JPH10308218A - Positive electrode active material for lithium ion secondary battery, and manufacture thereof - Google Patents
Positive electrode active material for lithium ion secondary battery, and manufacture thereofInfo
- Publication number
- JPH10308218A JPH10308218A JP9074907A JP7490797A JPH10308218A JP H10308218 A JPH10308218 A JP H10308218A JP 9074907 A JP9074907 A JP 9074907A JP 7490797 A JP7490797 A JP 7490797A JP H10308218 A JPH10308218 A JP H10308218A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- electrode active
- particles
- lithium ion
- 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]
【産業上の利用分野】本発明は、二次電池の正極活物質
に係り、特に、サイクル特性、及び熱安定性を向上でき
る非水系のリチウムイオン二次電池用正極活物質及びそ
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive electrode active material for a secondary battery, and more particularly to a positive electrode active material for a non-aqueous lithium ion secondary battery capable of improving cycle characteristics and thermal stability, and a method for producing the same. .
【０００２】[0002]
【従来の技術】近年、カメラ一体形ＶＴＲ、オーディオ
・ビデオ機器、ノート型パソコン、携帯電話などの新し
いコードレス型電子機器が次々と出現し、短期間で急速
に広く普及した。これら機器の小型・軽量化には、携帯
用電源である二次電池の高性能化は不可欠である。2. Description of the Related Art In recent years, new cordless electronic devices such as a camera-integrated VTR, an audio / video device, a notebook personal computer, and a mobile phone have appeared one after another, and have rapidly spread widely in a short time. In order to reduce the size and weight of these devices, it is essential to improve the performance of secondary batteries as portable power supplies.
【０００３】非水系リチウムイオン二次電池は、電池電
圧が高く、高放電容量、及びサイクル特性などに優れ、
このような用途に合致し最近盛んに研究されている。A non-aqueous lithium ion secondary battery has a high battery voltage, a high discharge capacity, and excellent cycle characteristics.
Recently, it has been actively studied to meet such applications.
【０００４】この電池の正極活物質にはコバルト酸リチ
ウム（ＬｉＣｏＯ2）を代表とするＬｉの重金属酸塩Ｌ
ｉＭＯ2（Ｍ＝Ｃｏ、Ｎｉ、Ｆｅ、Ｍｎ、Ｃｒ等）が使
用されている。The positive electrode active material of this battery is Li heavy metal salt L typified by lithium cobalt oxide (LiCoO 2).
iMO2 (M = Co, Ni, Fe, Mn, Cr, etc.) is used.
【０００５】従来、ＬｉＭＯ2を正極活物質に用いた非
水系二次電池では、充放電サイクルを繰り返し行うこと
により、その電池放電容量が徐々に減少するというサイ
クル特性の劣化の問題があった。この原因は、ＬｉＭＯ
2の結晶が崩れることによると考えられていた。特に、
充放電を繰り返すことにより、正極活物質を構成する微
小粒子のｃ軸方向への膨張、収縮が起こり、多結晶体等
の場合は結晶子の界面が多いので、そこから結晶が崩
れ、正極の集電体からの正極活物質の剥離が起こること
がサイクル特性を劣化する原因とされていた。これに対
し、サイクル特性の改善のために、結晶を単結晶化さ
せ、かつｃ軸に垂直な方向（（００３）面）に配向する
扁平粒子を成長させる方法が特開平９−２２６９３号公
報に提案されている。Conventionally, a non-aqueous secondary battery using LiMO2 as a positive electrode active material has had a problem of deterioration in cycle characteristics such that the battery discharge capacity is gradually reduced by repeatedly performing charge and discharge cycles. This is because LiMO
It was thought that the crystal of 2 collapsed. Especially,
By repeating charging and discharging, expansion and contraction of the fine particles constituting the positive electrode active material in the c-axis direction occur, and in the case of a polycrystal or the like, since there are many interfaces of crystallites, crystals collapse from there, and It has been considered that peeling of the positive electrode active material from the current collector causes deterioration of cycle characteristics. On the other hand, Japanese Unexamined Patent Publication No. 9-22693 discloses a method of improving the cycle characteristics by monocrystallizing a crystal and growing flat particles oriented in a direction perpendicular to the c-axis ((003) plane). Proposed.
【０００６】また、正極活物質のＬｉＣｏＯ2のＸ線回
折線の（００３）面と（１０４）面のピーク強度比を特
定の範囲に限定することにより、サイクル特性は向上す
ることが特開平５−２５８７５１号公報、特開平９−２
２６９２号公報、特開平９−２２６９３号公報、及び特
開平８−５５６２４号公報に記載されている。In addition, it is disclosed in Japanese Patent Application Laid-Open No. H05-205580 that by limiting the peak intensity ratio between the (003) plane and the (104) plane of the X-ray diffraction line of LiCoO2 as a positive electrode active material to a specific range. JP-A-2585751, JP-A-9-2
No. 2692, JP-A-9-22693, and JP-A-8-55624.
【０００７】さらに、リチウムイオン二次電池の正極活
物質は、高温空気中では安定であるが、充電状態におか
れることにより熱安定性が低下し、二次電池の電解液を
構成する有機溶媒を酸化分解し、場合によっては発火を
引き起こすという重大な問題が潜在している。Further, the positive electrode active material of a lithium ion secondary battery is stable in high-temperature air, but its thermal stability is reduced by being charged, and the organic solvent constituting the electrolyte of the secondary battery is poor. The potential problem is that it oxidatively decomposes and, in some cases, ignites.
【０００８】これまで、リチウムイオン二次電池用正極
活物質の特性については、充放電のサイクル特性を向上
するための研究が数々なされてきたが、充電時の熱安定
性についてはあまり触れられることはなかった。それは
充電時の熱安定性を改良すれば、充放電のサイクル特性
は低下するという相反する関係にあるとの見解が常識で
あったからである。[0008] A number of studies have been made on the characteristics of the positive electrode active material for lithium ion secondary batteries in order to improve the charge / discharge cycle characteristics. However, the thermal stability during charging has not been mentioned much. There was no. This is because it was common knowledge that if the thermal stability at the time of charging was improved, the charge-discharge cycle characteristics would be reduced.
【０００９】[0009]
【発明が解決しようとする課題】本発明は上述した事情
に鑑みなされ、リチウムイオン二次電池の充電時の熱安
定性を改善し、さらに良好な充放電サイクル特性を両立
する正極活物質を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and provides a positive electrode active material that improves the thermal stability during charging of a lithium ion secondary battery and achieves good charge / discharge cycle characteristics. The purpose is to do.
