
i 0.02 Mg 0.01 O 2 ), and Al, Ti and Mn added C
o-based oxide (LiCo 0.97 Al 0.01 Ti 0.01 Mn 0.01 O
Using 2 ), button-type lithium secondary batteries were produced in the same manner as in Example 1.
【００４７】〔実施例 ９〕正極の塗布量が２５.５ｍ
ｇ／ｃｍ2、負極の塗布量が１５.７ｍｇ／ｃｍ2になる
ようにして、それぞれ電極を作製し、実施例１と同様に
してボタン型のリチウム二次電池を作製した。Example 9 The coating amount of the positive electrode was 25.5 m
g / cm 2 and the application amount of the negative electrode were 15.7 mg / cm 2 , respectively, to produce electrodes, and a button-type lithium secondary battery was produced in the same manner as in Example 1.
【００４８】〔実施例 １０〕正極の塗布量が２１.７
ｍｇ／ｃｍ2、負極の塗布量が１７.５ｍｇ／ｃｍ2にな
るようそれぞれ電極を作製し、実施例１と同様にしてボ
タン型のリチウム二次電池を作製した。Example 10 The coating amount of the positive electrode was 21.7.
mg / cm 2, the coating amount of the negative electrode to produce a respective electrode so as to be 17.5 mg / cm 2, to prepare a lithium secondary battery of the button type in the same manner as in Example 1.
【００４９】〔比較例 １〕導電材として、平均粒径５
μｍの内部が黒鉛で表面に非晶質炭素層を有する塊状の
炭素材（Ｂ）を用いた。この導電材のラマンスペクトル
を測定したところ１５８５ｃｍ~1のピークの半値幅は６
６ｃｍ~1であった。Comparative Example 1 As a conductive material, an average particle size of 5
A lump-shaped carbon material (B) having graphite inside and having an amorphous carbon layer on the surface was used. When the Raman spectrum of this conductive material was measured, the half-value width of the peak at 1585 cm- 1 was 6
It was 6 cm- 1 .
【００５０】平均粒径７μｍの従来型の元素無添加のＣ
ｏ系酸化物（ＬｉＣｏＯ2）を正極活物質とし、導電材
として炭素材（Ｂ）を用い、それ以外は実施例１と同様
にしてボタン型のリチウム二次電池を作製した。Conventional element-free C having an average particle size of 7 μm
A button-type lithium secondary battery was manufactured in the same manner as in Example 1 except that an o-based oxide (LiCoO 2 ) was used as a positive electrode active material and a carbon material (B) was used as a conductive material.
【００５１】〔比較例 ２〕正極の塗布量が２６.５ｍ
ｇ／ｃｍ2、負極の塗布量が１５.３ｍｇ／ｃｍ2になる
ようそれぞれ電極を作製し、比較例１と同様にしてボタ
ン型のリチウム二次電池を作製した。[Comparative Example 2] The coating amount of the positive electrode was 26.5 m.
g / cm 2 , and an application amount of the negative electrode of 15.3 mg / cm 2 , respectively, and an electrode was produced, and a button-type lithium secondary battery was produced in the same manner as in Comparative Example 1.
【００５２】前記実施例１〜８および比較例１のボタン
型のリチウム二次電池について、充電電流０.５ｍＡ、
正極電位が金属Ｌｉ基準で４.５Ｖまで充電し、４.５Ｖ
に達した後は４.５Ｖの定電圧で２時間保持し、放電は
０.５ｍＡで３.０Ｖまで放電するサイクルを繰り返す、
充放電試験を行った。The charge current of the button-type lithium secondary batteries of Examples 1 to 8 and Comparative Example 1 was 0.5 mA,
The positive electrode potential is charged up to 4.5 V based on metal Li, and 4.5 V
After that, the battery is held at a constant voltage of 4.5 V for 2 hours, and the discharge is repeated at a current of 0.5 mA until the voltage reaches 3.0 V.
A charge / discharge test was performed.
【００５３】前記実施例９のボタン型のリチウム二次電
池については、上記の充放電試験における充電正極電位
を金属Ｌｉ基準で４.４Ｖとした充放電試験を行った。The button-type lithium secondary battery of Example 9 was subjected to a charge / discharge test in which the charge positive electrode potential in the above charge / discharge test was 4.4 V based on metal Li.
