JP2003238162A - Lithium manganese composite oxide powder and its manufacturing method - Google Patents

Lithium manganese composite oxide powder and its manufacturing method

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Publication number
JP2003238162A
JP2003238162A JP2002039173A JP2002039173A JP2003238162A JP 2003238162 A JP2003238162 A JP 2003238162A JP 2002039173 A JP2002039173 A JP 2002039173A JP 2002039173 A JP2002039173 A JP 2002039173A JP 2003238162 A JP2003238162 A JP 2003238162A
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JP
Japan
Prior art keywords
lithium
composite oxide
oxide powder
manganese composite
compound
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
Application number
JP2002039173A
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Japanese (ja)
Other versions
JP4019729B2 (en
Inventor
Yoshifumi Miyamoto
良文 宮本
Kenichi Kobayashi
謙一 小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nichia Chemical Industries Ltd
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Nichia Chemical Industries Ltd
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    • 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

<P>PROBLEM TO BE SOLVED: To provide a lithium manganese composite oxide powder which is excellent in a preservation property, with little gas generation accompanying to the charge and discharge of electricity, and excellent in cyclic charge and discharge characteristics, and to provide its manufacturing method. <P>SOLUTION: The constitution of the lithium manganese composite oxide powder is expressed by general formula: Li<SB>1+a</SB>M<SB>b</SB>Mn<SB>2-a-b</SB>X<SB>c</SB>B<SB>d</SB>S<SB>e</SB>O<SB>4+f</SB>. (wherein M is aluminum and/or magnesium; X is a halogen element selected from among fluorine, chlorine, bromine, and iodine; B is boron; S is sulfur; and 0<a≤0.2, 0<b≤0.2, 0≤c≤0.05, 0<d≤0.02, 0<e≤0.1, 0≤f<0.5). <P>COPYRIGHT: (C)2003,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は非水電解液二次電池
及びその正極活物質に係り、特に保存特性に優れ、また
充放電に伴うガスの発生がほとんど無く、かつサイクル
充放電特性に優れたリチウムマンガン複合酸化物粉末及
びその製造方法、並びにそれを用いてなるリチウムイオ
ン二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery and a positive electrode active material thereof, and particularly has excellent storage characteristics, almost no generation of gas during charge / discharge, and excellent cycle charge / discharge characteristics. The present invention also relates to a lithium manganese composite oxide powder, a method for producing the same, and a lithium ion secondary battery using the same.

【０００２】[0002]

【従来の技術】リチウムイオン二次電池は、従来のニッ
ケルカドミウム二次電池などに比べて作動電圧が高く、
かつエネルギー密度が高いという特徴を有し、電子機器
の電源として広く利用されている。このリチウムイオン
二次電池の正極活物質としてはＬｉＣｏＯ２、ＬｉＭｎ
２Ｏ４に代表されるリチウム遷移金属複合酸化物が挙げ
られる。2. Description of the Related Art Lithium ion secondary batteries have higher operating voltage than conventional nickel-cadmium secondary batteries,
In addition, it has a feature of high energy density and is widely used as a power source for electronic devices. The positive electrode active material of this lithium ion secondary battery includes LiCoO 2 and LiMn.
Lithium transition metal composite oxide represented by 2 O 4 can be mentioned.

【０００３】なかでもＬｉＭｎ２Ｏ４は、構成元素であ
るマンガンが資源として多量に存在するため、原料が安
価に入手しやすい。また環境に対する負荷も少ないとい
う特徴がある。さらにデインターカレーション反応によ
って、結晶中のＬｉイオンが全量脱離しても、結晶構造
は安定に存在する。このためＬｉＣｏＯ２に比べて、Ｌ
ｉＭｎ２Ｏ４を用いた二次電池は、過充電状態において
発熱、発火の危険性が少なく、安全性に優れる。Among them, since LiMn 2 O 4 has a large amount of manganese, which is a constituent element, as a resource, the raw material is easily available at low cost. In addition, there is a characteristic that the load on the environment is small. Furthermore, even if the Li ions in the crystal are totally desorbed by the deintercalation reaction, the crystal structure is stable. Therefore, compared to LiCoO 2 , L
The secondary battery using iMn 2 O 4 is excellent in safety with less risk of heat generation and ignition in an overcharged state.

【０００４】しかしながらＬｉＭｎ２Ｏ４は、充放電に
伴いガスが発生し、電池が膨れる問題があった。また実
用レベルのサイクル充放電特性が得られない問題もあっ
た。これら問題点は高温度下において特に顕著に現れる
ため、例えば高温度下での使用が予想されるモバイル機
器などへ実用化できていないのが現状である。However, LiMn 2 O 4 has a problem in that gas is generated during charge and discharge and the battery swells. There is also a problem that a practical level cycle charge / discharge characteristic cannot be obtained. Since these problems are particularly remarkable under high temperature, the current situation is that they have not been put to practical use, for example, in mobile devices expected to be used under high temperature.

【０００５】上記した問題点の原因の１つとして、充放
電に伴いＬｉＭｎ２Ｏ４の結晶構造からマンガンイオン
が電解液に溶出することが挙げられる。この電解液に溶
出したマンガンイオンは、負極表面に析出し、リチウム
イオンの挿入、脱離の妨げとなり、サイクル充放電にお
ける放電容量の低下を引き起こす。さらにこの溶出した
マンガンイオンは、電解液中のエステル化合物の分解反
応を促進するといわれており、分解によってＣＯ２ガス
が発生し、電池の膨れを引き起こす。One of the causes of the above-mentioned problems is that manganese ions are eluted from the crystal structure of LiMn 2 O 4 into the electrolytic solution during charge and discharge. The manganese ions eluted in this electrolytic solution are deposited on the surface of the negative electrode, which hinders the insertion and desorption of lithium ions, causing a decrease in discharge capacity during cycle charge and discharge. Furthermore, the eluted manganese ions are said to accelerate the decomposition reaction of the ester compound in the electrolytic solution, and CO 2 gas is generated by the decomposition, causing the battery to swell.

【０００６】マンガンイオンの電解液への溶出を抑える
ために、ＬｉＭｎ２Ｏ４の粒子径を大きくし、表面積を
小さくすることで電解液との反応活性点を少なくし、マ
ンガンイオンの溶出を抑える技術が提案されている。例
えば平均粒子径、比表面積を規定した技術報告（特開２
０００−１２０３１）などがある。In order to suppress the elution of manganese ions into the electrolytic solution, the particle size of LiMn 2 O 4 is made large and the surface area is made small so that the reaction active points with the electrolytic solution are reduced and the elution of manganese ions is suppressed. Technology is proposed. For example, a technical report defining the average particle size and the specific surface area (Japanese Patent Laid-Open No.
000-12031) and the like.

【０００７】通常、粒子径の大きいＬｉＭｎ２Ｏ４を得
るためには、以下のような製造方法が用いられる。 （ａ）粒子径の大きいＭｎ化合物を原料として使用す
る。 （ｂ）高温度で焼成する。 （ｃ）低融点の融剤を使用する。 （ａ）〜（ｃ）を組み合わせることによって、ＬｉＭｎ
２Ｏ４の比表面積を小さくし、マンガンイオンの溶出を
ある程度抑えることはできるが、十分な特性の改善が得
られていない。特にサイクル充放電特性が実用レベルに
達していない。Usually, in order to obtain LiMn 2 O 4 having a large particle diameter, the following manufacturing method is used. (A) A Mn compound having a large particle diameter is used as a raw material. (B) Baking at high temperature. (C) Use a low melting point flux. By combining (a) to (c), LiMn
Although the specific surface area of 2 O 4 can be reduced and elution of manganese ions can be suppressed to some extent, sufficient improvement in characteristics has not been obtained. In particular, the cycle charge / discharge characteristics have not reached the practical level.

【０００８】更にマンガンイオンの電解液への溶出を抑
える手段として、ＬｉＭｎ２Ｏ４に他の元素を添加し、
結晶構造を安定化させ、サイクル充放電特性などを改善
する技術が知られている。例えば原子番号１１以上の金
属元素または遷移金属元素を添加することを要件とした
技術報告（特開平１１−１７１５５０）などが提案され
ている。Further, as a means for suppressing the elution of manganese ions into the electrolytic solution, other elements are added to LiMn 2 O 4 ,
Techniques for stabilizing the crystal structure and improving the cycle charge / discharge characteristics are known. For example, a technical report (Japanese Patent Application Laid-Open No. 11-171550), which requires addition of a metal element having an atomic number of 11 or more or a transition metal element, has been proposed.

【０００９】しかしながら上記した金属元素を添加する
技術では、金属元素の添加量と共に、初期放電容量は減
少する傾向があり、サイクル充放電特性、ガスの発生な
どの諸特性と初期放電容量とは、トレードオフの関係に
ある。However, in the above-mentioned technique of adding a metal element, the initial discharge capacity tends to decrease with the amount of the metal element added, and the characteristics such as cycle charge / discharge characteristics and gas generation and the initial discharge capacity are as follows: There is a trade-off relationship.

【００１０】サイクル充放電特性を左右する主な要因と
しては、電池を構成する各材料の変質、劣化と、リチウ
ムイオンの移動抵抗が挙げられる。またＬｉＭｎ２Ｏ４
は製造の際、原料混合物を８００℃以上で焼成すると結
晶構造中から酸素の脱離が生じ、結晶構造に歪みが生じ
る。結晶構造に歪みが存在すると、サイクル充放電に伴
い結晶構造の崩壊が生じ放電容量の低下を引き起こす。The main factors that influence the cycle charge / discharge characteristics are alteration and deterioration of each material forming the battery, and lithium ion transfer resistance. In addition, LiMn 2 O 4
In the production, when the raw material mixture is fired at 800 ° C. or higher, oxygen is desorbed from the crystal structure, and the crystal structure is distorted. If the crystal structure is distorted, the crystal structure collapses as a result of cycle charging / discharging, and the discharge capacity decreases.

【００１１】前述したＬｉＭｎ２Ｏ４結晶からマンガン
イオンが溶出することは、正極及び電解液の変質、劣化
を伴う。さらに負極に析出し、リチウムイオンの移動を
妨げるため、内部抵抗の増加も招くこととなる。このた
めサイクル充放電特性を改善するために、マンガンイオ
ンの溶出を抑えることは重要である。しかし実用レベル
のサイクル充放電特性を実現するためには、マンガンイ
オンの溶出を抑えるだけでは不十分であり、前記した比
表面積を小さくする技術、又は金属元素を添加する技術
では十分な改善が見られていないのが現状である。The elution of manganese ions from the LiMn 2 O 4 crystal described above is accompanied by alteration and deterioration of the positive electrode and the electrolytic solution. Furthermore, since it is deposited on the negative electrode and impedes the movement of lithium ions, it also causes an increase in internal resistance. Therefore, it is important to suppress the elution of manganese ions in order to improve the cycle charge / discharge characteristics. However, in order to achieve cycle charge / discharge characteristics at a practical level, it is not enough to suppress the elution of manganese ions, and the technology for reducing the specific surface area described above or the technology for adding a metal element has been sufficiently improved. The current situation is that it has not been done.

【００１２】[0012]

【発明が解決しようとする課題】上記したように、特に
高温度下で顕著に現れるガスの発生、サイクル充放電特
性の低下などの問題点を全て改善する技術は、十分に確
立されておらず、まだ実用化レベルに達していないのが
現状である。従って本発明の目的は上記した事情に鑑み
なされたものである。すなわち特に高温度下にて充放電
におけるガスの発生がほとんど無く、かつ優れたサイク
ル充放電特性などの電池特性を有するリチウムマンガン
複合酸化物粉末及びその製造方法、並びにそれを用いて
なるリチウムイオン二次電池を提供することにある。As described above, a technique for resolving all the problems such as the generation of gas, which appears remarkably at high temperature, and the deterioration of cycle charge / discharge characteristics, has not been sufficiently established. The current situation is that it has not yet reached the level of practical application. Therefore, the object of the present invention has been made in view of the above circumstances. That is, a lithium-manganese composite oxide powder having almost no generation of gas during charge and discharge at high temperature and having battery characteristics such as excellent cycle charge and discharge characteristics, a method for producing the same, and a lithium ion electrolyte using the same. It is to provide the next battery.

【００１３】[0013]

【課題を解決するための手段】本発明者は上記した問題
を解決するために鋭意検討した結果、立方晶スピネル型
マンガン酸リチウムに特定の元素を添加し、かつ各構成
元素の組成比、（４００）ベクトル方向の結晶子径、粉
体の比表面積を最適化することによって、上記した問題
点の全てを改善できることを見い出し、本発明を完成す
るに至った。Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventor has added a specific element to cubic spinel type lithium manganate and has a composition ratio of each constituent element, ( 400) It was found that all of the above problems can be solved by optimizing the crystallite diameter in the vector direction and the specific surface area of the powder, and completed the present invention.

【００１４】すなわち本発明の目的は、下記（１）〜
（６）の構成によって達成することができる。That is, the objects of the present invention are as follows.
This can be achieved by the configuration of (6).

【００１５】アルミニウム及び／又はマグネシウムと、
ホウ素と硫黄とを含むＬｉ１＋ａＭｎ ２−ａＯ
４＋ｆ（０＜ａ≦０．２、０≦ｆ＜０．５）で示される
リチウムマンガン複合酸化物粉末。Aluminum and / or magnesium,
Li containing boron and sulfur1 + aMn 2-aO
4 + f(0 <a ≦ 0.2, 0 ≦ f <0.5)
Lithium manganese composite oxide powder.

【００１６】（２）アルミニウム及び／又はマグネシウ
ムと、フッ素、塩素、臭素、ヨウ素から選ばれた少なく
とも一種類のハロゲン元素と、ホウ素と硫黄とを含むＬ
ｉ１ ＋ａＭｎ２−ａＯ４＋ｆ（０＜ａ≦０．２、０≦ｆ
＜０．５）で示されるリチウムマンガン複合酸化物粉
末。(2) L containing aluminum and / or magnesium, at least one halogen element selected from fluorine, chlorine, bromine and iodine, and boron and sulfur
i 1 + a Mn 2-a O 4 + f (0 <a ≦ 0.2, 0 ≦ f
A lithium manganese composite oxide powder represented by <0.5).

【００１７】（３）一般式Ｌｉ１＋ａＭｂＭｎ
２−ａ−ｂＸｃＢｄＳｅＯ４＋ｆ（Ｍはアルミニウム及
び／又はマグネシウム、Ｘはフッ素、塩素、臭素、ヨウ
素から選ばれた少なくとも一種類のハロゲン元素、Ｂは
ホウ素、Ｓは硫黄、０＜ａ≦０．２、０＜ｂ≦０．２、
０≦ｃ≦０．０５、０＜ｄ≦０．０２、０＜ｅ≦０．
１、０≦ｆ＜０．５）で表されることを特徴とする前記
（１）又は（２）に記載のリチウムマンガン複合酸化物
粉末。(3) General formula Li 1 + a M b Mn
2-a-b X c B d S e O 4 + f (M is aluminum and / or magnesium, X is fluorine, chlorine, bromine, at least one halogen element selected from iodine, B is boron, S is sulfur, 0 <a ≦ 0.2, 0 <b ≦ 0.2,
0 ≦ c ≦ 0.05, 0 <d ≦ 0.02, 0 <e ≦ 0.
1, 0 ≦ f <0.5), The lithium-manganese composite oxide powder according to (1) or (2) above.

【００１８】（４）前記一般式中の硫黄の組成比ｅは
０．００１≦ｅ≦０．０６であることを特徴とする前記
（３）に記載のリチウムマンガン複合酸化物粉末。(4) The lithium manganese composite oxide powder as described in (3) above, wherein the composition ratio e of sulfur in the general formula is 0.001≤e≤0.06.

【００１９】（５）前記リチウムマンガン複合酸化物粉
末の比表面積は０．２〜１．２ｍ２／ｇであることを特
徴とする前記（３）又は（４）に記載のリチウムマンガ
ン複合酸化物粉末。(5) The specific surface area of the lithium-manganese composite oxide powder is 0.2 to 1.2 m 2 / g, and the lithium-manganese composite oxide according to the above (3) or (4). Powder.

【００２０】（６）１μｍ以下の粒子は１体積％以下で
あることを特徴とする前記（３）及至（５）のいずれか
に記載のリチウムマンガン複合酸化物粉末。(6) The lithium manganese composite oxide powder according to any one of (3) to (5) above, wherein the content of particles of 1 μm or less is 1% by volume or less.

【００２１】（７）リチウム化合物、マンガン化合物、
ホウ素化合物、ハロゲン化合物、硫黄含有化合物、並び
にアルミニウム化合物及び／又はマグネシウム化合物を
混合し、焼成することを特徴とする前記（３）及至
（６）のいずれかに記載のリチウムマンガン複合酸化物
粉末の製造方法。(7) Lithium compound, manganese compound,
The lithium-manganese composite oxide powder according to any one of (3) to (6), characterized in that a boron compound, a halogen compound, a sulfur-containing compound, and an aluminum compound and / or a magnesium compound are mixed and fired. Production method.

【００２２】（８）一般式Ｌｉ１＋ａＭｂＭｎ
２−ａ−ｂＸｃＢｄＳｅＯ４＋ｆ（Ｍはアルミニウム及
び／又はマグネシウム、Ｘはフッ素、塩素、臭素、ヨウ
素から選ばれた少なくとも一種類のハロゲン元素、Ｂは
ホウ素、Ｓは硫黄、０＜ａ≦０．２、０＜ｂ≦０．２、
０＜ｃ≦０．０５、０＜ｄ≦０．０２、０＜ｅ≦０．
１、０≦ｆ＜０．５）で表され、かつ（４００）ベクト
ル方向の結晶子径は７５０〜１０００オングストローム
であることを特徴とする前記（１）又は（２）に記載の
リチウムマンガン複合酸化物粉末。(8) General formula Li 1 + a M b Mn
2-a-b X c B d S e O 4 + f (M is aluminum and / or magnesium, X is fluorine, chlorine, bromine, at least one halogen element selected from iodine, B is boron, S is sulfur, 0 <a ≦ 0.2, 0 <b ≦ 0.2,
0 <c ≦ 0.05, 0 <d ≦ 0.02, 0 <e ≦ 0.
1, 0 ≦ f <0.5), and the crystallite size in the (400) vector direction is 750 to 1000 angstroms. The lithium manganese composite according to (1) or (2) above. Oxide powder.