【００１０】[0010]
【課題を解決するための手段】本発明者は正極活物質の
粒子形状及び構造について鋭意検討したところ、正極活
物質は、結晶子と呼ばれる微小な単結晶が集合した粒子
からなり、この結晶子及び一次粒子の大きさ或いは形状
がリチウムイオン電池の熱安定性及び充放電サイクル特
性に密接に関係することを見出し本発明を完成させるに
至った。Means for Solving the Problems The present inventors have made intensive studies on the particle shape and structure of the positive electrode active material, and found that the positive electrode active material is composed of particles in which fine single crystals called crystallites are aggregated. The inventors have found that the size or shape of the primary particles is closely related to the thermal stability and charge / discharge cycle characteristics of the lithium ion battery, and have completed the present invention.
【００１１】すなわち、本発明のリチウムイオン二次電
池用正極活物質は、一般式ＬｉＭＯ2で表現されるリチ
ウムイオン二次電池用正極活物質であって、その粒子構
造は、微小な結晶子を単位とする単結晶が集合した粒子
からなり、該結晶子及び該粒子の形状は立体的にほぼ等
方的形状であることを特徴とする。（但しＭはＣｏ、Ｎ
ｉ、Ｆｅ、Ｍｎ、Ｃｒの群から選ばれる少なくとも一種
の重金属元素）That is, the positive electrode active material for a lithium ion secondary battery of the present invention is a positive electrode active material for a lithium ion secondary battery represented by the general formula LiMO 2, and the particle structure of the positive electrode active material is small crystallites. And the shape of the crystallites and the particles is three-dimensionally substantially isotropic. (However, M is Co, N
i, at least one heavy metal element selected from the group consisting of Fe, Mn, and Cr)
【００１２】結晶子とは、単結晶と考えられる最大限の
集合を示し、ＸＲＤ（Ｘ−ｒａｙｄｉｆｆｒａｃｔｉｏ
ｎ）測定より、次のシェラーの式を用いることにより計
算できる。 ＜シェラーの式＞ 結晶子の大きさＤ(オングストローム)＝Ｋλ／（βｓｉ
ｎθ） Ｋ：シェラー定数 （βを積分幅より算出した場合Ｋ＝
１．０５） λ：使用Ｘ線管球の波長（ＣｕＫα１＝１．５４０５６
２オングストローム β：結晶子の大きさによる回折線の広がりの幅（ｒａｄ
ｉａｎ） θ：回折角２θ／２（ｄｅｇｒｅｅ）The term “crystallite” refers to the maximum set considered to be a single crystal, and is referred to as XRD (X-ray diffraction).
n) From the measurement, it can be calculated by using the following Scherrer equation. <Scherrer's formula> Crystallite size D (angstrom) = Kλ / (βsi
nθ) K: Scherrer's constant (when β is calculated from the integral width, K =
1.05) λ: wavelength of the used X-ray tube (CuKα1 = 1.40556)
2 angstrom β: width of spread of diffraction line due to crystallite size (rad)
ian) θ: diffraction angle 2θ / 2 (degree)
【００１３】ここでいう粒子とはＳＥＭで結像する最小
の粒子を指し、粒子が１つの単結晶で構成されている場
合は結晶子径と粒子径は同じ大きさである。一つの粒子
に複数の単結晶を包含する場合、当然その大きさは一致
しない。The term “particle” as used herein refers to the smallest particle that can be imaged by SEM. When the particle is formed of one single crystal, the crystallite diameter and the particle diameter are the same. When a single particle includes a plurality of single crystals, the sizes do not naturally match.
【００１４】立体的にほぼ等方的形状とは、粒子に配向
性がなく、空間の全ての方向に等方的に成長した形状を
いい、典型的には球状であるが、必ずしも真球に限定す
るものではなく、ほぼ球状であるものも含む。通常の結
晶性のある物質はその結晶構造を反映したような粒子形
状を有する。これに対し、本発明において有用な正極活
物質はそのような配向性を有しない特別な形状であると
いうことができる。The three-dimensionally isotropic shape refers to a shape in which the particles have no orientation and grow isotropically in all directions of the space, and are typically spherical, but not necessarily spherical. The present invention is not limited thereto, and includes those having a substantially spherical shape. An ordinary crystalline substance has a particle shape that reflects its crystal structure. On the other hand, it can be said that the positive electrode active material useful in the present invention has a special shape having no such orientation.
【００１５】該正極活物質の一次粒子を構成する結晶子
の立体形状を、層を重ねる方向（（００３）ベクトル方
向）、及びそれに垂直な方向（（１１０）ベクトル方
向）で表現する場合、（１１０）ベクトル方向の結晶子
径に対する（００３）方向の結晶子径の比率は、０．５
〜１．６の範囲であることが好ましい。層を重ねる方向
とは、正極活物質のＬｉＭＯ2の基本格子は六方晶系で
あり、ｃ軸方向を指す。従って、それに垂直な方向とは
ａ軸方向を指す。In the case where the three-dimensional shape of crystallites constituting the primary particles of the positive electrode active material is expressed by a direction in which layers are superposed ((003) vector direction) and a direction perpendicular thereto ((110) vector direction), 110) The ratio of the crystallite diameter in the (003) direction to the crystallite diameter in the vector direction is 0.5
It is preferably in the range of 1.6. The direction in which the layers are stacked indicates that the basic lattice of LiMO2 as the positive electrode active material is hexagonal, and points in the c-axis direction. Therefore, the direction perpendicular to the direction refers to the a-axis direction.
【００１６】該正極活物質の結晶子の（００３）ベクト
ル方向の結晶子径は５００〜７５０オングストロームの
範囲であることが好ましい。The crystallite diameter of the crystallite of the positive electrode active material in the (003) vector direction is preferably in the range of 500 to 750 angstroms.
【００１７】該正極活物質の結晶子の（１１０）ベクト
ル方向の結晶子径は４５０〜１０００オングストローム
の範囲であることが好ましい。The crystallite diameter of the crystallite of the positive electrode active material in the (110) vector direction is preferably in the range of 450 to 1000 Å.
【００１８】正極活物質の平均粒径は、空気透過法によ
り比表面積を測定し、一次粒子の粒径の平均値を求めた
ものであり、具体的にはフィッシャーサブシーブサイザ
ー（Ｆ．Ｓ．Ｓ．Ｓ．）を用いて測定した値である。The average particle diameter of the positive electrode active material is obtained by measuring the specific surface area by an air permeation method and calculating the average value of the particle diameters of the primary particles. Specifically, the average particle diameter is determined by a Fischer subsieve sizer (FS. SS).
【００１９】ＳＥＭ観察による該粒子の長軸粒子径に対
する短軸粒子径の比率は０．５〜１．０の範囲であるこ
とが好ましい。次のようにして該比率を計算する。図１
に示すように、ＳＥＭ写真からランダムに２０個抽出し
た粒子像の個々の中心を求め、中心を通る最長径を決定
し、これを長軸粒子径と定義する。次に中心を通り長軸
に垂直な方向の径を短軸粒子径として定義する。得られ
た個々の粒子の短軸粒子径／長軸粒子径の比率の平均を
算出する。The ratio of the minor axis particle diameter to the major axis particle diameter of the particles by SEM observation is preferably in the range of 0.5 to 1.0. The ratio is calculated as follows. FIG.