【００５４】同様に前記実施例１０のボタン型のリチウ
ム二次電池については、充電正極電位を金属Ｌｉ基準で
４.６Ｖとした充放電試験を行った。Similarly, for the button-type lithium secondary battery of Example 10, a charge / discharge test was performed with the charge positive electrode potential set to 4.6 V based on metal Li.
【００５５】前記比較例２のボタン型のリチウム二次電
池については、上記の充放電試験における充電正極電位
を、従来のリチウム二次電池と同様の金属Ｌｉ基準で
４.３Ｖとした充放電試験を行った。With respect to the button-type lithium secondary battery of Comparative Example 2, the charge / discharge test in which the positive electrode potential in the above-described charge / discharge test was 4.3 V based on the same metal Li as the conventional lithium secondary battery was performed. Was done.
【００５６】以上の充放電試験における電池の初期容量
値と、正極活物質初期放電容量および１０サイクル後の
電池の容量維持率を表１に示す。Table 1 shows the initial capacity value of the battery in the above charge / discharge test, the initial discharge capacity of the positive electrode active material, and the capacity retention rate of the battery after 10 cycles.
【００５７】[0057]
【表１】 [Table 1]
【００５８】従来のリチウム二次電池の構成では、比較
例１に示すよう充電電位を４.５Ｖとすることで、正極
活物質の初期放電容量は高いものの、容量維持率が低く
サイクル特性が劣る。さらに比較例２に示すよう、サイ
クル特性を維持するためには、充電電位を４.３Ｖと
し、正極活物質の初期放電容量を低く押さえなければな
らない。In the structure of the conventional lithium secondary battery, as shown in Comparative Example 1, by setting the charging potential to 4.5 V, the initial discharge capacity of the positive electrode active material is high, but the capacity retention ratio is low and the cycle characteristics are inferior. . Furthermore, as shown in Comparative Example 2, in order to maintain the cycle characteristics, the charging potential must be 4.3 V and the initial discharge capacity of the positive electrode active material must be kept low.
【００５９】これに対し、実施例１〜１０においては、
正極活物質の初期放電容量１６０ｍＡｈ／ｇ以上で電池
の放電容量が高く、かつ、容量維持率が８０％以上とサ
イクル特性にも優れることが分かる。On the other hand, in Examples 1 to 10,
It can be seen that the discharge capacity of the battery is high when the initial discharge capacity of the positive electrode active material is 160 mAh / g or more, and that the capacity retention rate is 80% or more and the cycle characteristics are also excellent.
【００６０】[0060]
【発明の効果】本発明によれば、正極にＭｇ、Ａｌ、Ｍ
ｎ、ＴｉおよびＳｒから選ばれる少なくとも１種を含有
するＣｏ系酸化物を活物質として用い、かつ、少なくと
も表層に非晶質炭素質を有する炭素導電材を用いること
で、エネルギー密度が高く、かつ、サイクル特性に優れ
たリチウム二次電池を提供することができる。According to the present invention, Mg, Al, M
By using a Co-based oxide containing at least one selected from n, Ti, and Sr as an active material and using a carbon conductive material having amorphous carbonaceous material at least in a surface layer, the energy density is high, and Thus, a lithium secondary battery having excellent cycle characteristics can be provided.
【図１】表層が非晶質炭素である炭素材のラマンスペク
トルのグラフである。FIG. 1 is a graph of a Raman spectrum of a carbon material whose surface layer is amorphous carbon.
【図２】本発明のリチウム二次電池の構成の一例を示す
ボタン型リチウム二次電池の縦断面図である。FIG. 2 is a longitudinal sectional view of a button-type lithium secondary battery showing an example of the configuration of the lithium secondary battery of the present invention.
【図３】本発明のリチウム二次電池の構成の一例を示す
正極の断面の拡大模式図である。FIG. 3 is an enlarged schematic diagram of a cross section of a positive electrode showing an example of a configuration of a lithium secondary battery of the present invention.