【００２３】（９）前記リチウムマンガン複合酸化物粉
末の比表面積は０．２〜１ｍ２／ｇであることを特徴と
する前記（８）に記載のリチウムマンガン複合酸化物粉
末。(9) The lithium manganese composite oxide powder according to (8), wherein the specific surface area of the lithium manganese composite oxide powder is 0.2 to 1 m 2 / g.

【００２４】（１０）リチウム化合物、マンガン化合
物、ホウ素化合物、ハロゲン化合物、硫黄含有化合物、
並びにアルミニウム化合物及び／又はマグネシウム化合
物を混合し、酸素濃度が１８％以上の雰囲気中で焼成す
ることを特徴とする前記（８）又は（９）に記載のリチ
ウムマンガン複合酸化物粉末。(10) Lithium compound, manganese compound, boron compound, halogen compound, sulfur-containing compound,
And an aluminum compound and / or a magnesium compound, and the mixture is fired in an atmosphere having an oxygen concentration of 18% or more, the lithium manganese composite oxide powder according to (8) or (9).

【００２５】（１１）アルミニウム及び／又はマグネシ
ウムと、ホウ素と硫黄とナトリウム及び／又はカルシウ
ムとを含むＬｉ１＋ａＭｎ２−ａＯ４＋ｆ（０＜ａ≦
０．２、０≦ｆ＜０．５）で示されるリチウムマンガン
複合酸化物粉末。(11) Li 1 + a Mn 2-a O 4 + f (0 <a ≦ containing aluminum and / or magnesium, boron, sulfur, sodium and / or calcium)
0.2, 0 ≦ f <0.5) lithium manganese composite oxide powder.

【００２６】（１２）アルミニウム及び／又はマグネシ
ウムと、フッ素、塩素、臭素、ヨウ素から選ばれた少な
くとも一種類のハロゲン元素と、ホウ素と硫黄とナトリ
ウム及び／又はカルシウムとを含むＬｉ１＋ａＭｎ
２−ａＯ４＋ｆ（０＜ａ≦０．２、０≦ｆ＜０．５）で
示されるリチウムマンガン複合酸化物粉末。(12) Li 1 + a Mn containing aluminum and / or magnesium, at least one halogen element selected from fluorine, chlorine, bromine and iodine, and boron, sulfur, sodium and / or calcium
2- aO 4 + f (0 <a ≦ 0.2, 0 ≦ f <0.5) lithium manganese composite oxide powder.

【００２７】（１３）一般式Ｌｉ１＋ａＭｂＭｎ
２−ａ−ｂＸｃＢｄＳｅＡｇＯ４＋ｆ（Ｍはアルミニウ
ム及び／又はマグネシウム、Ｘはフッ素、塩素、臭素、
ヨウ素から選ばれた少なくとも一種類のハロゲン元素、
Ｂはホウ素、Ｓは硫黄、Ａはナトリウム及び／又はカル
シウム、０＜ａ≦０．２、０＜ｂ≦０．２、０≦ｃ≦
０．０５、０＜ｄ≦０．０２、０＜ｅ≦０．１、０≦ｆ
＜０．５、０．００００４≦ｇ≦０．０１５）で表され
ることを特徴とする前記（１１）又は（１２）に記載の
リチウムマンガン複合酸化物粉末。(13) General formula Li 1 + a M b Mn
2-a-b X c B d S e A g O 4 + f (M is aluminum and / or magnesium, X is fluorine, chlorine, bromine,
At least one halogen element selected from iodine,
B is boron, S is sulfur, A is sodium and / or calcium, 0 <a ≦ 0.2, 0 <b ≦ 0.2, 0 ≦ c ≦
0.05, 0 <d ≦ 0.02, 0 <e ≦ 0.1, 0 ≦ f
<0.5, 0.00004 ≦ g ≦ 0.015), The lithium-manganese composite oxide powder according to (11) or (12) above.

【００２８】（１４）前記リチウムマンガン複合酸化物
粉末の比表面積は０．２〜１．２ｍ ２／ｇであることを
特徴とする前記（１３）に記載のリチウムマンガン複合
酸化物粉末。(14) The lithium manganese composite oxide
The specific surface area of the powder is 0.2 to 1.2 m Two/ G
The lithium manganese composite according to (13), which is characterized in that
Oxide powder.

【００２９】すなわち化学量論組成比よりも過剰量のリ
チウムと、アルミニウム及び／又はマグネシウムとの相
乗効果によって結晶構造の安定化を図る。また過剰量の
リチウムとホウ素、硫黄との相乗効果によって、焼結を
促進し、更なる結晶構造の安定化を実現する。またこの
とき焼結により比表面積の小さい粉末となるため、電解
液との反応活性点を低減できる。以上によりマンガンイ
オンの溶出を抑えることができ、ガスの発生による電池
の膨れ及びサイクル充放電時の悪化を改善できる。That is, the crystal structure is stabilized by a synergistic effect of aluminum and / or magnesium in excess of the stoichiometric composition ratio. In addition, the synergistic effect of excessive amounts of lithium, boron and sulfur promotes sintering and realizes further stabilization of the crystal structure. Further, at this time, since the powder becomes a powder having a small specific surface area due to sintering, it is possible to reduce the reaction active points with the electrolytic solution. As described above, the elution of manganese ions can be suppressed, and the swelling of the battery due to the generation of gas and the deterioration during cycle charge / discharge can be improved.

【００３０】更に化学量論組成比よりも過剰量のリチウ
ム、ホウ素、硫黄との相乗効果によってリチウムマンガ
ン複合酸化物の自己放電が抑制される。これにより保存
特性が向上する。Further, the self-discharge of the lithium-manganese composite oxide is suppressed by the synergistic effect with the excess amount of lithium, boron and sulfur over the stoichiometric composition ratio. This improves the storage characteristics.

【００３１】また本発明では特にハロゲン元素を含有す
ることが好ましい。ホウ素とハロゲン元素との相乗効果
によって粒子性状を球状とする。球状の粒子は充填性に
優れ、かつバインダーとなじみやすい。このため高い充
放電容量を有し、かつ結着性、表面の平滑性に優れた正
極板を作製できる。更に正極板の塗膜面が剥がれにく
く、また塗膜面表面のリチウムイオンの出入りが均一に
行われるため、サイクル充放電特性が改善できる。In the present invention, it is particularly preferable to contain a halogen element. The particle properties are made spherical by the synergistic effect of boron and halogen elements. The spherical particles have excellent filling properties and are easily compatible with the binder. Therefore, it is possible to produce a positive electrode plate having a high charge / discharge capacity, excellent binding property and surface smoothness. Furthermore, the coating film surface of the positive electrode plate is not easily peeled off, and lithium ions on and off the surface of the coating film surface are uniformly introduced, so that cycle charge / discharge characteristics can be improved.

【００３２】更に硫黄、過剰量のリチウム、ハロゲン元
素との相乗効果によって、リチウムマンガン複合酸化物
の粒子表面と電解液との界面におけるリチウムイオンの
移動抵抗が低減する。これにより実用レベルのサイクル
充放電特性を実現する。このように本発明では構成元素
の相乗効果を利用することによって、マンガンイオンの
溶出を抑え、かつリチウムイオンの移動抵抗を低減す
る。これにより電池の膨れを抑え、かつ実用レベルのサ
イクル充放電特性を実現する。Further, due to the synergistic effect of sulfur, an excessive amount of lithium, and a halogen element, the transfer resistance of lithium ions at the interface between the surface of the lithium manganese composite oxide particles and the electrolytic solution is reduced. As a result, a practical level of cycle charge / discharge characteristics is realized. As described above, in the present invention, by utilizing the synergistic effect of the constituent elements, the elution of manganese ions is suppressed and the migration resistance of lithium ions is reduced. As a result, the swelling of the battery is suppressed and the practical cycle charge / discharge characteristics are realized.

【００３３】更に本発明では（４００）ベクトル方向の
結晶子径を規格化し、結晶構造の歪みを低減することに
よって、サイクル充放電に伴う結晶構造の崩壊を抑制す
る。これによりサイクル充放電特性は更に向上し、実用
レベルのサイクル充放電特性が実現できる。Further, in the present invention, the crystallite diameter in the (400) vector direction is standardized to reduce the distortion of the crystal structure, thereby suppressing the collapse of the crystal structure due to cycle charge / discharge. As a result, the cycle charge / discharge characteristics are further improved and the cycle charge / discharge characteristics of a practical level can be realized.

【００３４】なお本発明のリチウムマンガン複合酸化物
粉末を構成する各元素の組成比は以下の方法によって定
量し、算出される。ハロゲン元素、酸素、ナトリウム以
外の各構成元素の含有量については、リチウムマンガン
複合酸化物粉末を硝酸に溶解し、プラズマ発光分光（Ｉ
ＣＰ）分析法により定量する。ハロゲン元素については
以下の方法にて定量する。まず純水にリチウムマンガン
複合酸化物粉末を投入し撹拌する。この後粉末をろ過し
て得られる上澄み水溶液に参照電極と指示電極のアニオ
ン選択性電極とを浸す。両電極間の起電力を測定し、発
生する起電力と水溶液中のハロゲン元素濃度との関係よ
りハロゲン元素を定量する。ナトリウムについては、原
子吸光分析法により定量する。酸素については他の構成
元素の含有量（重量％）の和を１００％から差し引いた
差分として算出する。そして一般式Ｌｉ１＋ａＭｂＭｎ
２−ａ−ｂＸｃＢｄＳｅＯ４＋ｆ及びＬｉ１＋ａＭｂＭ
ｎ ２−ａ−ｂＸｃＢｄＳｅＡｇＯ４＋ｆの各組成比を算
出する。The lithium manganese composite oxide of the present invention
The composition ratio of each element that constitutes the powder is determined by the following method.
Measured and calculated. Halogen element, oxygen, sodium or more
Regarding the content of each of the other constituent elements, lithium manganese
The complex oxide powder is dissolved in nitric acid and plasma emission spectroscopy (I
CP) Quantify by analytical method. About halogen element
Quantify by the following method. First, pure manganese in pure water
Add the complex oxide powder and stir. After this the powder is filtered
Anion of the reference electrode and the indicator electrode was added to the supernatant solution obtained by
Bath with selective electrodes. Measure the electromotive force between both electrodes and
It depends on the relationship between the electromotive force generated and the halogen element concentration in the aqueous solution.
Quantify halogen elements. For sodium,
Quantification by spectrophotometry. Other configurations for oxygen
The sum of element contents (% by weight) was subtracted from 100%
Calculate as a difference. And the general formula Li1 + aMbMn
2-a-bXcBdSeO4 + fAnd Li1 + aMbM
n 2-a-bXcBdSeAgO4 + fCalculate each composition ratio of
Put out.

【００３５】本発明では更に前記（５）、（９）及び
（１４）に記載したように、比表面積を規格化したリチ
ウムマンガン複合酸化物粉末とすることが好ましく、こ
れにより更に電池膨張の抑制、サイクル充放電特性の改
善が実現できる。なお前記（５）、（９）及び（１４）
では、窒素ガスを用いた定圧式ＢＥＴ吸着法によりリチ
ウムマンガン複合酸化物粉末の比表面積を測定する。In the present invention, as described in (5), (9) and (14) above, it is preferable to use a lithium manganese composite oxide powder having a standardized specific surface area, which further suppresses battery expansion. It is possible to improve the cycle charge / discharge characteristics. The above (5), (9) and (14)
Then, the specific surface area of the lithium-manganese composite oxide powder is measured by the constant pressure BET adsorption method using nitrogen gas.

【００３６】また前記（６）に記載したように、リチウ
ムマンガン複合酸化物粉末の１μｍ以下の粒子量を規格
化することが好ましく、これにより更に電池膨張の抑制
が実現できる。本発明ではレーザー回折散乱法により体
積基準の粒度分布を測定し、１μｍ以下の粒子量を算出
する。As described in (6) above, it is preferable to standardize the amount of particles of the lithium-manganese composite oxide powder of 1 μm or less, which can further suppress the battery expansion. In the present invention, the volume-based particle size distribution is measured by the laser diffraction scattering method, and the amount of particles of 1 μm or less is calculated.

【００３７】また本発明では、（４００）ベクトル方向
の結晶子径は、ＣｕＫα１をＸ線源とする粉末Ｘ線回折
法によりＸ線回折パターンを測定し、（４００）面に起
因する回折ピークより求める。結晶子とは単結晶と考え
られる最大限の集合を示し、結晶子径は以下の式（I）
で表されるシェラーの式によって算出される。Further, in the present invention, the crystallite diameter in the (400) vector direction is determined by measuring the X-ray diffraction pattern by the powder X-ray diffraction method using CuKα1 as the X-ray source. Ask. The crystallite refers to the maximum aggregate that can be considered as a single crystal, and the crystallite diameter is expressed by the following formula (I)
It is calculated by the Scherrer's formula represented by.

【００３８】[0038]

【数１】 [Equation 1]

【００３９】なお式（I）中のＤは結晶子の大きさ（オ
ングストローム）、Ｋはシェラー定数（βを積分幅より
算出した場合はＫ＝１．０５）、λはＸ線源の波長（Ｃ
ｕＫα１＝１．５４０５６２オングストローム）、βは
結晶子の大きさによる回折線の広がりの幅（ｒａｄｉａ
ｎ）、θは回折角２θ／２（ｄｅｇｒｅｅ）を示す。In the formula (I), D is the crystallite size (angstrom), K is the Scherrer constant (K = 1.05 when β is calculated from the integral width), and λ is the wavelength of the X-ray source ( C
uKα1 = 1.540562 angstrom), β is the width of the spread of the diffraction line (radia) depending on the size of the crystallite.
n) and θ represent diffraction angles 2θ / 2 (degree).

【００４０】また本発明のリチウムマンガン複合酸化物
粉末は、前記（８）に記載した組成となるように原料と
なる化合物を混合し、前記（１０）に記載したように酸
素濃度を規格化した雰囲気中で焼成することによって製
造できる。焼成雰囲気の酸素濃度を規格化することによ
って、結晶構造中の酸素欠損を抑制でき、結晶の歪みが
ほとんど無く、（４００）ベクトル方向の結晶子径が大
きなリチウムマンガン複合酸化物粉末を製造できる。In the lithium-manganese composite oxide powder of the present invention, the starting compounds were mixed so as to have the composition described in (8) above, and the oxygen concentration was standardized as described in (10) above. It can be manufactured by firing in an atmosphere. By normalizing the oxygen concentration in the firing atmosphere, oxygen vacancies in the crystal structure can be suppressed, crystal distortion is scarce, and a lithium-manganese composite oxide powder having a large crystallite size in the (400) vector direction can be produced.

【００４１】また本発明では、ナトリウム、カルシウム
とホウ素、硫黄との相乗効果によって、更に電解液との
反応活性点を低減でき、マンガンイオンの溶出を抑える
ことができる。これによりガス発生による電池の膨れを
更に抑え、実用レベルのサイクル充放電特性が実現でき
る。Further, in the present invention, the synergistic effect of sodium, calcium, boron and sulfur can further reduce the reaction active sites with the electrolytic solution and suppress the elution of manganese ions. As a result, swelling of the battery due to gas generation can be further suppressed, and practical level cycle charge / discharge characteristics can be realized.

【００４２】[0042]

【発明の実施の形態】次に本発明のリチウムマンガン複
合酸化物粉末について詳細に説明する。本発明は一般式
Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＯ４＋ｆで
表され、アルミニウムとマグネシウムとの合計量は、上
記一般式中の組成比ｂで表される。ｂは０＜ｂ≦０．２
であり、更に好ましくは０．０１≦ｂ≦０．１５、より
好ましくは０．０５≦ｂ≦０．１５である。このとき充
放電に伴うガスの発生が少なくなり、電池の膨れが抑え
られる。これは結晶構造が安定化し、マンガンイオンの
溶出が抑えられ、電解液の分解によるＣＯ２ガスの発生
が抑えられるためと考えられる。しかしｂ＞０．２では
添加量が増加してもガスの発生量はほぼ同等となる。ま
た添加量の増加による放電容量の低下が顕著に現れ、好
ましくない。ｂ＝０ではガス発生が改善できず好ましく
ない。BEST MODE FOR CARRYING OUT THE INVENTION Next, the lithium manganese composite oxide powder of the present invention will be described in detail. The present invention is represented by the general formula Li 1 + a M b Mn 2 -a-b X c B d S e O 4 + f, the total amount of aluminum and magnesium is represented by the composition ratio b in the general formula. b is 0 <b ≦ 0.2
And more preferably 0.01 ≦ b ≦ 0.15, and more preferably 0.05 ≦ b ≦ 0.15. At this time, gas generation due to charging / discharging is reduced and swelling of the battery is suppressed. It is considered that this is because the crystal structure is stabilized, the elution of manganese ions is suppressed, and the generation of CO 2 gas due to the decomposition of the electrolytic solution is suppressed. However, when b> 0.2, the gas generation amount becomes almost the same even if the addition amount increases. In addition, the discharge capacity remarkably decreases due to an increase in the addition amount, which is not preferable. When b = 0, gas generation cannot be improved, which is not preferable.