As shown in (1), the center of each of 20 randomly extracted particle images is determined from the SEM photograph, the longest diameter passing through the center is determined, and this is defined as the long-axis particle diameter. Next, the diameter in the direction perpendicular to the major axis passing through the center is defined as the minor axis particle diameter. The average of the ratio of the minor axis particle diameter / major axis particle diameter of each of the obtained particles is calculated.
【００２０】本発明のリチウムイオン二次電池用正極活
物質の製造方法は、原料の重金属酸化物とリチウム塩を
Ｌｉ／Ｍ比が０．９８〜１．０１の範囲となるように混
合して焼成する正極活物質の製造方法において、重金属
酸化物の粒子形状は、立体的にほぼ等方的形状を有する
一次粒子又は一次粒子が集合した二次粒子からなり、そ
の中心粒径は０．１〜１０μｍであることを特徴とす
る。（但しＭはＣｏ、Ｎｉ、Ｆｅ、Ｍｎ、Ｃｒの群から
選ばれる少なくとも一種の重金属元素）In the method for producing a positive electrode active material for a lithium ion secondary battery according to the present invention, the raw metal oxide and the lithium salt are mixed so that the Li / M ratio is in the range of 0.98 to 1.01. In the method for producing a positive electrode active material to be fired, the particle shape of the heavy metal oxide is composed of primary particles having a substantially three-dimensionally isotropic shape or secondary particles in which the primary particles are aggregated, and the central particle size is 0.1%. -10 μm. (Where M is at least one heavy metal element selected from the group consisting of Co, Ni, Fe, Mn, and Cr)
【００２１】原料の重金属酸化物の中心粒径は、電気抵
抗法の粒度分布測定装置を用いて測定される値であり、
ここではＣｏｕｌｔｅｒ Ｍｕｌｔｉｓｉｚｅｒ２を用
いて測定した中心粒径である。これは測定原理から分散
状態にあるか凝集状態にあるかの知見を含んだ粒径とい
うことができる。The center particle diameter of the raw material heavy metal oxide is a value measured by using a particle size distribution measuring device of an electric resistance method.
Here, it is the central particle diameter measured using Coulter Multisizer 2. This can be said to be a particle size that includes a knowledge of whether it is in a dispersed state or an aggregated state from the measurement principle.
【００２２】[0022]
＜粒子形状＞本発明に於いて、正極活物質の粒子内の結
晶子の成長度が、電池特性に影響を及ぼすこと、また特
定のベクトル方向への成長度が、個々の特性と相関があ
ることを見いだした。リチウムイオン二次電池の正極活
物質であるＬｉＭＯ2は本来層状構造を有している。本
発明の正極活物質の結晶子の粒子形状は図２（ａ）に示
すように空間に等方的に成長しており、（ｂ）比較例の
ようなｃ軸配向のないものである。そのことをシェラー
の式による結晶子径を用いて表現すると、（００３）ベ
クトル方向に５００〜７５０オングストロームの範囲、
（１１０）ベクトル方向に４５０〜１０００オングスト
ロームの範囲、（１０５）ベクトル方向に５００〜９０
０オングストロームの範囲、（１１３）ベクトル方向に
４５０〜１０００オングストロームの範囲にあるという
ことができる。<Particle Shape> In the present invention, the degree of growth of crystallites in the particles of the positive electrode active material affects battery characteristics, and the degree of growth in a specific vector direction has a correlation with individual characteristics. I found something. LiMO2, which is a positive electrode active material of a lithium ion secondary battery, originally has a layered structure. The crystal shape of the crystallite of the positive electrode active material of the present invention grows isotropically in the space as shown in FIG. 2A, and does not have c-axis orientation as in the comparative example. If this is expressed using the crystallite diameter according to Scherrer's formula, the range of 500 to 750 angstroms in the (003) vector direction,
(110) Range of 450-1000 Angstroms in vector direction, (105) 500-90 in vector direction
It can be said that it is in the range of 0 angstroms and in the range of 450 to 1000 angstroms in the (113) vector direction.
【００２３】本発明において、（１０５）、（１１３）
ベクトル方向についても言及したが、これは、結晶が三
次元的に成長しているか否かを表現するための手段であ
り、層に平行、垂直でないような面であれば（１０４）
や（１０８）ベクトル方向の様な他の面方向をとって表
現してもかまわない。但し、これらの結晶子も大きすぎ
ると、Ｌｉイオンの拡散を阻害し、小さすぎると結晶の
崩れの原因となると考えられる。In the present invention, (105), (113)
Although the vector direction was also mentioned, this is a means for expressing whether or not the crystal is growing three-dimensionally. If the plane is not parallel or perpendicular to the layer (104)
Alternatively, other plane directions such as the (108) vector direction may be used. However, it is considered that if these crystallites are too large, the diffusion of Li ions is hindered, and if they are too small, they cause crystal collapse.
【００２４】＜重金属酸化物原料＞本発明のリチウムイ
オン二次電池用正極活物質は、上述したような粒子形状
に特徴がある。このような粒子構造とするためには、原
料として二次粒子が球状であり、一次粒子の結晶子径の
小さな重金属酸化物原料を選択する。正極活物質の粒子
形状は、原料の粒子形状をそのまま引き継ぎやすい。例
えば、重金属原料の二次粒子の形状が八面体構造である
場合、得られるＬｉＭＯ2の結晶子及び粒子は八面体構
造となりやすく、また、重金属酸化物の形状が球状の場
合、得られるＬｉＭＯ2の結晶子及び粒子は球状構造と
なりやすい。さらに、二次粒子の形状が六角板状構造の
場合、得られるＬｉＭＯ2の結晶子及び粒子は六角板状
構造となりやすい。本発明は、六角板状の構造は除外さ
れる。特に、重金属元素ＭがＣｏであるＣｏ3Ｏ4の場合
は、（２２２）ベクトル方向の結晶子のサイズが１００
〜４００オングストロームの範囲であることが好まし
い。<Material for Heavy Metal Oxide> The positive electrode active material for a lithium ion secondary battery of the present invention is characterized by the particle shape as described above. In order to obtain such a particle structure, a heavy metal oxide raw material whose secondary particles are spherical and whose primary particles have a small crystallite diameter is selected as a raw material. As for the particle shape of the positive electrode active material, it is easy to take over the particle shape of the raw material as it is. For example, when the shape of the secondary particles of the heavy metal raw material is an octahedral structure, the obtained LiMO2 crystallites and particles are likely to have an octahedral structure, and when the shape of the heavy metal oxide is spherical, the obtained LiMO2 crystal Particles and particles tend to have a spherical structure. Further, when the secondary particles have a hexagonal plate-like structure, the obtained LiMO2 crystallites and particles tend to have a hexagonal plate-like structure. The present invention excludes a hexagonal plate-like structure. In particular, when the heavy metal element M is Co 3 O 4 where Co is Co, the crystallite size in the (222) vector direction is 100.