１…正極、２…負極、３…セパレータ、４…有機電解
液、５…電池ケース、６…封口板、７…パッキング、８
…正極集電体、９…Ｃｏ系酸化物、１０…導電材、１１
…黒鉛、１２…非晶質炭素層、１３…結着剤、１４…Ａ
ｌ箔シート。DESCRIPTION OF SYMBOLS 1 ... Positive electrode, 2 ... Negative electrode, 3 ... Separator, 4 ... Organic electrolyte, 5 ... Battery case, 6 ... Sealing plate, 7 ... Packing, 8
... Positive electrode current collector, 9 ... Co-based oxide, 10 ... Conductive material, 11
... graphite, 12 ... amorphous carbon layer, 13 ... binder, 14 ... A
l foil sheet.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 本棒 英利 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 喜多 房次 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 (72)発明者 伊津 哲夫 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 Ｆターム(参考） 5H003 AA02 AA04 BB05 BC01 BC06 BD00 BD03 5H014 AA01 EE10 HH00 HH01 HH04 5H029 AJ03 AJ05 AK03 AL06 AL07 AM03 AM05 AM07 BJ03 DJ16 DJ17 HJ02 HJ13 HJ19 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Eritoshi Honbo 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd. 1-88 Inside Hitachi Maxell Co., Ltd. (72) Inventor Tetsuo Itsu 1-88 Ushitora, Ibaraki-shi, Osaka F-term inside Hitachi Maxell Co., Ltd. 5H003 AA02 AA04 BB05 BC01 BC06 BD00 BD03 5H014 AA01 EE10 HH00 HH01 HH04 5H029 AJ03 AJ05 AK03 AL06 AL07 AM03 AM05 AM07 BJ03 DJ16 DJ17 HJ02 HJ13 HJ19
Claims (4)
するＣｏ系酸化物と、主成分が炭素である導電材とを含
む正極と、負極と、有機電解液を有するリチウム二次電
池において、前記Ｃｏ系酸化物がＭｇ、Ａｌ、Ｍｎ、Ｔ
ｉおよびＳｒから選ばれる少なくとも１種を含有し、か
つ、前記導電材の少なくともその表層に非晶質炭素質を
有することを特徴とするリチウム二次電池。1. A lithium secondary battery comprising: a positive electrode including a Co-based oxide containing Li and Co as a positive electrode active material; a conductive material whose main component is carbon; a negative electrode; and an organic electrolyte. Co-based oxide is Mg, Al, Mn, T
A lithium secondary battery comprising at least one selected from i and Sr, and having an amorphous carbonaceous material in at least a surface layer of the conductive material.
ＡzＯ2（但し、ＡはＭｇ、Ａｌ、Ｍｎ、ＴｉおよびＳｒ
から選ばれる少なくとも１種で、ｘ、ｙ、ｚはそれぞれ
０.９≦ｘ≦１.１、０.９７≦ｙ≦１.００、０.０１≦
ｚ≦０.０３）で示されることを特徴とする請求項１に
記載のリチウム二次電池。2. The Co-based oxide has a general formula: Li x Co y
A z O 2 (where A is Mg, Al, Mn, Ti and Sr
Wherein x, y and z are 0.9 ≦ x ≦ 1.1, 0.97 ≦ y ≦ 1.00 and 0.01 ≦, respectively.
2. The lithium secondary battery according to claim 1, wherein z ≦ 0.03). 3.
る１５４０ｃｍ~1〜１６００ｃｍ~1の範囲に存在するピ
ークの半値幅が１００ｃｍ~1以上である請求項１または
２に記載のリチウム二次電池。Wherein said conductive material is a lithium secondary battery according to claim 1 or 2 half-width of the peaks present in the range of 1540cm ~ 1 ~1600cm ~ 1 in the Raman spectrum is 100 cm ~ 1 or more.
ｇ以上で、かつ、充放電を１０回繰り返した際の容量保
持率が８０％以上である請求項１〜３のいずれかに記載
のリチウム二次電池。4. The discharge capacity of the positive electrode active material is 160 mAh /
The lithium secondary battery according to any one of claims 1 to 3, wherein the capacity retention rate is 80% or more when charging and discharging are repeated 10 times or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34978299A JP2001167763A (en) | 1999-12-09 | 1999-12-09 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34978299A JP2001167763A (en) | 1999-12-09 | 1999-12-09 | Lithium secondary battery |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006018522A Division JP2006173137A (en) | 2006-01-27 | 2006-01-27 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001167763A true JP2001167763A (en) | 2001-06-22 |
| JP2001167763A5 JP2001167763A5 (en) | 2006-03-16 |
Family
ID=18406086
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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