【００４３】次に立方晶スピネル型マンガン酸リチウム
では、リチウムは８ａの四面体サイトを占有する。しか
し化学量論組成比よりも過剰にリチウムを添加すると、
過剰量のリチウムの一部は、マンガンが存在する１６ｄ
の八面体サイトを占有することが知られている。化学量
論組成比よりも過剰にリチウムを添加することで、マン
ガンの一部をリチウムで置換できる。Next, in cubic spinel type lithium manganate, lithium occupies the tetrahedral sites of 8a. However, if lithium is added in excess of the stoichiometric composition ratio,
16d where manganese is present as part of excess lithium
It is known to occupy an octahedral site. By adding lithium in excess of the stoichiometric composition ratio, part of manganese can be replaced with lithium.

【００４４】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＯ４＋ｆにて、リチウムの組成比は（１＋ａ）
によって表される。化学量論組成比よりも過剰量のリチ
ウムはａで表され、０＜ａ≦０．２である。好ましくは
０＜ａ≦０．１５である。このように１６ｄの八面体サ
イトを占有するマンガンの一部をアルミニウムやマグネ
シウムに加えて、リチウムによって置換すると、相乗効
果が得られ、電池の膨れが抑えられるだけでなく、特に
サイクル充放電特性が向上する。これはマンガンの一部
がリチウムで置換されることによって、格子定数が小さ
くなり、スピネル構造が収縮することでイオン結合力が
増加し、結晶構造が更に安定化するためと考えられる。
しかしａ＞０．２では添加量が増加してもガスの発生量
はほぼ同等となり、また添加量の増加による放電容量の
低下が顕著に現れるため好ましくない。ａ＝０では上記
したアルミニウムやマグネシウムとの相乗効果による結
晶構造の安定化が行えなくなるため、好ましくない。The general formula Li 1 + a M b Mn 2-a-b X c
At B d S e O 4 + f , the composition ratio of lithium (1 + a)
Represented by An excess amount of lithium with respect to the stoichiometric composition ratio is represented by a, and 0 <a ≦ 0.2. Preferably 0 <a ≦ 0.15. As described above, when a part of manganese occupying the octahedral site of 16d is added to aluminum or magnesium and replaced with lithium, a synergistic effect is obtained and not only the swelling of the battery is suppressed but also the cycle charge / discharge characteristics are particularly improved. improves. It is considered that this is because when a part of manganese is replaced with lithium, the lattice constant becomes smaller, the spinel structure contracts, the ionic bond strength increases, and the crystal structure further stabilizes.
However, when a> 0.2, the gas generation amount becomes almost the same even if the addition amount increases, and the discharge capacity significantly decreases due to the increase of the addition amount, which is not preferable. When a = 0, the crystal structure cannot be stabilized due to the synergistic effect with aluminum and magnesium, which is not preferable.

【００４５】本発明の構成元素であるホウ素は、焼成の
ときに原料混合物中のリチウムと反応し、リチウム、ホ
ウ素、酸素からなる化合物を形成する。この化合物は融
剤（フラックス）として作用するため、リチウムマンガ
ン複合酸化物は、結晶成長が促進し、結晶性が高まる。
図１に示したように、ホウ素が増加すると共にリチウム
マンガン複合酸化物粉末の比表面積が小さくなっていく
のが分かる。このように化学量論比よりも過剰のリチウ
ムと共にホウ素を添加することによって、結晶粒子の焼
結が進行し、結晶性に優れ、かつ粒子径の大きなリチウ
ムマンガン複合酸化物粉末が得られる。また図１に示し
たようにハロゲン元素を含有しない場合でも前記した過
剰のリチウムとホウ素との効果は得られ、ホウ素量が増
加すると共に比表面積が小さくなることが分かる。Boron, which is a constituent element of the present invention, reacts with lithium in the raw material mixture during firing to form a compound consisting of lithium, boron and oxygen. Since this compound acts as a flux, the lithium-manganese composite oxide promotes crystal growth and enhances crystallinity.
As shown in FIG. 1, it can be seen that the specific surface area of the lithium-manganese composite oxide powder becomes smaller as the amount of boron increases. As described above, by adding boron together with lithium in excess of the stoichiometric ratio, sintering of crystal particles proceeds, and a lithium-manganese composite oxide powder having excellent crystallinity and a large particle size can be obtained. Further, as shown in FIG. 1, it can be seen that even when the halogen element is not contained, the effect of the excess lithium and boron is obtained, and the specific surface area becomes smaller as the amount of boron increases.

【００４６】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＯ４＋ｆにおいて、ホウ素の組成比はｄで表さ
れる。０＜ｄ≦０．０２であり、このとき図２に示した
ように電池膨張率が低下することが分かる。ホウ素を付
与することで焼結が進行し、結晶が緻密化し、結晶構造
が安定化する。さらに比表面積が小さくなり電解液との
反応活性点が少なくなる。このためマンガンイオンの溶
出が抑えられ、充放電に伴うガスの発生が抑制できたと
考えられる。しかしホウ素量がｄ＞０．０２のとき、電
池膨張率が大きくなっており、充放電時のガスの発生が
顕著になり好ましくない。The general formula Li 1 + a M b Mn 2-a-b X c
In B d S e O 4 + f , the composition ratio of boron expressed d. In It is understood that 0 <d ≦ 0.02, and at this time, the battery expansion rate decreases as shown in FIG. By adding boron, sintering proceeds, the crystal becomes dense, and the crystal structure is stabilized. Furthermore, the specific surface area becomes smaller, and the number of active sites for reaction with the electrolytic solution becomes smaller. Therefore, it is considered that the elution of manganese ions was suppressed, and the generation of gas due to charge / discharge could be suppressed. However, when the amount of boron is d> 0.02, the battery expansion rate becomes large, and the generation of gas during charging and discharging becomes remarkable, which is not preferable.

【００４７】また本発明では図２に示したように硫黄を
付与しないときに比べて、ホウ素と硫黄とを共に用いた
とき相乗効果が得られ、電池膨張率が大幅に低下するこ
とが分かる。理由は定かではないがホウ素がリチウム、
酸素と共に低融点化合物（フラックス）を形成する反応
を硫黄が促進すると考えられる。このため焼成の初期段
階にて低温度から低融点化合物が原料混合物全体に形成
され、フラックスの効果が得られると考えられる。これ
により原料混合物全体が均等に焼結し、局所的な異常粒
成長、微小粒子の残留をなくすことができる。このよう
にホウ素は硫黄と共に付与することでフラックスの効果
が均一に得られ、結晶性のばらつきがなく、より結晶構
造の安定化が実現できる。また図２に示したようにハロ
ゲン元素を含有しないときも、ホウ素と硫黄との相乗効
果が得られ、電池膨張率が低減できることが分かる。Further, in the present invention, as shown in FIG. 2, as compared with the case where sulfur is not added, a synergistic effect is obtained when boron and sulfur are used together, and it is understood that the battery expansion coefficient is significantly reduced. Although the reason is not clear, boron is lithium,
It is believed that sulfur promotes the reaction that forms a low melting point compound (flux) with oxygen. Therefore, it is considered that a compound having a low melting point is formed in the entire raw material mixture from a low temperature in the initial stage of firing, and the effect of the flux is obtained. As a result, the entire raw material mixture is uniformly sintered, and local abnormal grain growth and residual fine particles can be eliminated. Thus, by adding boron together with sulfur, the effect of the flux can be uniformly obtained, the crystallinity does not vary, and more stable crystal structure can be realized. Further, as shown in FIG. 2, it is understood that the synergistic effect of boron and sulfur can be obtained even when the halogen element is not contained, and the battery expansion coefficient can be reduced.

【００４８】本発明ではさらにハロゲン元素を付与する
ことが好ましい。焼成時にホウ素が融剤として作用する
とき、ハロゲン元素は粒子表面に偏析し、粒子性状を改
善する効果を示す。つまりホウ素とハロゲン元素とを共
に用いることで、結晶性に優れ、比表面積が小さく、粗
大粒子を含まず、かつ球状で、粒子径の揃ったリチウム
マンガン複合酸化物粉末が得られる。In the present invention, it is preferable to add a halogen element. When boron acts as a flux during firing, the halogen element segregates on the surface of the particles and exhibits the effect of improving the particle properties. That is, by using both boron and a halogen element, it is possible to obtain a lithium-manganese composite oxide powder having excellent crystallinity, a small specific surface area, no coarse particles, a spherical shape, and a uniform particle size.

【００４９】球状で、粒子径の揃った粉末となること
で、正極板を作製する際、カーボン材料で代表される導
電剤粉末との混合性が良くなり、電池の内部抵抗は減少
する。このため充放電特性、特に放電容量が向上する。
またバインダーと混練するときも、本発明のリチウムマ
ンガン複合酸化物粉末は、流動性に優れ、またバインダ
ーの高分子と絡まりやすく、表４に示したように優れた
結着性を有する。さらに粗大粒子を含まず、球状である
ため、作製した正極の塗膜面の表面は平滑性に優れる。
このため正極板の塗膜面は結着性に優れ剥がれにくく、
また表面が平滑で充放電に伴う塗膜面表面のリチウムイ
オンの出入りが均一に行われるため、図３に示したよう
にサイクル充放電特性において顕著な改善が得られる。The powder having a spherical shape and a uniform particle diameter improves the mixing property with the conductive agent powder typified by a carbon material when manufacturing the positive electrode plate, and reduces the internal resistance of the battery. Therefore, the charge / discharge characteristics, especially the discharge capacity is improved.
Further, when kneaded with a binder, the lithium manganese composite oxide powder of the present invention has excellent fluidity, is easily entangled with the binder polymer, and has excellent binding properties as shown in Table 4. Further, since it does not contain coarse particles and is spherical, the surface of the coating film of the produced positive electrode is excellent in smoothness.
For this reason, the coating surface of the positive electrode plate has excellent binding properties and is difficult to peel off,
Further, since the surface is smooth and the lithium ions in and out of the surface of the coating film during charge and discharge are uniformly performed, a remarkable improvement in cycle charge and discharge characteristics can be obtained as shown in FIG.

【００５０】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＯ４＋ｆにおいて、Ｘはフッ素、塩素、臭素、
ヨウ素から選ばれた少なくとも一種類のハロゲン元素を
表し、ｃはその組成比を表す。ハロゲン元素は上記のう
ち一種または二種以上を併用して用いてもよい。特に実
施例に示したようにフッ素、塩素が好ましい。本発明で
はハロゲン元素の組成比ｃは０≦ｃ≦０．０５であり、
このとき図３に示したように優れたサイクル充放電特性
が得られる。しかしｃ＞０．０５では、ハロゲン元素の
量が増加しても、サイクル充放電特性は低く、好ましく
ない。更に図３に示したように、ホウ素が含有されてい
ないときはサイクル充放電特性に改善が得られにくいこ
とが分かる。これは粒子性状を球状とする効果がハロゲ
ン元素とホウ素とを共に用いた相乗効果によるためであ
り、本発明ではホウ素と共にハロゲン元素を使用するこ
とが好ましい。The general formula Li 1 + a M b Mn 2-a-b X c
In B d S e O 4 + f , X is fluorine, chlorine, bromine,
It represents at least one kind of halogen element selected from iodine, and c represents its composition ratio. The halogen element may be used alone or in combination of two or more. Fluorine and chlorine are particularly preferable as shown in the examples. In the present invention, the composition ratio c of the halogen element is 0 ≦ c ≦ 0.05,
At this time, excellent cycle charge / discharge characteristics are obtained as shown in FIG. However, when c> 0.05, the cycle charge / discharge characteristics are poor even if the amount of the halogen element increases, which is not preferable. Further, as shown in FIG. 3, it is understood that it is difficult to improve the cycle charge / discharge characteristics when boron is not contained. This is because the effect of making the particle properties spherical is due to the synergistic effect of using both the halogen element and boron, and in the present invention, it is preferable to use the halogen element together with boron.

【００５１】本発明は更に組成中に硫黄を含有してな
る。正極板の抵抗を図４に示す。図４では交流インピー
ダンス法により試験電池の内部インピーダンスを測定
し、設定した等価回路に基づき解析した。なお測定方
法、等価回路の設定、解析方法は逢坂哲彌、２Ｄ１６、
電池討論会予稿集（１９９９）、及び角崎、富山県工業
技術センター技報（１９９９）などをもとに行った。図
４より硫黄を添加することによって正極板の抵抗が低減
することが分かる。比較例である組成中の化学量論組成
比よりも過剰のＬｉ比ａ＝０かつハロゲン元素の比ｃ＝
０のときに比べて、本発明のリチウムマンガン複合酸化
物は正極抵抗が低いことが分かる。理由は定かではない
が、化学量論比よりも過剰量のリチウムと共に硫黄を付
与することによって、リチウムイオンの移動抵抗が低減
することが分かる。特に本発明ではハロゲン元素を含有
することが好ましく、このとき更にリチウムイオンの移
動抵抗は低減する。ハロゲン元素及び化学量論比よりも
過剰量のリチウムと共に硫黄を付与することによって、
相乗効果が生じ、リチウムマンガン複合酸化物の粒子表
面と電解液との界面におけるリチウムイオンの移動抵抗
が低減すると考えられる。The present invention further comprises sulfur in the composition. The resistance of the positive electrode plate is shown in FIG. In FIG. 4, the internal impedance of the test battery was measured by the AC impedance method and analyzed based on the set equivalent circuit. The measurement method, the setting of the equivalent circuit, and the analysis method are Tetsuya Osaka and 2D16,
It was conducted based on the battery discussion meeting proceedings (1999) and Kadosaki, Toyama Industrial Technology Center Technical Report (1999). It can be seen from FIG. 4 that the resistance of the positive electrode plate is reduced by adding sulfur. The Li ratio a = 0 and the halogen element ratio c = in excess of the stoichiometric composition ratio in the composition of the comparative example
It can be seen that the lithium manganese composite oxide of the present invention has a lower positive electrode resistance than when it is zero. Although the reason is not clear, it is understood that the transfer resistance of lithium ions is reduced by adding sulfur together with an amount of lithium in excess of the stoichiometric ratio. In particular, the present invention preferably contains a halogen element, and at this time, the migration resistance of lithium ions is further reduced. By providing sulfur with halogen elements and an excess of lithium over stoichiometry,
It is considered that a synergistic effect occurs and the lithium ion transfer resistance at the interface between the lithium manganese composite oxide particle surface and the electrolytic solution is reduced.

【００５２】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＯ４＋ｆにおいて、硫黄の組成比はｅで表され
る。０＜ｅ≦０．１であり、このとき図５に示したよう
に実用レベルのサイクル充放電特性が得られる。特に
０．００１≦ｅ≦０．０６が好ましく、このとき容量維
持率が６０％以上の優れたサイクル充放電特性が得られ
る。前述したように正極抵抗が低減し、電池の内部抵抗
が減少したため、サイクル充放電特性が向上したと考え
られる。ｅ＞０．１ではサイクル充放電特性が低下し、
好ましくない。図５に示したように、特に本発明では硫
黄と共にハロゲン元素を含有することが好ましく、この
とき特に優れたサイクル充放電特性が得られる。The general formula Li 1 + a M b Mn 2-a-b X c
In B d S e O 4 + f , the composition ratio of sulfur is represented by e. 0 <e ≦ 0.1, and at this time, practical level cycle charge / discharge characteristics are obtained as shown in FIG. In particular, 0.001 ≦ e ≦ 0.06 is preferable, and at this time, excellent cycle charge / discharge characteristics with a capacity retention ratio of 60% or more can be obtained. It is considered that the cycle charge / discharge characteristics were improved because the positive electrode resistance was reduced and the internal resistance of the battery was reduced as described above. When e> 0.1, the cycle charge / discharge characteristics deteriorate,
Not preferable. As shown in FIG. 5, particularly in the present invention, it is preferable to contain a halogen element together with sulfur, and at this time, particularly excellent cycle charge / discharge characteristics can be obtained.

【００５３】また本発明では図６に示したように優れた
保存特性を実現できる。比較例のホウ素又は硫黄を含有
しない場合に比べて、本発明のリチウムマンガン複合酸
化物粉末は優れた保存特性であることが分かる。これは
化学量論比よりも過剰のリチウム、ホウ素、硫黄が粒子
表面に保護膜を形成し、自己放電を抑制するためである
と考えられる。これにより優れた保存特性が実現でき
る。Further, according to the present invention, excellent storage characteristics can be realized as shown in FIG. It can be seen that the lithium-manganese composite oxide powder of the present invention has excellent storage characteristics as compared with the comparative example containing no boron or sulfur. It is considered that this is because the excess amount of lithium, boron, or sulfur than the stoichiometric ratio forms a protective film on the particle surface and suppresses self-discharge. Thereby, excellent storage characteristics can be realized.

【００５４】更に本発明のリチウムマンガン複合酸化物
粉末は、比表面積についても規格化することで、さらに
優れた電池特性が得られる。すなわちリチウムマンガン
複合酸化物粉末の比表面積は０．２〜１．２ｍ２／ｇで
あることが好ましい。さらに好ましくは０．３〜０．７
ｍ２／ｇである。このとき図７に示したように、電池の
膨張率を抑えることができる。しかし図７中の比較例に
見られるように、本発明の構成元素のうちいずれかを含
有していない場合、比表面積を規格化しても優れた特性
は得られないことが分かる。Further, the lithium-manganese composite oxide powder of the present invention can obtain more excellent battery characteristics by standardizing the specific surface area. That is, the specific surface area of the lithium-manganese composite oxide powder is preferably 0.2 to 1.2 m 2 / g. More preferably 0.3 to 0.7
m 2 / g. At this time, as shown in FIG. 7, the expansion coefficient of the battery can be suppressed. However, as can be seen from the comparative example in FIG. 7, it can be seen that excellent characteristics cannot be obtained even if the specific surface area is standardized when any of the constituent elements of the present invention is not contained.