Preferably, it is in the range of ４００400 Å.
【００２５】重金属酸化物は一次粒子の粒径が０．０１
〜０．５μｍのほぼ球状の形状であり、二次粒子の粒径
は０．１〜１０．０μｍの範囲が好ましい。例えば、Ｍ
がＣｏである場合、炭酸コバルトＣｏＣＯ3であって、
短軸粒子径／長軸粒子径の比率が０．５〜１．０の範囲
である粒子を熱分解することで得ることができる。The heavy metal oxide has a primary particle size of 0.01
The diameter of the secondary particles is preferably in the range of 0.1 to 10.0 μm. For example, M
Is Co, cobalt carbonate CoCO3,
It can be obtained by thermally decomposing particles having a ratio of short axis particle diameter / long axis particle diameter in the range of 0.5 to 1.0.
【００２６】重金属元素酸化物の二次粒子の短軸粒子径
／長軸粒子径の比率、重金属酸化物の二次粒子の中心粒
径を上記した範囲に選択するのは、それは前述したよう
に、Ｍ3Ｏ4の粒子構造がそのままＬｉＭＯ2の粒子構造
に反映されるため、この原料粒子のパラメータの限定は
非常に重要となるからである。The reason for selecting the ratio of the short axis particle diameter to the long axis particle diameter of the secondary particles of the heavy metal element oxide and the center particle diameter of the secondary particles of the heavy metal oxide in the above ranges is as described above. This is because the particle structure of M3O4 is directly reflected on the particle structure of LiMO2, so that the limitation of the parameters of the raw material particles is very important.
【００２７】＜リチウム原料＞本発明においてリチウム
二次電池に使用する原料のＬｉ塩としては、種々検討し
た結果、融点が比較的高いＬｉ2ＣＯ3、Ｌｉ2（ＣＯ
Ｏ）2又はＬｉＯＨが好ましく使用できる。<Lithium raw material> As a result of various studies, as a raw material Li salt used in the lithium secondary battery in the present invention, Li2CO3 and Li2 (CO2
O) 2 or LiOH can be preferably used.
【００２８】＜重金属原料とリチウムの混合＞本発明に
おいて、Ｍ3Ｏ4とリチウム塩をＬｉ／Ｍ比が０．９８〜
１．０１の範囲となるように混合する。それはＬｉ／Ｍ
比がこの範囲から逸脱すると、過剰分が融剤として作用
することで粒子が異常成長し、粒子径及び粒子形状を制
御困難となるからである。<Mixing of Heavy Metal Raw Material and Lithium> In the present invention, M3O4 and a lithium salt are mixed with a Li / M ratio of 0.98 to 0.98.
Mix so as to be in the range of 1.01. It is Li / M
If the ratio deviates from this range, the excess acts as a flux, causing abnormal growth of the particles, making it difficult to control the particle diameter and particle shape.
【００２９】＜焼成＞得られた混合原料を大気雰囲気下
で、７５０〜１１００℃で焼成する。融剤として、アル
カリ金属塩類や、Ｂさらには、Ｂｉ、Ｐｂ等を加える場
合、もしくは、造粒する場合は、（１１０）ベクトル方
向の成長を促進しやすくなり、サイクル特性を低下する
ので（１１０）ベクトル方向の成長を制御する必要があ
る。<Firing> The obtained mixed raw material is fired at 750 to 1100 ° C. in an air atmosphere. When an alkali metal salt, B, Bi, Pb, or the like is added as a flux, or when granulation is performed, the growth in the (110) vector direction is easily promoted, and the cycle characteristics are reduced. ) It is necessary to control the growth in the vector direction.
【００３０】[0030]
【作用】リチウムイオン二次電池の正極活物質は、充電
することによりＬｉが結晶中から脱離し、ＬｉｘＭＯ2
（ｘ＜１．０）の状態に変化し、六方晶系であるＬｉＭ
Ｏ2が単斜晶系へと転移する。この転移により結晶が崩
れることが正極活物質の充電時の熱安定性の最も大きな
低下要因である。これは次のようなメカニズムにより熱
安定性が低下する。The positive electrode active material of the lithium ion secondary battery is charged with Li, which is desorbed from the crystal, and LixMO2
(X <1.0), and the hexagonal LiM
O2 is transformed into a monoclinic system. Distortion of the crystal due to this transition is the largest cause of the decrease in thermal stability during charging of the positive electrode active material. This lowers the thermal stability by the following mechanism.
【００３１】充電時に結晶が崩れると正極活物質から酸
素が遊離する。正極活物質はＥＣ（エチレンカーボネー
ト）等の電解液に接触した状態で電池を構成している
が、この遊離酸素が電解液を酸化分解することによって
酸化反応が起こり、発熱し、場合によっては発火に至る
という重大な問題に発展する可能性がある。When the crystal collapses during charging, oxygen is released from the positive electrode active material. The positive electrode active material constitutes the battery in a state of being in contact with an electrolytic solution such as EC (ethylene carbonate). The free oxygen oxidizes and decomposes the electrolytic solution to cause an oxidation reaction, thereby generating heat and, in some cases, igniting. Could lead to serious problems.
【００３２】＜熱安定性＞本発明において熱安定性が改
善されるのは次のような理由による。本発明の正極物質
のＬｉＭＯ2は、基本的に結晶子の形状が空間に等方的
に成長した球状であり、しかも結晶子径を大きくしてい
る。結晶子の形状を球形の等方的構造とすることで、充
放電に伴うＬｉの移動による結晶の歪みの方向が全ての
空間方向に均等となるため、一定方向に配向した従来の
結晶構造に比べ、崩れを最小に抑えることが可能とな
る。また、結晶子を大きくすることによりＬｉイオンの
脱離時に生じる結晶構造の崩れを軽減できる。このよう
な理由で、（００３）ベクトル方向の結晶子は５００オ
ングストローム以上、（１１０）ベクトル方向の結晶子
は４５０オングストローム以上が好ましい。<Thermal Stability> The thermal stability is improved in the present invention for the following reasons. LiMO2 of the positive electrode material of the present invention is basically a crystallite having a spherical shape with isotropic growth in space, and has a large crystallite diameter. By making the crystallite shape a spherical isotropic structure, the direction of crystal distortion due to the movement of Li due to charge and discharge becomes uniform in all spatial directions, so that the conventional crystal structure oriented in a certain direction In comparison, collapse can be minimized. In addition, by increasing the crystallite, it is possible to reduce the collapse of the crystal structure that occurs when Li ions are eliminated. For these reasons, the crystallite in the (003) vector direction is preferably 500 Å or more, and the crystallite in the (110) vector direction is preferably 450 Å or more.
【００３３】本発明の正極活物質の熱安定性について次
のようにして測定した。充電を完了したリチウムイオン
二次電池をドライボックス中で分解し、正極板を取り出
して約１０ｍｇを切り出し測定試料とする。得られた測
定試料をＴｈｅｒｍａｌ Ｇｒａｖｉｍｅｔｒｉｃ Ａ
ｎａｌｙｚｅｒ（ＴＧＡ）を用いて熱重量分析を行っ
た。（Solid State Ionics vol.69,No.3/4 Page 265-27
0(1994)）基本的にはその試料の温度を外部から上昇さ
せながら試料の重量変化を引き起こす限界温度を測定す
る方法である。この重量変化は主として正極活物質から
酸素が遊離することによる重量減少に基づく。電池の電
解液中にこの酸素濃度が増加すると異常発熱の原因とな
る。従って、限界温度は高いほど異常発熱の問題は低下
し好ましい。The thermal stability of the positive electrode active material of the present invention was measured as follows. The charged lithium ion secondary battery is disassembled in a dry box, the positive electrode plate is taken out, and about 10 mg is cut out to be a measurement sample. The obtained measurement sample was subjected to Thermal Gravimetric A
Thermogravimetric analysis was performed using a analyzer (TGA). (Solid State Ionics vol.69, No.3 / 4 Page 265-27
0 (1994)) Basically, a method of measuring a limit temperature that causes a change in weight of a sample while increasing the temperature of the sample from the outside. This weight change is mainly based on the weight loss due to liberation of oxygen from the positive electrode active material. An increase in the oxygen concentration in the battery electrolyte causes abnormal heat generation. Therefore, the higher the limit temperature, the lower the problem of abnormal heat generation, which is preferable.
【００３４】結晶子径と、ＴＧＡ装置の限界温度の関係
について、ほぼ球状をした結晶子を有する正極活物質に
ついて測定し図３にプロットした。本発明の正極活物質
はほぼ球状であるのでの結晶子径はどのようなベクトル
方向で測定しても同等であるが、ここでは（００３）ベ
クトル方向の結晶子径を上述したシェラーの式を用いて
計算した。図２よりＬｉＭＯ2の充電時の熱安定性と一
次関数的に相関しており、結晶子径の大きい方が限界温
度が高くなり、すなわち熱安定性が向上していることが
理解できる。これは上述したように結晶子径が大きいと
充電時のＬｉの離脱による結晶の崩れの影響は小さくな
り、遊離酸素濃度が低下することによる。The relationship between the crystallite diameter and the critical temperature of the TGA apparatus was measured for a cathode active material having substantially spherical crystallites and plotted in FIG. Since the cathode active material of the present invention is substantially spherical, the crystallite diameter is the same regardless of the vector direction, but here, the (003) crystallite diameter in the vector direction is calculated by the above-mentioned Scherrer equation. Calculated using FIG. 2 shows that the thermal stability during charging of LiMO2 is linearly related to the thermal stability, and it can be understood that the larger the crystallite diameter, the higher the limit temperature, that is, the higher the thermal stability. This is because, as described above, when the crystallite diameter is large, the influence of crystal breakage due to detachment of Li during charging is reduced, and the free oxygen concentration is reduced.
【００３５】＜充放電サイクル特性＞充放電サイクルに
ついては、（１１０）ベクトル方向への結晶子径が１０
００オングストローム以上に成長し過ぎないことが重要
である。これは、（１１０）ベクトル方向に結晶を成長
し過ぎると、図２（ｂ）に示すように、正極活物質にＬ
ｉを挿入（放電）する際、層に対して平行な方向しかＬ
ｉイオンが挿入できないため、相対的にＬｉイオン挿入
可能な面が減少し、粒子界面でのＬｉイオンの拡散が悪
化するためである。特に、高い電流密度で放電させた場
合、この傾向が顕著になる。<Charge / Discharge Cycle Characteristics> Regarding the charge / discharge cycle, the crystallite diameter in the (110) vector direction is 10
It is important that they do not grow too much above 00 Angstroms. This is because if the crystal grows too much in the (110) vector direction, as shown in FIG.
When inserting (discharging) i, only the direction parallel to the layer is L
This is because, since i-ions cannot be inserted, the surface into which Li ions can be inserted relatively decreases, and the diffusion of Li ions at the particle interface deteriorates. In particular, when discharging at a high current density, this tendency becomes remarkable.
【００３６】図４に本発明の正極活物質の結晶子径と１
００サイクル劣化率の関係をプロットした。ここで本発
明品は球形であることから、結晶子径はどの方向で評価
してもほぼ同じであるが、ここでは（１１０）ベクトル
方向の結晶子径に対してプロットした。図３より結晶子
径が５００からおよそ１０００オングストロームの範囲
ではサイクル特性はほぼ変化しないが、およそ１０００
オングストロームを超えると後に定義する容量維持率は
低下することが分かる。FIG. 4 shows the crystallite diameter of the positive electrode active material of the present invention and 1
The relationship of the 00 cycle deterioration rate was plotted. Here, since the product of the present invention is spherical, the crystallite diameter is almost the same no matter which direction is evaluated. Here, however, the crystallite diameter is plotted with respect to the crystallite diameter in the (110) vector direction. As shown in FIG. 3, when the crystallite diameter is in the range of 500 to about 1000 angstroms, the cycle characteristics hardly change.
It is understood that the capacity retention ratio defined later decreases when the thickness exceeds Å.
【００３７】リチウム二次電池の充放電試験は次のよう
にして行う。先ず、正極としてＬｉＭＯ2を７０重量
部、アセチレンブラックを１５重量部、ＰＴＦＴ（ポリ
テトラフルオロエチレン）１５重量部をエタノールで混
合し練り延ばしたものをペースト状とし、ＳＵＳメッシ
ュ上に圧着し、それを乾燥して正極板を得る。これに対
し、Ｌｉ金属を負極として、これら両電極をＥＣ（エチ
レンカーボネート）、ＤＥＣ（ジエチレンカーボネー
ト）及び電解質ＬｉＰＣｌ4を混合した電解液に浸漬す
る。充電は０．２Ｃ（１Ｃは１時間で充電又は放電が終
了する電流負荷）の電流負荷に設定し、充電上限電圧を
４．２０Ｖとする。放電は０．６Ｃ電流負荷に設定し、
下限電圧を２．７５Ｖとし、１００サイクルの充放電を
行う。容量維持率は（１０回目の放電容量）／（１回目
の放電容量）×１００の（％）式により算出する。The charge / discharge test of the lithium secondary battery is performed as follows. First, as a positive electrode, 70 parts by weight of LiMO2, 15 parts by weight of acetylene black, and 15 parts by weight of PTFT (polytetrafluoroethylene) were mixed with ethanol and kneaded to form a paste, which was then pressed on a SUS mesh and pressed. Dry to obtain a positive electrode plate. On the other hand, both electrodes are immersed in an electrolytic solution in which EC (ethylene carbonate), DEC (diethylene carbonate) and the electrolyte LiPCl4 are mixed, using Li metal as a negative electrode. The charging is set to a current load of 0.2 C (1 C is a current load at which charging or discharging is completed in one hour), and the charging upper limit voltage is set to 4.20 V. Discharge is set to 0.6C current load,
The lower limit voltage is set to 2.75 V, and charge / discharge for 100 cycles is performed. The capacity retention ratio is calculated by the (%) formula of (10th discharge capacity) / (1st discharge capacity) × 100.