【００５５】粉末粒子の比表面積が０．２ｍ２／ｇ未満
では、粒子径が大きすぎてしまい、充放電においてリチ
ウムイオンの固体内拡散が進行しにくく、放電容量が低
下する。また１．２ｍ２／ｇより大きい場合、粒子径が
小さいために充放電特性、サイクル充放電特性が向上し
ないため好ましくない。If the specific surface area of the powder particles is less than 0.2 m 2 / g, the particle diameter becomes too large, and diffusion of lithium ions in the solid is difficult to proceed during charge and discharge, resulting in a decrease in discharge capacity. On the other hand, when it is larger than 1.2 m 2 / g, the particle size is small and the charge / discharge characteristics and cycle charge / discharge characteristics are not improved, which is not preferable.

【００５６】また本発明では、１μｍ以下の粒子量につ
いても規格化することで、更に電池膨張率を低減でき
る。本発明のリチウムマンガン複合酸化物粉末の１μｍ
以下の粒子は１体積％以下であることが好ましい。この
とき図８に示したように、電池膨張率を低減できる。し
かし図８中の比較例に見られるように、本発明の構成元
素のうちいずれかを含有していない場合、比表面積を規
格化しても優れた特性は得られないことが分かる。In the present invention, the battery expansion rate can be further reduced by standardizing the particle amount of 1 μm or less. 1 μm of the lithium manganese composite oxide powder of the present invention
The following particles are preferably 1% by volume or less. At this time, the battery expansion rate can be reduced as shown in FIG. However, as can be seen from the comparative example in FIG. 8, it can be seen that excellent characteristics cannot be obtained even if the specific surface area is standardized when any of the constituent elements of the present invention is not contained.

【００５７】また本発明では、リチウムマンガン複合酸
化物の結晶子の（４００）ベクトル方向の結晶子径を規
格化する。前述したように結晶子は単結晶と考えられる
最大限の集合を示す。このため結晶子径が大きいほど結
晶性に優れ、結晶構造の歪みが少ないことになる。立方
晶スピネル構造であるリチウムマンガン複合酸化物で
は、特に（４００）ベクトル方向の結晶子径を用いるこ
とによって単位格子の規則的な配列度が分かる。すなわ
ち（４００）ベクトル方向の結晶子径が大きいほど結晶
性に優れ、結晶構造の歪みが少ない。In the present invention, the crystallite diameter in the (400) vector direction of the crystallite of the lithium manganese oxide is standardized. As mentioned above, the crystallites show the maximum set that is considered to be a single crystal. Therefore, the larger the crystallite diameter, the better the crystallinity and the less the distortion of the crystal structure. In the lithium manganese composite oxide having a cubic spinel structure, the regular array degree of the unit cell can be found by using the crystallite diameter in the (400) vector direction. That is, the larger the crystallite diameter in the (400) vector direction, the better the crystallinity and the less the distortion of the crystal structure.

【００５８】本発明では（４００）ベクトル方向の結晶
子径は７５０〜１０００オングストロームである。この
とき図１０に示したように実用レベルの優れたサイクル
充放電特性を実現できる。（４００）ベクトル方向の結
晶子径が７５０オングストローム未満、又は請求項に記
載した本発明の組成を満たさない場合は、図１０に示し
たように実用レベルのサイクル充放電特性が得られず好
ましくない。In the present invention, the crystallite diameter in the (400) vector direction is 750 to 1000 angstroms. At this time, as shown in FIG. 10, excellent cycle charge / discharge characteristics of a practical level can be realized. If the crystallite diameter in the (400) vector direction is less than 750 angstroms or does not satisfy the composition of the present invention described in the claims, it is not preferable because practical level cycle charge / discharge characteristics cannot be obtained as shown in FIG. .

【００５９】更に（４００）ベクトル方向の結晶子径が
７５０〜１０００オングストロームに規格化したリチウ
ムマンガン複合酸化物粉末は、比表面積についても規格
化することで、さらに優れた電池特性が得られる。すな
わちリチウムマンガン複合酸化物粉末の比表面積は０．
２〜１ｍ２／ｇであることが好ましい。さらに好ましく
は０．３〜０．７ｍ２／ｇである。このとき図１１に示
したように、電池の膨張率を抑えることができる。しか
し図１１中の比較例に見られるように、本発明の構成元
素のうちいずれかを含有していない場合、比表面積を規
格化しても優れた特性は得られないことが分かる。Further, the lithium manganese composite oxide powder whose crystallite diameter in the (400) vector direction is standardized to 750 to 1000 angstroms can be obtained by further standardizing the specific surface area. That is, the specific surface area of the lithium manganese composite oxide powder is 0.
It is preferably 2-1 m 2 / g. More preferably, it is 0.3 to 0.7 m 2 / g. At this time, as shown in FIG. 11, the expansion coefficient of the battery can be suppressed. However, as seen in the comparative example in FIG. 11, it can be seen that excellent characteristics cannot be obtained even if the specific surface area is standardized when any of the constituent elements of the present invention is not contained.

【００６０】本発明はＬｉ１＋ａＭｂＭｎ２−ａ−ｂＸ
ｃＢｄＳｅＡｇＯ４＋ｆで表され、リチウム、アルミニ
ウム、マグネシウム、ホウ素、ハロゲン元素、硫黄の組
成比はそれぞれ上記の値が好ましい。ナトリウムとカル
シウムとの合計量は、上記一般式中の組成比ｇで表され
る。ｇは０．００００４≦ｇ≦０．０１５であり、ナト
リウムのみの場合は、０．００００８≦ｇ≦０．０１、
カルシウムのみの場合は、０．００００４≦ｇ≦０．０
０５が好ましい。The present invention is based on Li 1 + a M b Mn 2-a-b X.
represented by c B d S e A g O 4 + f, lithium, aluminum, magnesium, boron, halogens, the composition ratio of sulfur each above values preferred. The total amount of sodium and calcium is represented by the composition ratio g in the above general formula. g is 0.00004 ≦ g ≦ 0.015, and in the case of only sodium, 0.00008 ≦ g ≦ 0.01,
In the case of calcium only, 0.00004 ≦ g ≦ 0.0
05 is preferable.

【００６１】ナトリウム、カルシウムはホウ素と硫黄と
共に用いたときに相乗効果が得られ、電池膨張率を大幅
に低下する。理由は定かでないがナトリウム、カルシウ
ム、ホウ素、硫黄との化合物がリチウムマンガン複合酸
化物粒子の一部、もしくは全面を覆い電解質との反応性
を制御すると考えられる。このためマンガンイオンの溶
出が抑えられ、充放電に伴うガスの発生が抑制できると
考えられる。ナトリウム、カルシウムはリチウムに比べ
充放電容量を減少させる効果が少ないため、効果を上乗
せし、図１４、図１５に示すようにさらに電池膨張率を
低下させることができる。また、ｇ＞０．０１５ではホ
ウ素のフラックス効果を阻害するため好ましくない。ホ
ウ素の添加量を増やすか焼成温度を上げることで粒子を
成長させることはできるが、ホウ素を添加しすぎるとガ
スの発生を招き、焼成温度を上げすぎると放電容量やサ
イクル充放電特性を低下させるため好ましくない。When sodium and calcium are used together with boron and sulfur, a synergistic effect is obtained and the expansion coefficient of the battery is significantly reduced. Although the reason is not clear, it is considered that a compound with sodium, calcium, boron or sulfur covers a part or the whole surface of the lithium manganese composite oxide particles and controls the reactivity with the electrolyte. Therefore, it is considered that the elution of manganese ions can be suppressed and the generation of gas due to charge / discharge can be suppressed. Since sodium and calcium have less effect of reducing the charge / discharge capacity than lithium, the effect can be added and the expansion coefficient of the battery can be further reduced as shown in FIGS. 14 and 15. If g> 0.015, the flux effect of boron is hindered, which is not preferable. Particles can be grown by increasing the addition amount of boron or raising the firing temperature, but if boron is added too much, gas is generated, and if the firing temperature is raised too much, discharge capacity and cycle charge / discharge characteristics are deteriorated. Therefore, it is not preferable.

【００６２】リチウム、ナトリウム、カルシウム、ホウ
素、硫黄、焼成温度、表面積の全てのバランスが整うこ
とで、充放電に伴うガスの発生がほとんどなく、かつサ
イクル充放電特性と保存特性に優れたリチウムマンガン
複合酸化物を得ることができる。本発明では、さらにハ
ロゲン元素を含有しても同様の効果を得ることができ
る。Since lithium, sodium, calcium, boron, sulfur, calcination temperature, and surface area are all balanced, there is almost no generation of gas during charge / discharge, and lithium manganese is excellent in cycle charge / discharge characteristics and storage characteristics. A complex oxide can be obtained. In the present invention, the same effect can be obtained even if a halogen element is further contained.

【００６３】本発明のリチウムマンガン複合酸化物粉末
を製造するための原料混合物は、リチウム化合物、マン
ガン化合物、ホウ素化合物、ハロゲン化合物、硫黄含有
化合物、ナトリウム化合物、カルシウム化合物、並びに
アルミニウム化合物及び／又はマグネシウム化合物を混
合してなる。この原料混合物を焼成することによって製
造される。製造方法については以下に詳細に説明する。The raw material mixture for producing the lithium-manganese composite oxide powder of the present invention is a lithium compound, a manganese compound, a boron compound, a halogen compound, a sulfur-containing compound, a sodium compound, a calcium compound, and an aluminum compound and / or magnesium. It is prepared by mixing the compounds. It is produced by firing this raw material mixture. The manufacturing method will be described in detail below.

【００６４】（原料混合物の作製）本発明において原料
となるリチウム化合物は特に限定されないが、例えばＬ
ｉ ２ＣＯ３、ＬｉＯＨ、ＬｉＯＨ・Ｈ２Ｏ、Ｌｉ２Ｏ、
ＬｉＣｌ、ＬｉＮＯ３、Ｌｉ２ＳＯ４、ＬｉＨＣＯ３、
Ｌｉ(ＣＨ３ＣＯＯ)等が用いられる。またマンガン化合
物としては、ＭｎＯ２、ＭｎＣＯ３、Ｍｎ２Ｏ３、Ｍｎ
３Ｏ４などが用いられるが、特に制限されるものではな
い。(Preparation of Raw Material Mixture) In the present invention, raw materials
The lithium compound to be
i TwoCOThree, LiOH, LiOH / HTwoO, LiTwoO,
LiCl, LiNOThree, LiTwoSOFour, LiHCOThree,
Li (CHThreeCOO) or the like is used. Also manganese compound
As a product, MnOTwo, MnCOThree, MnTwoOThree, Mn
ThreeOFourAre used, but are not particularly limited.
Yes.

【００６５】マグネシウム化合物としては、ＭｇＯ、Ｍ
ｇＣＯ３、Ｍｇ（ＯＨ）２、ＭｇＣｌ２、ＭｇＳＯ４、
Ｍｇ（ＮＯ３）２、Ｍｇ（ＣＨ３ＣＯＯ）２、またアル
ミニウム化合物としては、Ａｌ２Ｏ３、Ａｌ（ＮＯ３）
３、Ａｌ２（ＳＯ４）３、Ａｌ２（ＣＯ３）３、Ａｌ
（ＣＨ３ＣＯＯ）３などが用いられるが、特に制限され
るものではない。As the magnesium compound, MgO, M
gCO 3 , Mg (OH) 2 , MgCl 2 , MgSO 4 ,
Mg (NO 3 ) 2 , Mg (CH 3 COO) 2 , and aluminum compounds such as Al 2 O 3 and Al (NO 3 ).
3 , Al 2 (SO 4 ) 3 , Al 2 (CO 3 ) 3 , Al
(CH 3 COO) 3 and the like are used, but are not particularly limited.

【００６６】本発明に使用されるホウ素化合物として
は、Ｂ２Ｏ３（融点４６０℃）、Ｈ３ＢＯ３（分解温度
１７３℃）が好ましい。ハロゲン元素を含む化合物も特
に限定されないが、ＮＨ４Ｆ、ＮＨ４Ｃｌ、ＮＨ４Ｂ
ｒ、ＮＨ４Ｉ、ＬｉＦ、ＬｉＣｌ、ＬｉＢｒ、ＬｉＩ、
ＭｎＦ２、ＭｎＣｌ２、ＭｎＢｒ２、ＭｎＩ２等が好ま
しい。The boron compound used in the present invention is preferably B 2 O 3 (melting point 460 ° C.) and H 3 BO 3 (decomposition temperature 173 ° C.). The compound containing a halogen element is also not particularly limited, but NH 4 F, NH 4 Cl, NH 4 B
r, NH 4 I, LiF, LiCl, LiBr, LiI,
MnF 2 , MnCl 2 , MnBr 2 , MnI 2 and the like are preferable.

【００６７】本発明で使用できる硫黄含有化合物は特に
限定されないが、Ｌｉ２ＳＯ４、ＭｎＳＯ４、（Ｎ
Ｈ４）２ＳＯ４、Ａｌ２（ＳＯ４）３、ＭｇＳＯ４など
が好ましく用いられる。The sulfur-containing compound which can be used in the present invention is not particularly limited, but Li 2 SO 4 , MnSO 4 , (N
H 4) 2 SO 4, Al 2 (SO 4) 3, etc. MgSO 4 is preferably used.

【００６８】本発明で使用できるナトリウム化合物とし
ては、Ｎａ２ＣＯ３、ＮａＯＨ、Ｎａ２Ｏ、ＮａＣｌ、
ＮａＮＯ３、Ｎａ２ＳＯ４、ＮａＨＣＯ３、Ｎａ(ＣＨ
３ＣＯＯ)などが用いられるがＭｎ原料、Ｌｉ原料中に
あらかじめ含有したものを用いてもよく、特に制限され
るものではない。The sodium compounds usable in the present invention include Na 2 CO 3 , NaOH, Na 2 O, NaCl,
NaNO 3 , Na 2 SO 4 , NaHCO 3 , Na (CH
3 COO) or the like is used, but those preliminarily contained in the Mn raw material or the Li raw material may be used and are not particularly limited.

【００６９】本発明で使用できるカルシウム化合物とし
ては、ＣａＯ、ＣａＣＯ３、Ｃａ（ＯＨ）２、ＣａＣｌ
２、ＣａＳＯ４、Ｃａ（ＮＯ３）２、Ｃａ（ＣＨ３ＣＯ
Ｏ） ２などが用いられるがＭｎ原料、Ｌｉ原料中にあら
かじめ含有したものを用いてもよく、特に制限されるも
のではない。Calcium compounds that can be used in the present invention
For CaO, CaCOThree, Ca (OH)Two, CaCl
Two, CaSOFour, Ca (NOThree)Two, Ca (CHThreeCO
O) TwoEtc. are used, but in Mn raw material and Li raw material
It is possible to use the one containing caulking, which is not particularly limited.
Not of.

【００７０】上記したリチウム化合物、マンガン化合
物、ホウ素化合物、ハロゲン化合物、硫黄含有化合物、
ナトリウム化合物、カルシウム化合物、並びにアルミニ
ウム化合物及び／又はマグネシウム化合物を各構成元素
が所定の組成比となるように混合する。このとき粉末状
の化合物をそのまま混合しても良く、水又は有機溶媒を
用いてスラリー状として混合しても良い。スラリー状の
混合物は乾燥して原料混合物とする。The above-mentioned lithium compound, manganese compound, boron compound, halogen compound, sulfur-containing compound,
A sodium compound, a calcium compound, and an aluminum compound and / or a magnesium compound are mixed so that each constituent element has a predetermined composition ratio. At this time, the powdery compound may be mixed as it is, or may be mixed as a slurry by using water or an organic solvent. The slurry-like mixture is dried to obtain a raw material mixture.

【００７１】（原料混合物の焼成）上記した方法で得ら
れる原料混合物を空気中または弱酸化雰囲気にて、６５
０〜１０００℃の温度で１〜２４時間焼成を行い、リチ
ウムマンガン複合酸化物粉末を合成する。図９に示した
ように、目的とする比表面積のリチウムマンガン複合酸
化物粉末が得られる。特に焼成の温度は７５０〜９５０
℃が好ましく、また焼成の時間は６〜１２時間が好まし
い。(Calcination of Raw Material Mixture) The raw material mixture obtained by the above method is subjected to 65% in air or in a weakly oxidizing atmosphere.
The lithium-manganese composite oxide powder is synthesized by firing at a temperature of 0 to 1000 ° C. for 1 to 24 hours. As shown in FIG. 9, a lithium manganese composite oxide powder having a target specific surface area can be obtained. Especially the firing temperature is 750 to 950.
C. is preferable, and the firing time is preferably 6 to 12 hours.

【００７２】焼成温度が６５０℃よりも低い場合、未反
応の原料がリチウムマンガン複合酸化物粉末中に残留
し、本発明の目的を達成できる十分な特性が得られな
い。また、１０００℃よりも高い温度で焼成した場合、
Ｌｉ２ＭｎＯ３やＬｉＭｎＯ２等の副生成物が生成しや
すくなり、単位重量当たりの放電容量の低下、サイクル
充放電特性の低下、動作電圧の低下を招く。焼成の時間
は、１時間未満では原料混合物の粒子間の拡散反応が進
行せず、目的とするリチウムマンガン複合酸化物粉末が
得られない。また２４時間より長く焼成を行うと焼結に
よる粗大粒子が形成され、好ましくない。When the firing temperature is lower than 650 ° C., the unreacted raw material remains in the lithium manganese composite oxide powder, and sufficient characteristics for achieving the object of the present invention cannot be obtained. Also, when fired at a temperature higher than 1000 ° C,
By-products such as Li 2 MnO 3 and LiMnO 2 are likely to be generated, leading to a decrease in discharge capacity per unit weight, a decrease in cycle charge / discharge characteristics, and a decrease in operating voltage. If the firing time is less than 1 hour, the diffusion reaction between particles of the raw material mixture does not proceed, and the desired lithium manganese oxide powder cannot be obtained. Further, if the firing is performed for more than 24 hours, coarse particles are formed by sintering, which is not preferable.