【００３８】前述したように従来技術では、サイクル特
性を向上させるために、粒子を平板状単結晶にし、ｃ軸
方向の粒子の伸縮を一定方向にすることにより、粒子の
崩れを防止し、集電体からの剥離を防止するとしてい
る。これに対し、本発明では逆に、結晶を配向性のない
球状に近い形状とした。そのことで、粒子そのものの集
電体への接着力が増大し、充放電サイクルによる正極活
物質の集電体からの剥離を防止し、さらに、粒子界面で
のＬｉ挿入可能な面を増加させることにより、サイクル
特性が改善される。As described above, in the prior art, in order to improve the cycle characteristics, the particles are made into a flat plate single crystal, and the expansion and contraction of the particles in the c-axis direction are made in a certain direction, thereby preventing the particles from collapsing and collecting. It is said to prevent peeling from the conductor. On the other hand, in the present invention, on the contrary, the crystal was formed into a shape close to a spherical shape without orientation. This increases the adhesion of the particles themselves to the current collector, prevents the positive electrode active material from peeling off from the current collector due to charge / discharge cycles, and further increases the surface on the particle interface where Li can be inserted. Thereby, the cycle characteristics are improved.
【００３９】[0039]
【実施例】本発明の実施例を正極活物質としてＬｉＣｏ
Ｏ2について説明するが、この組成に限定するものでは
なく、ＬｉＭＯ2（但しＭはＣｏ、Ｎｉ、Ｆｅ、Ｃｒの
群から選ばれる少なくとも一種の重金属元素）の全ての
可能な組成についても同様である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention uses LiCo as a positive electrode active material.
O2 will be described, but the composition is not limited to this. The same applies to all possible compositions of LiMO2 (where M is at least one heavy metal element selected from the group consisting of Co, Ni, Fe, and Cr).
【００４０】 ［実施例１］ ＜原料仕込み＞ ・四三酸化コバルト（Ｃｏ3Ｏ4）・・・・・ ３．０００ｋｇ ・炭酸リチウム（Ｌｉ2ＣＯ3）・・・・・・ １．３８０ｋｇ 四三酸化コバルトは（２２２）ベクトル方向の結晶子径
が２００オングストロームであり、二次粒子の形状がほ
ぼ球状の多結晶の粒子である。二次粒子径について、Ｃ
ｏｕｌｔｅｒ Ｍｕｌｔｉｓｉｚｅｒ２を用いて測定し
たところ中心粒径は５．０μｍであった。上記原料のＬ
ｉ／Ｃｏの仕込み比率は１．００である。これら原料を
セラミックポットに仕込み、ボールミルを行い正極活物
質の混合原料を得る。Example 1 <Preparation of Raw Materials> Cobalt tetroxide (Co 3 O 4) 3.000 kg Lithium carbonate (Li 2 CO 3) 1.380 kg Cobalt tetroxide was (222 2) The crystallite diameter in the vector direction is 200 angstroms, and the secondary particles are substantially spherical polycrystalline particles. Regarding the secondary particle size, C
The center particle size was 5.0 μm as measured using an Oulter Multisizer 2. L of the above raw materials
The charging ratio of i / Co is 1.00. These raw materials are charged into a ceramic pot and ball milled to obtain a mixed raw material of the positive electrode active material.
【００４１】得られた混合原料を空気中９００℃で１０
時間焼成し、粉砕し、目的とするＬｉＣｏＯ2を合成し
た。The obtained mixed raw material was heated at 900 ° C. in air for 10 hours.
After firing for a period of time and pulverizing, the desired LiCoO2 was synthesized.
【００４２】得られたＬｉＣｏＯ2をＣｕＫαを線源と
する粉末Ｘ線回折を測定し、シェラーの式を用いて計算
したところ、（００３）ベクトル方向の結晶子径は６０
６オングストローム、及び（１１０）ベクトル方向の結
晶子径は８７９オングストロームであり、その他（１１
５）ベクトル方向の結晶子径は７９５オングストロー
ム、（１１３）ベクトル方向の結晶子径は８４８オング
ストロームであった。The obtained LiCoO 2 was measured for powder X-ray diffraction using CuKα as a radiation source, and was calculated using Scherrer's formula. As a result, the crystallite diameter in the (003) vector direction was 60%.
The crystallite diameter in the 6 Å and (110) vector directions is 879 Å, and the other (11
5) The crystallite diameter in the vector direction was 795 angstroms, and the crystallite diameter in the (113) vector direction was 848 angstroms.
【００４３】ＬｉＣｏＯ2正極活物質の粒子径につい
て、Ｆ．Ｓ．Ｓ．Ｓ．を用いて測定したところ平均粒径
は４．０μｍであり、個々の粒子の短軸粒子径／長軸粒
子径の比率の平均を計算したところ０．９であった。Ｓ
ＥＭに供する測定用試料を作製する場合、圧力を加えて
作製すると、本発明の等方的形状の粒子と見分けが付け
にくくなる。そこで、ＳＥＭ測定試料を作製する場合、
粒子の形状を受けにくくするため試料面に圧力をかけな
いように準備した。Regarding the particle size of the LiCoO 2 cathode active material, S. S. S. The average particle size was 4.0 μm as measured by using the formula (1), and the average of the ratio of the short axis particle diameter / the long axis particle diameter of each particle was 0.9. S
When preparing a measurement sample to be subjected to EM, if it is prepared by applying pressure, it will be difficult to distinguish it from the isotropically shaped particles of the present invention. Therefore, when preparing a SEM measurement sample,
The sample surface was prepared so as not to apply pressure to make it difficult to receive the shape of the particles.
【００４４】＜サイクル特性＞得られた正極活物質Ｌｉ
ＣｏＯ2を７０重量部、アセチレンブラックを１５重量
部、ＰＴＦＴ（ポリテトラフルオロエチレン）１５重量
部をエタノールで混合し練り延ばしたものをペースト状
とし、ＳＵＳメッシュ上に圧着し、それを乾燥して正極
板を得る。これに対しＬｉ金属を負極として、これら両
電極をＥＣ（エチレンカーボネート）、ＤＥＣ（ジエチ
レンカーボネート）及び電解質ＬｉＰＣｌ4を混合した
電解液に浸漬する。充電は０．２Ｃ（１Ｃは１時間で充
電又は放電が終了する電流負荷）の電流負荷に設定し、
充電上限電圧を４．２０Ｖとする。放電は０．６Ｃ電流
負荷に設定し、下限電圧を２．７５Ｖとし、１００サイ
クルの充放電を行う。容量維持率は（１００回目の放電
容量）／（１回目の放電容量）×１００の式により求め
た結果９５．２％であった。<Cycle characteristics> The obtained positive electrode active material Li
A mixture of 70 parts by weight of CoO2, 15 parts by weight of acetylene black, and 15 parts by weight of PTFT (polytetrafluoroethylene) mixed with ethanol and kneaded into a paste was pressed on a SUS mesh, dried and dried to form a positive electrode. Get the board. On the other hand, both electrodes are immersed in an electrolytic solution in which EC (ethylene carbonate), DEC (diethylene carbonate) and the electrolyte LiPCl4 are mixed, using Li metal as a negative electrode. The charging is set to a current load of 0.2C (1C is a current load at which charging or discharging is completed in one hour),
The charging upper limit voltage is set to 4.20V. The discharge is set to a 0.6 C current load, the lower limit voltage is set to 2.75 V, and charge / discharge for 100 cycles is performed. The capacity retention ratio was 95.2% as a result of an expression of (100th discharge capacity) / (first discharge capacity) × 100.
【００４５】＜熱安定性＞得られた正極活物質ＬｉＣＯ
2を使用し、サイクル特性測定と同じ条件の二次電池を
作製し、充電負荷０．２Ｃ、充電上限電圧４．２０Ｖの
条件で充電を行い、次に、リチウムイオン二次電池をド
ライボックス中で分解し、正極板を取り出してその内の
約１０ｍｇを切り出し測定試料とする。得られた測定試
料をＴＧＡ装置を用いて熱重量分析を行った結果、２１
８．０℃で酸素遊離に基づく重量変化が観測され、限界
温度はすなわち２１８．０℃であった。<Thermal stability> The obtained positive electrode active material LiCO
2 was used to prepare a secondary battery under the same conditions as the cycle characteristics measurement, charging was performed under the conditions of a charging load of 0.2 C and a charging upper limit voltage of 4.20 V, and then the lithium ion secondary battery was placed in a dry box. The positive electrode plate is taken out, and about 10 mg thereof is cut out to obtain a measurement sample. As a result of performing thermogravimetric analysis on the obtained measurement sample using a TGA device,
At 8.0 ° C., a weight change due to oxygen release was observed, with a limiting temperature of 218.0 ° C.
【００４６】［比較例１］四三酸化コバルト粒子はＳＥ
Ｍによる観察によると六角板状粒子であり、（２２２）
ベクトル方向の結晶子径が１００オングストローム、Ｃ
ｏｕｌｔｅｒ Ｍｕｌｔｉｓｉｚｅｒ２を用いて測定し
た二次粒子の中心粒径が６．２μｍであるものを使用す
る以外実施例１と同じ条件で原料を混合し、焼成するこ
とでＬｉＣｏＯ2を合成した。Comparative Example 1 Cobalt tetroxide particles were SE
According to observation by M, the particles were hexagonal plate-like particles, and (222)
The crystallite diameter in the vector direction is 100 Å, C
LiCoO2 was synthesized by mixing and firing the raw materials under the same conditions as in Example 1 except that secondary particles having a center particle diameter of 6.2 μm measured using an Oulter Multisizer 2 were used.
【００４７】得られたＬｉＣｏＯ2を実施例１と同様に
してシェラーの式を用いて計算したところ、（００３）
ベクトル方向の結晶子径は６４９オングストローム、及
び（１１０）ベクトル方向の結晶子径は１１５０オング
ストロームであり、その他（１１５）ベクトル方向の結
晶子径は７９８オングストローム、（１１３）ベクトル
方向の結晶子径は８６８オングストロームであった。When the obtained LiCoO 2 was calculated using Scherrer's formula in the same manner as in Example 1, (003)
The crystallite diameter in the vector direction is 649 angstroms, the crystallite diameter in the (110) vector direction is 1150 angstroms, the crystallite diameter in the (115) vector direction is 798 angstroms, and the crystallite diameter in the (113) vector direction is It was 868 angstroms.
【００４８】ＬｉＣｏＯ2正極活物質の粒子径について
Ｆ．Ｓ．Ｓ．Ｓ．を用いて測定したところ平均粒径は
３．５μｍであった。Regarding the particle size of the LiCoO 2 cathode active material S. S. S. As a result, the average particle size was 3.5 μm.
【００４９】さらに、ＳＥＭ観察によるＬｉＣｏＯ2の
粒子の長軸粒子径に対する短軸粒子径の比率は０．３で
あった。Further, the ratio of the minor axis particle diameter to the major axis particle diameter of the LiCoO 2 particles observed by SEM was 0.3.
【００５０】＜サイクル特性＞得られた正極活物質を使
用する以外実施例１と同様にして二次電池を作製し、１
００サイクル充放電を行った。容量維持率は８５．０％
であった。<Cycle Characteristics> A secondary battery was prepared in the same manner as in Example 1 except that the obtained positive electrode active material was used.
The charge and discharge were performed for 00 cycles. 85.0% capacity retention
Met.
【００５１】＜熱安定性＞得られた正極活物質ＬｉＣＯ
2を使用し、実施例１と同様にしてＴＧＡを用いて熱重
量分析を行った結果、酸素遊離に基づく重量変化が観測
される限界温度は１９０．８℃であった。<Thermal stability> The obtained positive electrode active material LiCO
As a result of performing thermogravimetric analysis using TGA and using TGA in the same manner as in Example 1, the limit temperature at which a weight change due to oxygen release was observed was 190.8 ° C.
【００５２】[0052]
【発明の効果】以上説明したように、本発明の正極物質
のＬｉＭＯ2は、基本的に結晶子の形状が空間に等方的
に成長した球状であり、しかも結晶子径を大きくしてい
る。結晶子の形状を球形の等方的構造とすることで、充
放電に伴うＬｉの移動による結晶の歪みの方向が全ての
空間方向に均等となるため、一定方向に配向した従来の
結晶構造に比べ、崩れを最小に抑えることが可能とな
る。また、さらに結晶子を特定の範囲に大きくすること
によりＬｉイオンの脱離時に生じる結晶構造の崩れを軽
減できる。これらの点で本発明品は従来品に比べ正極活
物質の熱安定性及びサイクル特性を著しく改善すること
ができた。As described above, LiMO2 of the cathode material of the present invention is basically a sphere in which the crystallite shape is isotropically grown in space, and has a larger crystallite diameter. By making the crystallite shape a spherical isotropic structure, the direction of crystal distortion due to the movement of Li due to charge and discharge becomes uniform in all spatial directions, so that the conventional crystal structure oriented in a certain direction In comparison, collapse can be minimized. Further, by further increasing the crystallite to a specific range, the collapse of the crystal structure that occurs when Li ions are eliminated can be reduced. In these respects, the product of the present invention was able to significantly improve the thermal stability and cycle characteristics of the positive electrode active material as compared with the conventional product.