【００７３】また、上記した方法で得られる原料混合物
を酸素濃度１８％以上の酸化雰囲気にて焼成する。図１
２に示したように焼成雰囲気中の酸素濃度が１８％以上
のとき、（４００）ベクトル方向の結晶子径が８００オ
ングストローム以上のリチウムマンガン複合酸化物粉末
が得られる。焼成雰囲気中の酸素濃度を最適に制御し、
結晶構造中に十分な酸素を供給することで（４００）ベ
クトル方向の結晶子径を７５０〜１０００オングストロ
ームのリチウムマンガン複合酸化物粉末とすることがで
きる。The raw material mixture obtained by the above method is fired in an oxidizing atmosphere having an oxygen concentration of 18% or more. Figure 1
As shown in 2, when the oxygen concentration in the firing atmosphere is 18% or more, a lithium manganese composite oxide powder having a crystallite size in the (400) vector direction of 800 angstroms or more is obtained. Optimum control of oxygen concentration in the firing atmosphere,
By supplying sufficient oxygen into the crystal structure, a lithium manganese composite oxide powder having a crystallite size in the (400) vector direction of 750 to 1000 angstroms can be obtained.

【００７４】上記焼成により得られるリチウムマンガン
複合酸化物粉末をらいかい乳鉢やボールミル、振動ミル
などにより粉砕しても構わない。上記方法によって比表
面積が０．２〜１．２ｍ２／ｇである本発明のリチウム
マンガン複合酸化物粉末を得ることができる。The lithium-manganese composite oxide powder obtained by the above firing may be pulverized by a mortar, ball mill, vibration mill or the like. The lithium manganese composite oxide powder of the present invention having a specific surface area of 0.2 to 1.2 m 2 / g can be obtained by the above method.

【００７５】本発明のリチウムイオン二次電池は、正極
活物質に本発明のリチウムマンガン複合酸化物粉末を使
用してなる。負極活物質には金属リチウム、リチウム合
金、又はリチウムイオンを吸蔵放出可能な化合物が使用
できる。リチウム合金としては例えばＬｉＡｌ合金，Ｌ
ｉＳｎ合金，ＬｉＰｂ合金などが使用できる。リチウム
イオンを吸蔵放出可能な化合物としては例えばグラファ
イト，黒鉛などの炭素材料が使用できる。The lithium ion secondary battery of the present invention comprises the lithium manganese composite oxide powder of the present invention as the positive electrode active material. As the negative electrode active material, metallic lithium, a lithium alloy, or a compound capable of inserting and extracting lithium ions can be used. Examples of the lithium alloy include LiAl alloy and L
An iSn alloy, a LiPb alloy, etc. can be used. A carbon material such as graphite or graphite can be used as the compound capable of inserting and extracting lithium ions.

【００７６】電解液としては作動電圧で変質、分解しな
い化合物であれば特に限定されず使用できる。溶媒とし
て例えばジメトキシエタン，ジエトキシエタン，エチレ
ンカーボネート，プロピレンカーボネート，ジメチルカ
ーボネート，ジエチルカーボネート，エチルメチルカー
ボネート，メチルホルメート，γ−ブチロラクトン，２
−メチルテトラヒドロフラン，ジメチルスルホキシド，
スルホランなどの有機溶媒が使用でき、また前記した有
機溶媒群から選ばれた２種以上を混合して使用しても構
わない。電解質としては例えば過塩素酸リチウム，四フ
ッ化ホウ酸リチウム，四フッ化リン酸リチウム，トリフ
ルオロメタン酸リチウムなどのリチウム塩などが使用で
きる。上記した電解液と電解質とを混合して電解液とし
て使用する。ここでゲル化剤などを添加し、ゲル状とし
て使用してもよく、また吸湿性ポリマーに吸収させて使
用しても構わない。更に無機系又は有機系のリチウムイ
オンの導電性を有する固体電解質を使用しても構わな
い。The electrolytic solution is not particularly limited as long as it is a compound that does not deteriorate or decompose at the operating voltage. Examples of the solvent include dimethoxyethane, diethoxyethane, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, methyl formate, γ-butyrolactone, 2
-Methyltetrahydrofuran, dimethylsulfoxide,
An organic solvent such as sulfolane can be used, and two or more kinds selected from the above-mentioned organic solvent group may be mixed and used. As the electrolyte, for example, lithium salts such as lithium perchlorate, lithium tetrafluoroborate, lithium tetrafluorophosphate and lithium trifluoromethanoate can be used. The above-mentioned electrolytic solution and electrolyte are mixed and used as an electrolytic solution. Here, a gelling agent or the like may be added and used as a gel, or may be used after being absorbed by a hygroscopic polymer. Further, an inorganic or organic solid electrolyte having lithium ion conductivity may be used.

【００７７】更にセパレーターとしてポリエチレン製、
ポリプロピレン製等の多孔性膜等が使用できる。本発明
のリチウムマンガン複合酸化物粉末、上記した負極活物
質、電解液、セパレーターを用いて定法に従いリチウム
イオン二次電池とする。これにより従来達成できなかっ
た優れた電池特性が実現できる。Further, as a separator, made of polyethylene,
A porous film made of polypropylene or the like can be used. A lithium-ion secondary battery is prepared according to a standard method using the lithium-manganese composite oxide powder of the present invention, the above-mentioned negative electrode active material, electrolytic solution, and separator. As a result, excellent battery characteristics that could not be achieved in the past can be realized.

【００７８】[0078]

【実施例】以下、本発明の実施例について説明するが、
本発明は具体的実施例のみに限定されるものではない。
以下、請求項１乃至７に記載の本発明の実施例について
説明する。 〔実施例１〕原料となる化合物として炭酸リチウム（Ｌ
ｉ２ＣＯ３）、三酸化二マンガン（Ｍｎ２Ｏ３）、炭酸
マグネシウム（ＭｇＣＯ３）、フッ化リチウム（Ｌｉ
Ｆ）、ホウ素酸（Ｈ３ＢＯ３）、硫酸リチウム（Ｌｉ２
ＳＯ４）を使用した。ここで三酸化二マンガンには体積
基準の５０％径が１５μｍ、含有硫酸分（ＳＯ４）が
０．０１重量％未満の粉末を用いた。EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to the specific examples.
Examples of the present invention described in claims 1 to 7 will be described below. [Example 1] Lithium carbonate (L
i 2 CO 3 ), dimanganese trioxide (Mn 2 O 3 ), magnesium carbonate (MgCO 3 ), lithium fluoride (Li
F), boric acid (H 3 BO 3 ), lithium sulfate (Li 2
SO 4) was used. Here, for dimanganese trioxide, a powder having a volume-based 50% diameter of 15 μm and a sulfuric acid content (SO 4 ) of less than 0.01% by weight was used.

【００７９】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＯ４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハ
ロゲン元素を示す。）において、Ｌｉの組成比が１＋ａ
＝１．０９、Ｍｇの組成比がｂ＝０．０１、Ｆの組成比
がｃ＝０．０５、Ｂの組成比がｄ＝０．００５、Ｓの組
成比がｅ＝０．００１となるように前記原料となる化合
物を秤量し、乾式混合して原料混合粉末とした。得られ
た原料混合物を大気雰囲気中にて８５０℃で１０時間焼
成した。そしてライカイ乳鉢にて粉砕し、粉末の比表面
積が０．４ｍ２／ｇのリチウムマンガン複合酸化物粉末
が得られた。なお原料の三酸化二マンガンの５０％径、
及びリチウムマンガン複合酸化物粉末の比表面積は、後
述する（粉体の評価）に従い測定した。The general formula Li 1 + a M b Mn 2-a-b X c
In B d S e O 4 + f (M represents Al and / or Mg, and X represents a halogen element), the composition ratio of Li is 1 + a.
= 1.09, the composition ratio of Mg is b = 0.01, the composition ratio of F is c = 0.05, the composition ratio of B is d = 0.005, and the composition ratio of S is e = 0.001. Thus, the raw material compound was weighed and dry mixed to obtain a raw material mixed powder. The obtained raw material mixture was fired at 850 ° C. for 10 hours in the air atmosphere. Then, it was crushed in a mortar mortar to obtain a lithium manganese composite oxide powder having a specific surface area of 0.4 m 2 / g. The 50% diameter of the raw material dimanganese trioxide,
The specific surface area of the lithium-manganese composite oxide powder was measured according to (Evaluation of powder) described later.

【００８０】〔実施例２及び比較例１，２〕原料となる
化合物のうち、炭酸マグネシウムの代わりに酸化アルミ
ニウム（Ａｌ２Ｏ３）を使用し、表１に示した組成比と
なるように原料となる各化合物を秤量し、原料混合粉末
とする以外は、実施例１と同様にして、リチウムマンガ
ン複合酸化物粉末を作製した。得られた結果を表２に示
した。[Example 2 and Comparative Examples 1 and 2] Of the compounds used as raw materials, aluminum oxide (Al 2 O 3 ) was used instead of magnesium carbonate, and the raw materials were adjusted to have the composition ratios shown in Table 1. Lithium-manganese composite oxide powder was produced in the same manner as in Example 1 except that each of the compounds described below was weighed and used as the raw material mixed powder. The obtained results are shown in Table 2.

【００８１】[0081]

【表１】 [Table 1]

【００８２】[0082]

【表２】 [Table 2]

【００８３】〔実施例３〜５及び比較例３，４〕一般式
Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＯ
４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハロゲン元素
を示す。）において、Ｌｉの組成比が１＋ａ＝１．０
４、Ａｌの組成比がｂ＝０．１、Ｆの組成比がｃ＝０．
０５、Ｓの組成比がｅ＝０．０２、Ｂの組成比が表３に
示した値となるように原料となる化合物を秤量し、原料
混合粉末とする以外は実施例２と同様にして、リチウム
マンガン複合酸化物粉末を作製した。Examples 3 to 5 and Comparative Examples 3 and 4 General Formula Li 1 + a M b Mn 2-a−b X c B d S e O
In 4 + f (M represents Al and / or Mg, and X represents a halogen element), the composition ratio of Li is 1 + a = 1.0.
4, the Al composition ratio is b = 0.1, and the F composition ratio is c = 0.
In the same manner as in Example 2 except that the raw material compound powder was weighed so that the composition ratio of 05 and S was e = 0.02 and the composition ratio of B was the value shown in Table 3. A lithium manganese composite oxide powder was prepared.

【００８４】[0084]

【表３】 [Table 3]

【００８５】〔実施例６，７及び比較例５〕一般式Ｌｉ
１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＯ４＋ｆ（Ｍは
Ａｌ及び／またはＭｇ、Ｘはハロゲン元素を示す。）に
おいて、Ｌｉの組成比が１＋ａ＝１．０４、Ａｌの組成
比がｂ＝０．１、Ｂの組成比がｄ＝０．００５、Ｓの組
成比がｅ＝０．０２、Ｆの組成比が表４に示した値とな
るように原料の化合物を秤量し、原料混合粉末とする以
外は、実施例２と同様にして、リチウムマンガン複合酸
化物粉末を作製した。Examples 6 and 7 and Comparative Example 5 General formula Li
1 + a M b Mn 2- a-b X c B d S e O 4 + f (M is Al and / or Mg, X represents a halogen element.) In the composition ratio of Li is 1 + a = 1.04, the composition of Al The raw material compounds are weighed so that the ratio is b = 0.1, the composition ratio of B is d = 0.005, the composition ratio of S is e = 0.02, and the composition ratio of F is the value shown in Table 4. Then, a lithium manganese composite oxide powder was produced in the same manner as in Example 2 except that the raw material mixed powder was used.

【００８６】[0086]

【表４】 [Table 4]

【００８７】〔実施例８〜１４及び比較例６，７〕一般
式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＯ４＋ｆ
（ＭはＡｌ及び／またはＭｇ、Ｘはハロゲン元素を示
す。）において、Ｌｉの組成比が１＋ａ＝１．０４、Ａ
ｌの組成比がｂ＝０．１、Ｂの組成比がｄ＝０．００
５、Ｆの組成比がｃ＝０．０５、Ｓの組成比が表５に示
した値となるように原料の化合物を秤量し、原料混合粉
末とする以外は、実施例２と同様にして、リチウムマン
ガン複合酸化物粉末を作製した。Examples 8 to 14 and Comparative Examples 6 and 7 General Formula Li 1 + a M b Mn 2-a−b X c B d S e O 4 + f
(M is Al and / or Mg, and X is a halogen element.), The composition ratio of Li is 1 + a = 1.04, A
The composition ratio of 1 is b = 0.1, and the composition ratio of B is d = 0.00.
5, in the same manner as in Example 2 except that the raw material compounds were weighed so that the composition ratio of F was c = 0.05 and the composition ratio of S was the value shown in Table 5 to prepare a raw material mixed powder. A lithium manganese composite oxide powder was prepared.

【００８８】[0088]

【表５】 [Table 5]

【００８９】〔実施例１５〜１９及び比較例８〕一般式
Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＯ
４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハロゲン元素
を示す。）において、Ｌｉの組成比が１＋ａ＝１．０
４、Ａｌの組成比がｂ＝０．１、Ｂの組成比がｄ＝０．
００５、Ｆの組成比がｃ＝０、Ｓの組成比が表６に示し
た値となるように原料の化合物を秤量し、原料混合粉末
とする以外は、実施例２と同様にして、リチウムマンガ
ン複合酸化物粉末を作製した。Examples 15 to 19 and Comparative Example 8 General formula Li 1 + a M b Mn 2-a−b X c B d S e O
In 4 + f (M represents Al and / or Mg, and X represents a halogen element), the composition ratio of Li is 1 + a = 1.0.
4, the Al composition ratio is b = 0.1, and the B composition ratio is d = 0.
Lithium was prepared in the same manner as in Example 2 except that the raw material compounds were weighed so that the composition ratio of 005 and F was c = 0 and the composition ratio of S was the value shown in Table 6 to prepare a raw material mixed powder. A manganese composite oxide powder was produced.

【００９０】[0090]

【表６】 [Table 6]

【００９１】〔実施例２０〜２２及び比較例９〜１２〕
一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＯ
４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハロゲン元素
を示す。）において、組成比が表７に示した値となるよ
うに原料の化合物を秤量し、原料混合粉末とする以外
は、実施例２と同様にして、リチウムマンガン複合酸化
物粉末を作製した。得られた結果を表８に示した。[Examples 20 to 22 and Comparative Examples 9 to 12]
Formula Li 1 + a M b Mn 2 -a-b X c B d S e O
In 4 + f (M is Al and / or Mg, and X is a halogen element), the raw material compounds are weighed so that the composition ratio becomes the values shown in Table 7, and the raw material mixed powder is used. Lithium-manganese composite oxide powder was produced in the same manner as in 2. The obtained results are shown in Table 8.

【００９２】[0092]

【表７】 [Table 7]

【００９３】[0093]

【表８】 [Table 8]

【００９４】〔比較例１３〜１６〕一般式Ｌｉ１＋ａＭ
ｂＭｎ２−ａ−ｂＸｃＢｄＳｅＯ４＋ｆ（ＭはＡｌ及び
／またはＭｇ、Ｘはハロゲン元素を示す。）において、
Ｌｉの組成比が１＋ａ＝１、Ａｌの組成比がｂ＝０．
１、Ｂの組成比がｄ＝０．００５、Ｆの組成比がｃ＝
０、Ｓの組成比が表９に示した値となるように原料の化
合物を秤量し、原料混合粉末とする以外は、実施例２と
同様にして、リチウムマンガン複合酸化物粉末を作製し
た。[Comparative Examples 13 to 16] General formula Li 1 + a M
b Mn 2-a-b X c B d S e O 4 + f (M is Al and / or Mg, X represents a halogen element.) In,
The composition ratio of Li is 1 + a = 1, and the composition ratio of Al is b = 0.
1, the composition ratio of B is d = 0.005, and the composition ratio of F is c =
A lithium manganese composite oxide powder was produced in the same manner as in Example 2 except that the raw material compounds were weighed so that the composition ratio of 0 and S became the values shown in Table 9 to obtain the raw material mixed powder.

【００９５】[0095]

【表９】 [Table 9]

【００９６】〔実施例２３〜２８〕表１０に示した焼成
温度で焼成する以外は、実施例２と同様にして、リチウ
ムマンガン複合酸化物粉末を作製した。[Examples 23 to 28] Lithium-manganese composite oxide powders were produced in the same manner as in Example 2 except that firing was performed at the firing temperature shown in Table 10.

【００９７】[0097]

【表１０】 [Table 10]

【００９８】得られたリチウムマンガン複合酸化物粉末
は、以下の方法にて組成分析、比表面積、粒度分布の測
定を行った。また試験電池を作製し、各評価を行った。 （組成分析）所定量のリチウムマンガン複合酸化物粉末
を硝酸に溶解し、プラズマ発光分光（ＩＣＰ）分析法に
より、ハロゲン元素、酸素以外の各構成元素の含有量の
定量を行った。また所定量のリチウムマンガン複合酸化
物粉末を純水に投入して撹拌し、上澄み水溶液を得た。
アニオン選択性電極を指示電極に用いたイオンメーター
により、上澄み水溶液中のハロゲン元素を定量した。な
お測定の結果、本実施例にて作製したリチウムマンガン
複合酸化物粉末の各構成元素の組成比は、原料となる化
合物を秤量したときの各構成元素の組成比と同一であっ
た。The obtained lithium manganese composite oxide powder was subjected to composition analysis, specific surface area and particle size distribution measurement by the following methods. A test battery was prepared and each evaluation was performed. (Composition analysis) A predetermined amount of lithium-manganese composite oxide powder was dissolved in nitric acid, and the content of each constituent element other than halogen element and oxygen was quantified by plasma emission spectroscopy (ICP) analysis method. Further, a predetermined amount of lithium-manganese composite oxide powder was put into pure water and stirred to obtain a supernatant aqueous solution.
The halogen element in the supernatant aqueous solution was quantified by an ion meter using an anion-selective electrode as an indicator electrode. As a result of the measurement, the composition ratio of each constituent element of the lithium-manganese composite oxide powder produced in this example was the same as the composition ratio of each constituent element when the raw material compound was weighed.