【図１】ＳＥＭ写真による長軸粒子径、短軸粒子径の評
価方法を示す模式図。FIG. 1 is a schematic view showing a method for evaluating a long axis particle diameter and a short axis particle diameter based on an SEM photograph.
【図２】（ａ）本発明品及び（ｂ）比較品の正極活物質
の粒子形状の比較を示す拡大模式図。FIG. 2 is an enlarged schematic diagram showing a comparison of the particle shapes of a positive electrode active material of (a) the present invention product and (b) a comparative product.
【図３】結晶子径と限界温度の関係を示す特性図。FIG. 3 is a characteristic diagram showing a relationship between a crystallite diameter and a limit temperature.
【図４】容量維持率と結晶子径の関係を示す特性図。FIG. 4 is a characteristic diagram showing a relationship between a capacity retention ratio and a crystallite diameter.
１・・・・・・・Ｌｉイオンが挿入可能な面 1 ····· The surface into which Li ions can be inserted
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤野 賢治 徳島県阿南市上中町岡491番地100 日亜化 学工業株式会社内 (72)発明者 藤井 孝浩 徳島県阿南市上中町岡491番地100 日亜化 学工業株式会社内 (72)発明者 一ノ宮 敬治 徳島県阿南市上中町岡491番地100 日亜化 学工業株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenji Fujino 491-100 Kaminakacho Oka, Anan City, Tokushima Prefecture Inside Nichia Kakoh Kogyo Co., Ltd. Within Aka Chemical Industry Co., Ltd.
Claims (6)
イオン二次電池用正極活物質であって、その粒子構造
は、結晶子を単位とし、それが集合した粒子からなり、
該結晶子及び該粒子の形状は立体的にほぼ等方的形状で
あることを特徴とするリチウムイオン二次電池用正極活
物質。（但しＭはＣｏ、Ｎｉ、Ｆｅ、Ｍｎ、Ｃｒの群か
ら選ばれる少なくとも一種の重金属元素）1. A positive electrode active material for a lithium ion secondary battery represented by the general formula LiMO2, wherein the particle structure is composed of particles in which a crystallite is a unit and which is aggregated,
The positive electrode active material for a lithium ion secondary battery, wherein the shape of the crystallite and the particles is three-dimensional and substantially isotropic. (Where M is at least one heavy metal element selected from the group consisting of Co, Ni, Fe, Mn, and Cr)
子の立体形状を、層を重ねる方向（（００３）ベクトル
方向）、及びそれに垂直な方向（（１１０）ベクトル方
向）で表現する場合、（１１０）ベクトル方向の結晶子
径に対する（００３）ベクトル方向の結晶子径の比率
は、０．５〜１．６の範囲であることを特徴とする請求
項１に記載のリチウムイオン二次電池用正極活物質。2. A case in which the three-dimensional shape of crystallites constituting the primary particles of the positive electrode active material is expressed by a direction in which layers are superposed ((003) vector direction) and a direction perpendicular thereto ((110) vector direction). 2. The lithium ion secondary according to claim 1, wherein a ratio of a crystallite diameter in the (003) vector direction to a crystallite diameter in the (110) vector direction is in a range of 0.5 to 1.6. 3. Positive electrode active material for batteries.
トル方向の結晶子径は５００〜７５０オングストローム
の範囲であることを特徴とする請求項１に記載のリチウ
ムイオン二次電池用正極活物質。3. The positive electrode active material for a lithium ion secondary battery according to claim 1, wherein a crystallite diameter in a (003) vector direction of a crystallite of the positive electrode active material is in a range of 500 to 750 Å. material.
トル方向の結晶子径は４５０〜１０００オングストロー
ムの範囲であることを特徴とする請求項１に記載のリチ
ウムイオン二次電池用正極活物質。4. The positive electrode active material for a lithium ion secondary battery according to claim 1, wherein the crystallite diameter of the crystallite of the positive electrode active material in the (110) vector direction is in a range of 450 to 1000 Å. material.
均粒径は０．１〜１０μｍであり、ＳＥＭ観察による該
粒子の長軸粒子径に対する短軸粒子径の比率は０．５〜
１．０の範囲であることを特徴とする請求項１に記載の
リチウムイオン二次電池用正極物質。5. The particle has a substantially spherical shape, an average particle diameter of 0.1 to 10 μm, and a ratio of a short axis particle diameter to a long axis particle diameter of the particle measured by SEM is 0.5 to 10 μm.
The positive electrode material for a lithium ion secondary battery according to claim 1, wherein the positive electrode material has a range of 1.0.
／Ｍ比が０．９８〜１．０１の範囲となるように混合し
て焼成する正極活物質の製造方法において、該重金属酸
化物の粒子形状は、立体的にほぼ等方的形状を有する一
次粒子又は一次粒子が集合した二次粒子からなり、その
中心粒径は０．１〜１０μｍであることを特徴とするリ
チウムイオン二次電池用正極活物質の製造方法。（但し
ＭはＣｏ、Ｎｉ、Ｆｅ、Ｍｎ、Ｃｒの群から選ばれる少
なくとも一種の重金属元素）6. A method for converting raw material heavy metal oxide and lithium salt into Li
In the method for producing a positive electrode active material, which is mixed and fired so that the / M ratio is in the range of 0.98 to 1.01, the particle shape of the heavy metal oxide is substantially three-dimensional. A method for producing a positive electrode active material for a lithium ion secondary battery, comprising secondary particles in which particles or primary particles are aggregated, and having a central particle size of 0.1 to 10 μm. (Where M is at least one heavy metal element selected from the group consisting of Co, Ni, Fe, Mn, and Cr)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07490797A JP3591195B2 (en) | 1997-03-07 | 1997-03-27 | Cathode active material for lithium ion secondary batteries |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-52900 | 1997-03-07 | ||
| JP5290097 | 1997-03-07 | ||
| JP07490797A JP3591195B2 (en) | 1997-03-07 | 1997-03-27 | Cathode active material for lithium ion secondary batteries |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003127719A Division JP4062165B2 (en) | 1997-03-07 | 2003-05-06 | Method for producing positive electrode active material for lithium ion secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10308218A true JPH10308218A (en) | 1998-11-17 |
| JP3591195B2 JP3591195B2 (en) | 2004-11-17 |
Family
ID=26393564
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|---|---|---|---|
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| Country | Link |
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| JP (1) | JP3591195B2 (en) |
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