【００９９】（粉末の評価）得られたリチウムマンガン
複合酸化物粉末の比表面積は、窒素ガスを用いた定圧式
ＢＥＴ吸着法により測定した。また５０％径はレーザー
回折散乱法により粒度分布を測定し、体積基準の粒子径
の対数を用いた積算分布を求め、この積算分布において
積算値が０．５となる粒子径として求めた。更に測定し
た体積基準の粒度分布の１μｍ以下の積算値を１μｍ以
下の粒子量（体積％）とした。(Evaluation of Powder) The specific surface area of the obtained lithium manganese composite oxide powder was measured by a constant pressure BET adsorption method using nitrogen gas. For the 50% size, the particle size distribution was measured by the laser diffraction scattering method, and the cumulative distribution using the logarithm of the volume-based particle size was determined, and the cumulative value was determined as the particle size at which the cumulative value was 0.5. Furthermore, the integrated value of 1 μm or less of the measured volume-based particle size distribution was defined as the particle amount (volume%) of 1 μm or less.

【０１００】（リチウムイオン二次電池の作製）ポリフ
ッ化ビニリデン５重量部を含有したノルマルメチルピロ
リドン溶液に正極活物質であるリチウムマンガン複合酸
化物粉末９０重量部、導電剤として炭素粉末５重量部と
を加え、混練してペーストを調製し、これをドクターブ
レード法にてアルミニウム極板に塗布し、乾燥して正極
板とした。また負極活物質に炭素材料を用いて同様にし
て銅極板に塗布し、負極板を作製した。セパレーターに
多孔性プロピレンフィルムを用い、電解液としてエチレ
ンカーボネイト：ジエチルカーボネイト＝１：１（体積
比）の混合溶媒にＬiＰＦ６を１ｍｏｌ／ｌの濃度で溶
解した溶液を用いてリチウムイオン二次電池を作製し
た。本実施例では正極板、負極板、セパレータを薄いシ
ート状に成形し、これらを巻回し、金属ラミネート樹脂
フィルムの電池ケースに収納し、ラミネート型電池とし
た。(Production of Lithium Ion Secondary Battery) 90 parts by weight of lithium manganese composite oxide powder as a positive electrode active material and 5 parts by weight of carbon powder as a conductive agent were added to a normal methylpyrrolidone solution containing 5 parts by weight of polyvinylidene fluoride. Was added and kneaded to prepare a paste, which was applied to an aluminum electrode plate by the doctor blade method and dried to obtain a positive electrode plate. Further, a carbon material was used for the negative electrode active material and similarly applied to a copper electrode plate to prepare a negative electrode plate. A porous propylene film was used as a separator, and a lithium ion secondary battery was prepared by using a solution prepared by dissolving LiPF 6 at a concentration of 1 mol / l in a mixed solvent of ethylene carbonate: diethyl carbonate = 1: 1 (volume ratio) as an electrolytic solution. It was made. In this example, a positive electrode plate, a negative electrode plate, and a separator were formed into a thin sheet shape, which were wound and housed in a battery case of a metal laminated resin film to obtain a laminated battery.

【０１０１】（電池膨張率の評価）ラミネート型電池を
６０℃にて電流密度０．５Ｃで４．３Ｖまで定電流充電
後、電流密度１．２Ｃで３．０Ｖまで放電する充放電を
３００サイクル行った。ガスの発生による電池の膨張率
（体積％）を下記の式（II）から求めた。なおここで
１．０Ｃは、１時間で充電又は放電が終了する電流密度
である。(Evaluation of Battery Expansion Rate) A laminate type battery was charged at 60 ° C. with a constant current density of 0.5 C to 4.3 V and then discharged with constant current of 1.2 C to 3.0 V for 300 cycles. went. The expansion coefficient (volume%) of the battery due to the generation of gas was obtained from the following formula (II). Here, 1.0 C is a current density at which charging or discharging is completed in 1 hour.

【０１０２】[0102]

【数２】 [Equation 2]

【０１０３】（サイクル充放電特性の評価）作製したラ
ミネート型電池を６０℃にて充電密度０．５Ｃで４．３
Ｖまで定電流充電後、１．２Ｃで３．０Ｖまで放電する
充放電を３００サイクル行い、３００サイクル目の容量
維持率（％）を下記の式（III）から求めた。(Evaluation of Cycle Charge / Discharge Characteristics) The produced laminate type battery was charged at 60 ° C. and a charge density of 0.5 C to 4.3.
After constant current charging to V, charging / discharging was performed at 1.2 C to 3.0 V for 300 cycles, and the capacity retention rate (%) at the 300th cycle was calculated from the following formula (III).

【０１０４】[0104]

【数３】 [Equation 3]

【０１０５】（正極板の剥がれの評価）上記したサイク
ル充放電特性の評価の後、アルゴンボックス中にて試験
電池を分解した。正極板を観察し、正極塗膜面の剥がれ
た部分の面積を算出した。(Evaluation of Peeling of Positive Electrode Plate) After the evaluation of the cycle charge / discharge characteristics, the test battery was disassembled in an argon box. The positive electrode plate was observed and the area of the peeled portion of the positive electrode coating film surface was calculated.

【０１０６】（保存特性の評価）作製したラミネート型
電池を６０℃にて充電密度０．５Ｃで４．３Ｖまで定電
流充電後、１．２Ｃで３．０Ｖまで放電した。次に再び
充電密度０．５Ｃで４．３Ｖまで定電流充電し、６０℃
で２０日間放置した。そして１．２Ｃで３．０Ｖまで放
電した。保存前後の放電容量の比（％）を下記の式（I
V）から求め、保存特性とした。(Evaluation of Storage Characteristics) The produced laminate type battery was charged at 60 ° C. with a constant charge of 0.5 C to 4.3 V and then discharged to 1.2 V at 3.0 V. Next, charge the battery again with a charge density of 0.5C to 4.3V at 60C.
Left for 20 days. And it discharged to 3.0V at 1.2C. The ratio (%) of the discharge capacity before and after storage can be calculated using the formula (I
V) and determined as storage characteristics.

【０１０７】[0107]

【数４】 [Equation 4]

【０１０８】（正極抵抗の測定）測定にはＳＩ１２８７
及びＳＩ１２６０（ＳＯＬＡＲＴＲＯＮ社製）を使用し
た。作製したラミネート型電池の正負極に設けたリード
線に測定機のクリップを取り付け、交流インピーダンス
法により内部インピーダンスを測定した。前述した逢坂
哲彌、２Ｄ１６、電池討論会予稿集（１９９９）と同形
状のＣｏｌｅ−Ｃｏｌｅプロットが得られた。図１３に
示した等価回路に従って解析し、正極抵抗を算出した。(Measurement of positive electrode resistance) SI1287 is used for measurement.
And SI1260 (manufactured by SOLARTRON) were used. Clips of a measuring instrument were attached to the lead wires provided on the positive and negative electrodes of the produced laminated battery, and the internal impedance was measured by the AC impedance method. The Cole-Cole plot having the same shape as the above-mentioned Tetsuya Osaka and 2D16, battery discussion meeting proceedings (1999) was obtained. Analysis was performed according to the equivalent circuit shown in FIG. 13 to calculate the positive electrode resistance.

【０１０９】以下、請求項８乃至１０に記載の本発明の
実施例について説明する。 〔実施例２９〕原料となる化合物として炭酸リチウム
（Ｌｉ２ＣＯ３）、三酸化二マンガン（Ｍｎ２Ｏ３）、
水酸化アルミニウム（Ａｌ（ＯＨ）３）、フッ化リチウ
ム（ＬｉＦ）、ホウ素酸（Ｈ３ＢＯ３）、硫酸リチウム
（Ｌｉ２ＳＯ４）を使用した。ここで三酸化二マンガン
には体積基準の５０％径が１５μｍ、含有硫酸分（ＳＯ
４）が０．０１重量％未満の粉末を用いた。The embodiments of the present invention described in claims 8 to 10 will be described below. Example 29 Lithium carbonate (Li 2 CO 3 ), dimanganese trioxide (Mn 2 O 3 ), as a raw material compound,
Aluminum hydroxide (Al (OH) 3 ), lithium fluoride (LiF), boric acid (H 3 BO 3 ), and lithium sulfate (Li 2 SO 4 ) were used. Here, the 50% diameter based on dimanganese trioxide has a diameter of 15 μm and contains sulfuric acid (SO
4 ) A powder having less than 0.01% by weight was used.

【０１１０】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＯ４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハ
ロゲン元素）において、Ｌｉの組成比が１＋ａ＝１．０
４、Ａｌの組成比がｂ＝０．１、Ｆの組成比がｃ＝０．
０５、Ｂの組成比がｄ＝０．００５、Ｓの組成比がｅ＝
０．０２となるように前記原料となる化合物を秤量し、
乾式混合して原料混合粉末とした。得られた原料混合粉
末を酸素濃度が２０％の雰囲気にて８５０℃で１０時間
焼成した。そしてライカイ乳鉢にて粉砕し、粉末の比表
面積が０．３ｍ２／ｇのリチウムマンガン複合酸化物粉
末が得られた。なお原料の三酸化二マンガンの５０％
径、及びリチウムマンガン複合酸化物粉末の比表面積
は、後述する（粉体の評価）に従い測定した。General formula Li 1 + a M b Mn 2-a-b X c
In B d S e O 4 + f (M is Al and / or Mg, X is a halogen element), the composition ratio of Li is 1 + a = 1.0.
4, the Al composition ratio is b = 0.1, and the F composition ratio is c = 0.
05, the composition ratio of B is d = 0.005, and the composition ratio of S is e =
The raw material compound is weighed so as to obtain 0.02,
Dry mixing was performed to obtain a raw material mixed powder. The obtained raw material mixed powder was fired at 850 ° C. for 10 hours in an atmosphere having an oxygen concentration of 20%. Then, it was crushed in a mortar mortar to obtain a lithium manganese composite oxide powder having a specific surface area of 0.3 m 2 / g. 50% of the raw material dimanganese trioxide
The diameter and the specific surface area of the lithium-manganese composite oxide powder were measured according to (Evaluation of powder) described later.

【０１１１】〔実施例３０〕原料となる化合物のうち、
水酸化アルミニウムの代わりに水酸化マグネシウム（Ｍ
ｇ（ＯＨ）２）を使用し、Ｌｉの組成比が１＋ａ＝１．
０９、Ｍｇの組成比がｂ＝０．０１となるように原料と
なる化合物を混合し、酸素濃度が２０％の雰囲気にて焼
成する以外は実施例２９と同様にして、リチウムマンガ
ン複合酸化物粉末を作製した。[Example 30] Of the compounds as the raw materials,
Instead of aluminum hydroxide, magnesium hydroxide (M
g (OH) 2 ) and the composition ratio of Li is 1 + a = 1.
09, lithium-manganese composite oxide was prepared in the same manner as in Example 29 except that the starting compounds were mixed so that the composition ratio of Mg was b = 0.01 and the mixture was fired in an atmosphere having an oxygen concentration of 20%. A powder was made.

【０１１２】〔実施例３１〕原料混合物を酸素濃度が３
０％の雰囲気にて６５０℃で焼成する以外は実施例３０
と同様にして、リチウムマンガン複合酸化物粉末を作製
した。実施例２９〜３１にて得られた結果を表１１に示
した。Example 31 A raw material mixture having an oxygen concentration of 3
Example 30 except firing at 650 ° C. in 0% atmosphere
Lithium-manganese composite oxide powder was produced in the same manner as. The results obtained in Examples 29 to 31 are shown in Table 11.

【０１１３】[0113]

【表１１】 [Table 11]

【０１１４】〔実施例３２，３３及び比較例１７，１
８〕一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅ
Ｏ４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハロゲン元
素）において、Ｌｉの組成比が１＋ａ＝１．０９、Ｍｇ
の組成比がｂ＝０．０１、Ｆの組成比がｃ＝０．０５、
Ｓの組成比がｅ＝０．０２、Ｂの組成比が表１２に示し
た値となるように原料となる化合物を混合し、酸素濃度
が３０％の雰囲気にて焼成する以外は実施例３０と同様
にして、リチウムマンガン複合酸化物粉末を作製した。[Examples 32 and 33 and Comparative Examples 17 and 1]
8] formula Li 1 + a M b Mn 2 -a-b X c B d S e
In O 4 + f (M is Al and / or Mg, X is a halogen element), the composition ratio of Li is 1 + a = 1.09, Mg
The composition ratio of b = 0.01, the composition ratio of F is c = 0.05,
Example 30 except that the starting compounds were mixed so that the composition ratio of S was e = 0.02 and the composition ratio of B was the value shown in Table 12, and firing was performed in an atmosphere with an oxygen concentration of 30%. Lithium-manganese composite oxide powder was produced in the same manner as.

【０１１５】[0115]

【表１２】 [Table 12]

【０１１６】〔実施例３４，３５及び比較例１９，２
０〕一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅ
Ｏ４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハロゲン元
素）において、Ｌｉの組成比が１＋ａ＝１．０９、Ｍｇ
の組成比がｂ＝０．０１、Ｂの組成比がｄ＝０．００
５、Ｓの組成比がｅ＝０．０２、Ｆの組成比が表１３に
示した値となるように原料の化合物を混合し、酸素濃度
が３０％の雰囲気にて焼成する以外は実施例３０と同様
にして、リチウムマンガン複合酸化物粉末を作製した。[Examples 34 and 35 and Comparative Examples 19 and 2]
0] formula Li 1 + a M b Mn 2 -a-b X c B d S e
In O 4 + f (M is Al and / or Mg, X is a halogen element), the composition ratio of Li is 1 + a = 1.09, Mg
Composition ratio of b = 0.01, composition ratio of B is d = 0.00
5, the composition of the raw materials was mixed so that the composition ratio of S was e = 0.02 and the composition ratio of F was the value shown in Table 13, and firing was performed in an atmosphere having an oxygen concentration of 30%. Lithium-manganese composite oxide powder was produced in the same manner as 30.

【０１１７】[0117]

【表１３】 [Table 13]

【０１１８】〔実施例３６〜３８及び比較例２１，２
２〕一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅ
Ｏ４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハロゲン元
素）において、Ｌｉの組成比が１＋ａ＝１．０９、Ｍｇ
の組成比がｂ＝０．０１、Ｂの組成比がｄ＝０．００
５、Ｆの組成比がｅ＝０．０５、Ｓの組成比が表１４に
示した値となるように原料の化合物を混合し、酸素濃度
が３０％の雰囲気にて焼成する以外は実施例３０と同様
にして、リチウムマンガン複合酸化物粉末を作製した。[Examples 36 to 38 and Comparative Examples 21 and 2]
2] formula Li 1 + a M b Mn 2 -a-b X c B d S e
In O 4 + f (M is Al and / or Mg, X is a halogen element), the composition ratio of Li is 1 + a = 1.09, Mg
Composition ratio of b = 0.01, composition ratio of B is d = 0.00
5, the composition of raw materials was mixed so that the composition ratio of F was e = 0.05, the composition ratio of S was the value shown in Table 14, and firing was performed in an atmosphere with an oxygen concentration of 30%. Lithium-manganese composite oxide powder was produced in the same manner as 30.

【０１１９】[0119]

【表１４】 [Table 14]

【０１２０】〔比較例２３〜２８〕一般式Ｌｉ１＋ａＭ
ｂＭｎ２−ａ−ｂＸｃＢｄＳｅＯ４＋ｆ（ＭはＡｌ及び
／またはＭｇ、Ｘはハロゲン元素）において、Ｍｇの組
成比がｂ＝０．０１、Ｂの組成比がｄ＝０．００５、Ｌ
ｉ、Ｆ、Ｓの組成比が表１５に示した値となるように原
料の化合物を混合し、酸素濃度が３０％の雰囲気にて焼
成する以外は実施例３０と同様にして、リチウムマンガ
ン複合酸化物粉末を作製した。[Comparative Examples 23 to 28] General formula Li 1 + a M
b Mn 2-a-b X c B d S e O 4 + f (M is Al and / or Mg, X is a halogen element) in the composition ratio of Mg is b = 0.01, the composition ratio of B is d = 0 0.005, L
A lithium manganese composite was prepared in the same manner as in Example 30 except that the starting compounds were mixed so that the composition ratios of i, F, and S were as shown in Table 15, and the mixture was fired in an atmosphere having an oxygen concentration of 30%. An oxide powder was produced.

【０１２１】[0121]

【表１５】 [Table 15]

【０１２２】〔実施例３９，４０及び比較例２９，３
０〕表１６に示した酸素濃度の雰囲気中で焼成する以外
は実施例３０と同様にして、リチウムマンガン複合酸化
物粉末を作製した。[Examples 39 and 40 and Comparative Examples 29 and 3
0] Lithium-manganese composite oxide powder was produced in the same manner as in Example 30 except that firing was performed in the atmosphere of oxygen concentration shown in Table 16.

【０１２３】[0123]

【表１６】 [Table 16]

【０１２４】得られたリチウムマンガン複合酸化物粉末
は、以下の方法にて組成分析、比表面積、粒度分布の測
定を行った。また試験電池を作製し、各評価を行った。 （組成分析）所定量のリチウムマンガン複合酸化物粉末
を硝酸に溶解し、プラズマ発光分光（ＩＣＰ）分析法に
より、ハロゲン元素、酸素以外の各構成元素の含有量の
定量を行った。また所定量のリチウムマンガン複合酸化
物粉末を純水に投入して撹拌し、上澄み水溶液を得た。
アニオン選択性電極を指示電極に用いたイオンメーター
により、上澄み水溶液中のハロゲン元素を定量した。な
お測定の結果、本実施例にて作製したリチウムマンガン
複合酸化物粉末の各構成元素の組成比は、原料となる化
合物を秤量したときの各構成元素の組成比と同一であっ
た。The obtained lithium manganese composite oxide powder was subjected to composition analysis, specific surface area and particle size distribution measurement by the following methods. A test battery was prepared and each evaluation was performed. (Composition analysis) A predetermined amount of lithium-manganese composite oxide powder was dissolved in nitric acid, and the content of each constituent element other than halogen element and oxygen was quantified by plasma emission spectroscopy (ICP) analysis method. Further, a predetermined amount of lithium-manganese composite oxide powder was put into pure water and stirred to obtain a supernatant aqueous solution.
The halogen element in the supernatant aqueous solution was quantified by an ion meter using an anion-selective electrode as an indicator electrode. As a result of the measurement, the composition ratio of each constituent element of the lithium-manganese composite oxide powder produced in this example was the same as the composition ratio of each constituent element when the raw material compound was weighed.

【０１２５】（粉末の評価）得られたリチウムマンガン
複合酸化物粉末の比表面積は、窒素ガスを用いた定圧式
ＢＥＴ吸着法により測定した。５０％径はレーザー回折
散乱法により粒度分布を測定し、体積基準の粒子径の対
数を用いた積算分布を求め、この積算分布において積算
値が０．５となる粒子径として求めた。(Evaluation of Powder) The specific surface area of the obtained lithium manganese composite oxide powder was measured by a constant pressure BET adsorption method using nitrogen gas. The 50% diameter was obtained by measuring the particle size distribution by the laser diffraction scattering method and determining the cumulative distribution using the logarithm of the particle diameter on a volume basis, and the cumulative distribution being 0.5.

【０１２６】（結晶子径の測定）理学電気（株）社製の
ＲＩＮＴ２５００Ｖを用いて測定した。Ｘ線源にはＣｕ
Ｋα１を用い、管電流１００ｍＡ、管電圧４０ｋＶにて
２θ＝４３．２〜４４．８°の範囲でＸ線回折パターン
を測定した。（４００）面に起因する回折ピークより以
下の式（I）で表されるシェラーの式によって算出され
る。(Measurement of Crystallite Diameter) RINT2500V manufactured by Rigaku Denki Co., Ltd. was used for measurement. Cu for the X-ray source
An X-ray diffraction pattern was measured using Kα1 at a tube current of 100 mA and a tube voltage of 40 kV in the range of 2θ = 43.2 to 44.8 °. It is calculated by the Scherrer's formula represented by the following formula (I) from the diffraction peak due to the (400) plane.

【０１２７】[0127]

【数５】 [Equation 5]

【０１２８】なお式（I）中のＤは結晶子の大きさ（オ
ングストローム）、Ｋはシェラー定数（βを積分幅より
算出した場合はＫ＝１．０５）、λはＸ線源の波長（Ｃ
ｕＫα１＝１．５４０５６２オングストローム）、βは
結晶子の大きさによる回折線の広がりの幅（ｒａｄｉａ
ｎ）、θは回折角２θ／２（ｄｅｇｒｅｅ）を示す。In the formula (I), D is the crystallite size (angstrom), K is the Scherrer constant (K = 1.05 when β is calculated from the integral width), and λ is the wavelength of the X-ray source ( C
uKα1 = 1.540562 angstrom), β is the width of the spread of the diffraction line (radia) depending on the size of the crystallite.
n) and θ represent diffraction angles 2θ / 2 (degree).

【０１２９】（リチウムイオン二次電池の作製）正極活
物質であるリチウムマンガン複合酸化物粉末９０重量
部、及び導電剤として炭素粉末５重量部、並びにポリフ
ッ化ビニリデン５重量部を含有したノルマルメチルピロ
リドン溶液とを混練してペーストを調製し、これをドク
ターブレード法にてアルミニウム極板に塗布し、乾燥し
て正極板とした。また負極活物質に炭素材料を用いて同
様にして銅極板に塗布し、負極板を作製した。セパレー
ターに多孔性プロピレンフィルムを用い、電解液として
エチレンカーボネイト：ジエチルカーボネイト＝１：１
（体積比）の混合溶媒にＬiＰＦ６を１ｍｏｌ／ｌの濃
度で溶解した溶液を用いてリチウムイオン二次電池を作
製した。本実施例では正極板、負極板、セパレータを薄
いシート状に成形し、これらを巻回し、金属ラミネート
樹脂フィルムの電池ケースに収納し、ラミネート型電池
とした。(Production of Lithium Ion Secondary Battery) Normal methyl pyrrolidone containing 90 parts by weight of lithium manganese composite oxide powder as a positive electrode active material, 5 parts by weight of carbon powder as a conductive agent, and 5 parts by weight of polyvinylidene fluoride. The solution was kneaded to prepare a paste, which was applied to an aluminum electrode plate by the doctor blade method and dried to obtain a positive electrode plate. Further, a carbon material was used for the negative electrode active material and similarly applied to a copper electrode plate to prepare a negative electrode plate. Porous propylene film is used for the separator, and ethylene carbonate: diethyl carbonate = 1: 1 as the electrolyte.
A lithium ion secondary battery was produced using a solution in which LiPF 6 was dissolved in a mixed solvent (volume ratio) at a concentration of 1 mol / l. In this example, a positive electrode plate, a negative electrode plate, and a separator were formed into a thin sheet shape, which were wound and housed in a battery case of a metal laminated resin film to obtain a laminated battery.

【０１３０】（電池膨張率の評価）ラミネート型電池を
６０℃にて電流密度０．５Ｃで４．３Ｖまで定電流充電
後、電流密度１．２Ｃで３．０Ｖまで放電する充放電を
３００サイクル行った。ガスの発生による電池の膨張率
（体積％）を下記の式（II）から求めた。なおここで
１．０Ｃは、１時間で充電又は放電が終了する電流密度
である。(Evaluation of Battery Expansion Rate) A laminated battery was charged at 60 ° C. with a constant current of 0.5 C to 4.3 V and then discharged with constant current of 1.2 C to 3.0 V for 300 cycles. went. The expansion coefficient (volume%) of the battery due to the generation of gas was obtained from the following formula (II). Here, 1.0 C is a current density at which charging or discharging is completed in 1 hour.

【０１３１】[0131]

【数６】 [Equation 6]

【０１３２】（サイクル充放電特性の評価）作製したラ
ミネート型電池を６０℃にて充電密度０．５Ｃで４．３
Ｖまで定電流充電後、１．２Ｃで２．７５Ｖまで放電す
る充放電を３００サイクル行い、３００サイクル目の容
量維持率（％）を下記の式（III）から求めた。(Evaluation of Cycle Charge / Discharge Characteristics) The produced laminate type battery was charged at 60 ° C. and a charge density of 0.5 C to 4.3.
After constant current charging to V, charging / discharging was performed at 1.2 C to 2.75 V for 300 cycles, and the capacity retention rate (%) at the 300th cycle was calculated from the following formula (III).

【０１３３】[0133]

【数７】 [Equation 7]

【０１３４】（正極板の剥がれの評価）上記したサイク
ル充放電特性の評価の後、アルゴンボックス中にて試験
電池を分解した。正極板を観察し、正極塗膜面の剥がれ
た部分の面積を算出した。(Evaluation of Peeling of Positive Electrode Plate) After the evaluation of the cycle charge / discharge characteristics, the test battery was disassembled in an argon box. The positive electrode plate was observed and the area of the peeled portion of the positive electrode coating film surface was calculated.

【０１３５】（正極抵抗の測定）測定にはＳＩ１２８７
及びＳＩ１２６０（ＳＯＬＡＲＴＲＯＮ社製）を使用し
た。作製したラミネート型電池の正負極に設けたリード
線に測定機のクリップを取り付け、交流インピーダンス
法により内部インピーダンスを測定した。前述した逢坂
哲彌、２Ｄ１６、電池討論会予稿集（１９９９）と同形
状のＣｏｌｅ−Ｃｏｌｅプロットが得られた。図１３に
示した等価回路に従って解析し、正極抵抗を算出した。(Measurement of positive electrode resistance) SI1287 is used for measurement.
And SI1260 (manufactured by SOLARTRON) were used. Clips of a measuring instrument were attached to the lead wires provided on the positive and negative electrodes of the produced laminated battery, and the internal impedance was measured by the AC impedance method. The Cole-Cole plot having the same shape as the above-mentioned Tetsuya Osaka and 2D16, battery discussion meeting proceedings (1999) was obtained. Analysis was performed according to the equivalent circuit shown in FIG. 13 to calculate the positive electrode resistance.

【０１３６】以下、請求項１１乃至１４に記載の本発明
の実施例について説明する。 〔実施例４１〕原料となる化合物として炭酸リチウム
（Ｌｉ２ＣＯ３）、三酸化二マンガン（Ｍｎ２Ｏ３）、
酸化アルミニウム（Ａｌ２Ｏ３）、フッ化リチウム（Ｌ
ｉＦ）、ホウ素酸（Ｈ３ＢＯ３）、硫酸リチウム（Ｌｉ
２ＳＯ４）、炭酸ナトリウム（Ｎａ２ＣＯ３）、酸化カ
ルシウム（ＣａＯ）を使用した。ここで三酸化二マンガ
ンには体積基準の５０％径が１５μｍ、含有硫酸分（Ｓ
Ｏ４）が０．０１重量％未満の粉末を用いた。Examples of the present invention described in claims 11 to 14 will be described below. Example 41 Lithium carbonate (Li 2 CO 3 ), dimanganese trioxide (Mn 2 O 3 ), as a raw material compound,
Aluminum oxide (Al 2 O 3 ), lithium fluoride (L
iF), boric acid (H 3 BO 3 ), lithium sulfate (Li
2 SO 4 ), sodium carbonate (Na 2 CO 3 ), calcium oxide (CaO) were used. Here, 50% by volume of dimanganese trioxide has a diameter of 15 μm and contains sulfuric acid (S
A powder having an O 4 ) content of less than 0.01% by weight was used.

【０１３７】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＡｇＯ４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘ
はハロゲン元素、ＡはＮａ及び／またはＣａを示す。）
において、Ｌｉの組成比が１＋ａ＝１．０５、Ａｌの組
成比がｂ＝０．１、Ｂの組成比がｄ＝０．０２、Ｓの組
成比がｅ＝０．００１、Ｎａの組成比がｆ＝０．０００
１となるように前記原料となる化合物を秤量し、乾式混
合して原料混合粉末とした。得られた原料混合物を大気
雰囲気中にて８５０℃で１０時間焼成した。そしてライ
カイ乳鉢にて粉砕し、粉末の比表面積が０．３ｍ２／ｇ
のリチウムマンガン複合酸化物粉末が得られた。なお原
料の三酸化二マンガンの５０％径、及びリチウムマンガ
ン複合酸化物粉末の比表面積は、後述する（粉体の評
価）に従い測定した。The general formula Li 1 + a M b Mn 2-a-b X c
B d S e A g O 4 + f (M is Al and / or Mg, X
Represents a halogen element, and A represents Na and / or Ca. )
In, the composition ratio of Li is 1 + a = 1.05, the composition ratio of Al is b = 0.1, the composition ratio of B is d = 0.02, the composition ratio of S is e = 0.001, and the composition ratio of Na is F = 0.000
The raw material compound was weighed so as to be 1, and dry-mixed to obtain a raw material mixed powder. The obtained raw material mixture was fired at 850 ° C. for 10 hours in the air atmosphere. Then, the powder was crushed in a mortar mortar and the specific surface area of the powder was 0.3 m 2 / g.
A lithium manganese composite oxide powder of was obtained. The 50% diameter of the raw material dimanganese trioxide and the specific surface area of the lithium-manganese composite oxide powder were measured according to (Powder evaluation) described later.

【０１３８】〔実施例４２，４３及び比較例３１乃至３
３〕一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅ
ＡｇＯ４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハロゲ
ン元素、ＡはＮａ及び／またはＣａを示す。）におい
て、組成比が表１７に示した値となるように原料の化合
物を秤量し、原料混合粉末とする以外は、実施例４１と
同様にして、リチウムマンガン複合酸化物粉末を作製し
た。得られた結果を表１８に示した。[Examples 42 and 43 and Comparative Examples 31 to 3]
3] formula Li 1 + a M b Mn 2 -a-b X c B d S e
In Ag O 4 + f (M is Al and / or Mg, X is a halogen element, A is Na and / or Ca), the raw material compounds are weighed so that the composition ratio becomes the value shown in Table 17. A lithium manganese composite oxide powder was produced in the same manner as in Example 41, except that the raw material mixed powder was used. The results obtained are shown in Table 18.

【０１３９】[0139]

【表１７】 [Table 17]

【０１４０】[0140]

【表１８】 [Table 18]

【０１４１】〔比較例３４乃至４３〕一般式Ｌｉ１＋ａ
ＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＡｇＯ４＋ｆ（ＭはＡ
ｌ及び／またはＭｇ、Ｘはハロゲン元素、ＡはＮａ及び
／またはＣａを示す。）において、組成比が表１９に示
した値となるように原料の化合物を秤量し、原料混合粉
末とする以外は、実施例４１と同様にして、リチウムマ
ンガン複合酸化物粉末を作製した。得られた結果を表２
０に示した。Comparative Examples 34 to 43 General formula Li 1 + a
M b Mn 2-a-b X c B d S e A g O 4 + f (M is A
1 and / or Mg, X is a halogen element, and A is Na and / or Ca. ), A lithium manganese composite oxide powder was produced in the same manner as in Example 41, except that the raw material compounds were weighed so that the composition ratio became the values shown in Table 19, and the raw material mixed powder was obtained. Table 2 shows the obtained results.
It was shown at 0.

【０１４２】[0142]

【表１９】 [Table 19]

【０１４３】[0143]

【表２０】 [Table 20]

【０１４４】〔実施例４４乃至４６及び比較例４４乃至
４６〕一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃＢｄＳ
ｅＡｇＯ４＋ｆ（ＭはＡｌ及び／またはＭｇ、Ｘはハロ
ゲン元素、ＡはＮａ及び／またはＣａを示す。）におい
て、組成比が表２１に示した値となるように原料の化合
物を秤量し、原料混合粉末とする以外は、実施例４１と
同様にして、リチウムマンガン複合酸化物粉末を作製し
た。得られた結果を表２２に示した。Examples 44 to 46 and Comparative Examples 44 to 46 General Formula Li 1 + a M b Mn 2-a−b X c B d S
In e Ag O 4 + f (M is Al and / or Mg, X is a halogen element, A is Na and / or Ca), the raw material compounds are weighed so that the composition ratio becomes the value shown in Table 21. Then, a lithium manganese composite oxide powder was produced in the same manner as in Example 41 except that the raw material mixed powder was used. The results obtained are shown in Table 22.

【０１４５】[0145]

【表２１】 [Table 21]

【０１４６】[0146]

【表２２】 [Table 22]

【０１４７】〔比較例４７乃至５６〕一般式Ｌｉ１＋ａ
ＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＡｇＯ４＋ｆ（ＭはＡ
ｌ及び／またはＭｇ、Ｘはハロゲン元素、ＡはＮａ及び
／またはＣａを示す。）において、組成比が表２３に示
した値となるように原料の化合物を秤量し、原料混合粉
末とする以外は、実施例４１と同様にして、リチウムマ
ンガン複合酸化物粉末を作製した。得られた結果を表２
４に示した。[Comparative Examples 47 to 56] General formula Li 1 + a
M b Mn 2-a-b X c B d S e A g O 4 + f (M is A
1 and / or Mg, X is a halogen element, and A is Na and / or Ca. In (), a lithium manganese composite oxide powder was produced in the same manner as in Example 41, except that the raw material compounds were weighed so that the composition ratio became the values shown in Table 23 and used as the raw material mixed powder. Table 2 shows the obtained results.
Shown in FIG.

【０１４８】[0148]

【表２３】 [Table 23]

【０１４９】[0149]

【表２４】 [Table 24]

【０１５０】〔実施例４７乃至５０〕一般式Ｌｉ１＋ａ
ＭｂＭｎ２−ａ−ｂＸｃＢｄＳｅＡｇＯ４＋ｆ（ＭはＡ
ｌ及び／またはＭｇ、Ｘはハロゲン元素、ＡはＮａ及び
／またはＣａを示す。）において、組成比が表２５に示
した値となるように原料の化合物を秤量し、原料混合粉
末とする以外は、実施例４１と同様にして、リチウムマ
ンガン複合酸化物粉末を作製した。実施例５０について
は、原料となる化合物のうち、酸化アルミニウムの代わ
りに炭酸マグネシウム（ＭｇＣＯ３）を使用した。得ら
れた結果を表２６に示した。[Examples 47 to 50] General formula Li 1 + a
M b Mn 2-a-b X c B d S e A g O 4 + f (M is A
1 and / or Mg, X is a halogen element, and A is Na and / or Ca. ), A lithium manganese composite oxide powder was produced in the same manner as in Example 41, except that the raw material compounds were weighed so that the composition ratio became the values shown in Table 25 and used as the raw material mixed powder. In Example 50, magnesium carbonate (MgCO 3 ) was used instead of aluminum oxide among the compounds as the raw material. The results obtained are shown in Table 26.

【０１５１】[0151]

【表２５】 [Table 25]

【０１５２】[0152]

【表２６】 [Table 26]

【０１５３】得られたリチウムマンガン複合酸化物粉末
は、以下の方法にて組成分析、比表面積、粒度分布の測
定を行った。また試験電池を作製し、各評価を行った。 （組成分析）所定量のリチウムマンガン複合酸化物粉末
を硝酸に溶解し、プラズマ発光分光（ＩＣＰ）分析法に
より、ハロゲン元素、酸素、ナトリウム以外の各構成元
素の含有量の定量を行った。また所定量のリチウムマン
ガン複合酸化物粉末を純水に投入して撹拌し、上澄み水
溶液を得た。アニオン選択性電極を指示電極に用いたイ
オンメーターにより、上澄み水溶液中のハロゲン元素を
定量した。ナトリウムについては、原子吸光分析法によ
り定量を行った。なお測定の結果、本実施例にて作製し
たリチウムマンガン複合酸化物粉末の各構成元素の組成
比は、原料となる化合物を秤量したときの各構成元素の
組成比と同一であった。The obtained lithium manganese composite oxide powder was subjected to composition analysis, specific surface area and particle size distribution measurement by the following methods. A test battery was prepared and each evaluation was performed. (Composition analysis) A predetermined amount of lithium-manganese composite oxide powder was dissolved in nitric acid, and the content of each constituent element other than halogen element, oxygen, and sodium was quantified by plasma emission spectroscopy (ICP) analysis method. Further, a predetermined amount of lithium-manganese composite oxide powder was put into pure water and stirred to obtain a supernatant aqueous solution. The halogen element in the supernatant aqueous solution was quantified by an ion meter using an anion-selective electrode as an indicator electrode. The amount of sodium was quantified by atomic absorption spectrometry. As a result of the measurement, the composition ratio of each constituent element of the lithium-manganese composite oxide powder produced in this example was the same as the composition ratio of each constituent element when the raw material compound was weighed.

【０１５４】（粉末の評価）得られたリチウムマンガン
複合酸化物粉末の比表面積は、窒素ガスを用いた定圧式
ＢＥＴ吸着法により測定した。また５０％径はレーザー
回折散乱法により粒度分布を測定し、体積基準の粒子径
の対数を用いた積算分布を求め、この積算分布において
積算値が０．５となる粒子径として求めた。(Evaluation of Powder) The specific surface area of the obtained lithium manganese composite oxide powder was measured by a constant pressure BET adsorption method using nitrogen gas. For the 50% size, the particle size distribution was measured by the laser diffraction scattering method, and the cumulative distribution using the logarithm of the volume-based particle size was determined, and the cumulative value was determined as the particle size at which the cumulative value was 0.5.

【０１５５】（リチウムイオン二次電池の作製）ポリフ
ッ化ビニリデン５重量部を含有したノルマルメチルピロ
リドン溶液に正極活物質であるリチウムマンガン複合酸
化物粉末９０重量部、導電剤として炭素粉末５重量部と
を加え、混練してペーストを調製し、これをドクターブ
レード法にてアルミニウム極板に塗布し、乾燥して正極
板とした。また負極活物質に炭素材料を用いて同様にし
て銅極板に塗布し、負極板を作製した。セパレーターに
多孔性プロピレンフィルムを用い、電解液としてエチレ
ンカーボネイト：ジエチルカーボネイト＝１：１（体積
比）の混合溶媒にＬiＰＦ６を１ｍｏｌ／ｌの濃度で溶
解した溶液を用いてリチウムイオン二次電池を作製し
た。本実施例では正極板、負極板、セパレータを薄いシ
ート状に成形し、これらを巻回し、金属ラミネート樹脂
フィルムの電池ケースに収納し、ラミネート型電池とし
た。(Production of Lithium Ion Secondary Battery) 90 parts by weight of lithium manganese composite oxide powder as a positive electrode active material and 5 parts by weight of carbon powder as a conductive agent were added to a normal methylpyrrolidone solution containing 5 parts by weight of polyvinylidene fluoride. Was added and kneaded to prepare a paste, which was applied to an aluminum electrode plate by the doctor blade method and dried to obtain a positive electrode plate. Further, a carbon material was used for the negative electrode active material and similarly applied to a copper electrode plate to prepare a negative electrode plate. A porous propylene film was used as a separator, and a lithium ion secondary battery was prepared by using a solution prepared by dissolving LiPF 6 at a concentration of 1 mol / l in a mixed solvent of ethylene carbonate: diethyl carbonate = 1: 1 (volume ratio) as an electrolytic solution. It was made. In this example, a positive electrode plate, a negative electrode plate, and a separator were formed into a thin sheet shape, which were wound and housed in a battery case of a metal laminated resin film to obtain a laminated battery.

【０１５６】（電池膨張率の評価）ラミネート型電池を
６０℃にて電流密度０．５Ｃで４．３Ｖまで定電流充電
後、電流密度１．２Ｃで３．０Ｖまで放電する充放電を
３００サイクル行った。ガスの発生による電池の膨張率
（体積％）を下記の式（II）から求めた。なおここで
１．０Ｃは、１時間で充電又は放電が終了する電流密度
である。(Evaluation of Battery Expansion Rate) A laminated battery was charged at 60 ° C. with a constant current density of 0.5 C to 4.3 V and then discharged with constant current of 1.2 C to 3.0 V for 300 cycles of charging / discharging. went. The expansion coefficient (volume%) of the battery due to the generation of gas was obtained from the following formula (II). Here, 1.0 C is a current density at which charging or discharging is completed in 1 hour.

【０１５７】[0157]

【数８】 [Equation 8]

【０１５８】[0158]

【発明の効果】以上説明したように、本発明のリチウム
マンガン複合酸化物粉末は、保存特性、高温時における
電池の膨れの抑制、サイクル充放電特性において優れた
特性を実現できた。これにより従来達成できなかった優
れた電池特性を有するリチウムイオン二次電池を実用化
することができ、種々の分野への応用が可能となる。ま
た本発明の製造方法によって、この優れた電池特性を有
するリチウムマンガン複合酸化物粉末を容易に提供する
ことができる。As described above, the lithium manganese composite oxide powder of the present invention has excellent storage characteristics, suppression of battery swelling at high temperature, and excellent cycle charge / discharge characteristics. As a result, a lithium-ion secondary battery having excellent battery characteristics that could not be achieved in the past can be put into practical use, and can be applied to various fields. The production method of the present invention can easily provide the lithium-manganese composite oxide powder having the excellent battery characteristics.

【図面の簡単な説明】[Brief description of drawings]

【図１】リチウムマンガン複合酸化物粉末の比表面積と
ホウ素量との関係を示す図。FIG. 1 is a diagram showing the relationship between the specific surface area of lithium manganese composite oxide powder and the amount of boron.

【図２】電池膨張率とホウ素量との関係を示す図。FIG. 2 is a diagram showing a relationship between a battery expansion coefficient and a boron amount.

【図３】サイクル充放電特性とフッ素量との関係を示す
図。FIG. 3 is a diagram showing the relationship between cycle charge / discharge characteristics and the amount of fluorine.

【図４】正極抵抗と硫黄量との関係を示す図。FIG. 4 is a graph showing the relationship between positive electrode resistance and sulfur content.

【図５】サイクル充放電特性と硫黄量との関係を示す
図。FIG. 5 is a graph showing the relationship between cycle charge / discharge characteristics and sulfur content.

【図６】保存特性と硫黄量との関係を示す図。FIG. 6 is a diagram showing the relationship between storage characteristics and sulfur content.

【図７】電池膨張率とリチウムマンガン複合酸化物粉末
の比表面積との関係を示す図。FIG. 7 is a graph showing the relationship between the battery expansion coefficient and the specific surface area of lithium-manganese composite oxide powder.

【図８】電池膨張率とリチウムマンガン複合酸化物粉末
の１μｍ以下の粒子量との関係を示す図。FIG. 8 is a diagram showing a relationship between a battery expansion coefficient and a particle amount of lithium manganese composite oxide powder of 1 μm or less.

【図９】リチウムマンガン複合酸化物粉末の比表面積と
焼成温度との関係を示す図。FIG. 9 is a graph showing the relationship between the specific surface area of lithium manganese composite oxide powder and the firing temperature.

【図１０】サイクル充放電特性とリチウムマンガン複合
酸化物粉末の（４００）ベクトル方向の結晶子径との関
係を示す図。FIG. 10 is a diagram showing a relationship between cycle charge / discharge characteristics and a crystallite diameter of a lithium manganese composite oxide powder in a (400) vector direction.

【図１１】電池膨張率とリチウムマンガン複合酸化物粉
末の比表面積との関係を示す図。FIG. 11 is a graph showing the relationship between the battery expansion coefficient and the specific surface area of lithium-manganese composite oxide powder.

【図１２】リチウムマンガン複合酸化物粉末の（４０
０）ベクトル方向の結晶子径と焼成雰囲気中の酸素濃度
との関係を示す図。FIG. 12 (40 of lithium manganese composite oxide powder)
0) A diagram showing the relationship between the crystallite diameter in the vector direction and the oxygen concentration in the firing atmosphere.

【図１３】電池の等価回路を示す図。FIG. 13 is a diagram showing an equivalent circuit of a battery.

【図１４】電池膨張率とナトリウム量との関係を示す
図。FIG. 14 is a diagram showing the relationship between the battery expansion coefficient and the amount of sodium.

【図１５】電池膨張率とカルシウム量との関係を示す
図。FIG. 15 is a diagram showing the relationship between the battery expansion coefficient and the amount of calcium.

【符号の説明】[Explanation of symbols]

Ｌ・・・極板のスパイラル成分 Ｒ・・・電解液、集電体の抵抗 Ｃｃ・・・正極板のコンデンサー成分 Ｃａ・・・負極板のコンデンサー成分 Ｒｃ・・・正極板の抵抗成分 Ｒａ・・・負極板の抵抗成分 Ｚｗ（ａ）・・・正極板の拡散係数 Ｚｗ（ｃ）・・・負極板の拡散係数 L: spiral component of electrode plate R: Resistance of electrolyte and current collector Cc: Capacitor component of positive plate Ca: Capacitor component of negative electrode plate Rc ... Resistance component of positive electrode plate Ra: Resistance component of negative electrode plate Zw (a) ... Diffusion coefficient of positive electrode plate Zw (c) ... Diffusion coefficient of negative electrode plate

───────────────────────────────────────────────────── フロントページの続き (31)優先権主張番号 特願2001−284564(P2001−284564) (32)優先日 平成13年９月19日(2001．9．19) (33)優先権主張国 日本（ＪＰ） (31)優先権主張番号 特願2001−368137(P2001−368137) (32)優先日 平成13年12月３日(2001．12．3) (33)優先権主張国 日本（ＪＰ） Ｆターム(参考） 4G048 AA03 AA04 AA05 AA06 AA07 AA10 AB06 AC06 AD03 AD06 AE05 AE06 5H029 AJ04 AJ05 AJ12 AK03 AL06 AM03 AM05 AM07 BJ02 BJ14 CJ02 CJ08 CJ28 DJ08 DJ16 EJ01 EJ07 HJ02 HJ05 HJ07 5H050 AA07 AA09 AA15 BA17 CA09 CB07 DA12 EA02 EA15 FA05 FA17 GA02 GA10 GA27 HA02 HA05 HA07    ─────────────────────────────────────────────────── ─── Continued front page    (31) Priority claim number Japanese Patent Application 2001-284564 (P2001-284564) (32) Priority date September 19, 2001 (September 19, 2001) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application 2001-368137 (P2001-368137) (32) Priority date December 3, 2001 (December 2001) (33) Priority claiming country Japan (JP) F-term (reference) 4G048 AA03 AA04 AA05 AA06 AA07                       AA10 AB06 AC06 AD03 AD06                       AE05 AE06                 5H029 AJ04 AJ05 AJ12 AK03 AL06                       AM03 AM05 AM07 BJ02 BJ14                       CJ02 CJ08 CJ28 DJ08 DJ16                       EJ01 EJ07 HJ02 HJ05 HJ07                 5H050 AA07 AA09 AA15 BA17 CA09                       CB07 DA12 EA02 EA15 FA05                       FA17 GA02 GA10 GA27 HA02                       HA05 HA07

Claims (14)

【特許請求の範囲】[Claims] 【請求項１】アルミニウム及び／又はマグネシウムと、
ホウ素と硫黄とを含むＬｉ１＋ａＭｎ２−ａＯ
４＋ｆ（０＜ａ≦０．２、０≦ｆ＜０．５）で示される
リチウムマンガン複合酸化物粉末。1. Aluminum and / or magnesium,
Li 1 + a Mn 2-a O containing boron and sulfur
4 + f (0 <a ≦ 0.2, 0 ≦ f <0.5), a lithium manganese composite oxide powder. 【請求項２】アルミニウム及び／又はマグネシウムと、
フッ素、塩素、臭素、ヨウ素から選ばれた少なくとも一
種類のハロゲン元素と、ホウ素と硫黄とを含むＬｉ
１＋ａＭｎ２−ａＯ４＋ｆ（０＜ａ≦０．２、０≦ｆ＜
０．５）で示されるリチウムマンガン複合酸化物粉末。2. Aluminum and / or magnesium,
Li containing at least one halogen element selected from fluorine, chlorine, bromine and iodine, and boron and sulfur
1 + a Mn 2−a O 4 + f (0 <a ≦ 0.2, 0 ≦ f <
0.5) Lithium-manganese composite oxide powder represented by 0.5). 【請求項３】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＯ４＋ｆ（Ｍはアルミニウム及び／又はマグネ
シウム、Ｘはフッ素、塩素、臭素、ヨウ素から選ばれた
少なくとも一種類のハロゲン元素、Ｂはホウ素、Ｓは硫
黄、０＜ａ≦０．２、０＜ｂ≦０．２、０≦ｃ≦０．０
５、０＜ｄ≦０．０２、０＜ｅ≦０．１、０≦ｆ＜０．
５）で表されることを特徴とする請求項１又は２に記載
のリチウムマンガン複合酸化物粉末。3. The general formula Li 1 + a M b Mn 2-a-b X c.
B d S e O 4 + f (M is aluminum and / or magnesium, X is at least one halogen element selected from fluorine, chlorine, bromine, and iodine, B is boron, S is sulfur, and 0 <a ≦ 0.2. , 0 <b ≦ 0.2, 0 ≦ c ≦ 0.0
5, 0 <d ≦ 0.02, 0 <e ≦ 0.1, 0 ≦ f <0.
The lithium manganese composite oxide powder according to claim 1 or 2, which is represented by 5). 【請求項４】前記一般式中の硫黄の組成比ｅは０．００
１≦ｅ≦０．０６であることを特徴とする請求項３に記
載のリチウムマンガン複合酸化物粉末。4. The composition ratio e of sulfur in the general formula is 0.00.
The lithium manganese composite oxide powder according to claim 3, wherein 1 ≦ e ≦ 0.06. 【請求項５】前記リチウムマンガン複合酸化物粉末の比
表面積は０．２〜１．２ｍ２／ｇであることを特徴とす
る請求項３又は４に記載のリチウムマンガン複合酸化物
粉末。5. The lithium manganese composite oxide powder according to claim 3, wherein the specific surface area of the lithium manganese composite oxide powder is 0.2 to 1.2 m 2 / g. 【請求項６】１μｍ以下の粒子は１体積％以下であるこ
とを特徴とする請求項３及至５のいずれかに記載のリチ
ウムマンガン複合酸化物粉末。6. The lithium manganese composite oxide powder according to any one of claims 3 to 5, wherein particles having a size of 1 μm or less account for 1% by volume or less. 【請求項７】リチウム化合物、マンガン化合物、ホウ素
化合物、ハロゲン化合物、硫黄含有化合物、並びにアル
ミニウム化合物及び／又はマグネシウム化合物を混合
し、焼成することを特徴とする請求項３及至６のいずれ
かに記載のリチウムマンガン複合酸化物粉末の製造方
法。7. A lithium compound, a manganese compound, a boron compound, a halogen compound, a sulfur-containing compound, and an aluminum compound and / or a magnesium compound are mixed and fired, according to any one of claims 3 to 6. Of the lithium manganese composite oxide powder according to claim 1. 【請求項８】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸｃ
ＢｄＳｅＯ４＋ｆ（Ｍはアルミニウム及び／又はマグネ
シウム、Ｘはフッ素、塩素、臭素、ヨウ素から選ばれた
少なくとも一種類のハロゲン元素、Ｂはホウ素、Ｓは硫
黄、０＜ａ≦０．２、０＜ｂ≦０．２、０≦ｃ≦０．０
５、０＜ｄ≦０．０２、０＜ｅ≦０．１、０≦ｆ＜０．
５）で表され、かつ（４００）ベクトル方向の結晶子径
は７５０〜１０００オングストロームであることを特徴
とする請求項１又は２に記載のリチウムマンガン複合酸
化物粉末。8. A general formula Li 1 + a M b Mn 2-a-b X c.
B d S e O 4 + f (M is aluminum and / or magnesium, X is at least one halogen element selected from fluorine, chlorine, bromine, and iodine, B is boron, S is sulfur, and 0 <a ≦ 0.2. , 0 <b ≦ 0.2, 0 ≦ c ≦ 0.0
5, 0 <d ≦ 0.02, 0 <e ≦ 0.1, 0 ≦ f <0.
The lithium manganese composite oxide powder according to claim 1 or 2, which is represented by 5) and has a crystallite diameter in the (400) vector direction of 750 to 1000 angstroms. 【請求項９】前記リチウムマンガン複合酸化物粉末の比
表面積は０．２〜１ｍ２／ｇであることを特徴とする請
求項８に記載のリチウムマンガン複合酸化物粉末。9. The lithium manganese composite oxide powder according to claim 8, wherein the specific surface area of the lithium manganese composite oxide powder is 0.2 to 1 m 2 / g. 【請求項１０】リチウム化合物、マンガン化合物、ホウ
素化合物、ハロゲン化合物、硫黄含有化合物、並びにア
ルミニウム化合物及び／又はマグネシウム化合物を混合
し、酸素濃度が１８％以上の雰囲気中で焼成することを
特徴とする請求項８又は９に記載のリチウムマンガン複
合酸化物粉末の製造方法。10. A lithium compound, a manganese compound, a boron compound, a halogen compound, a sulfur-containing compound, and an aluminum compound and / or a magnesium compound are mixed and fired in an atmosphere having an oxygen concentration of 18% or more. A method for producing the lithium-manganese composite oxide powder according to claim 8. 【請求項１１】アルミニウム及び／又はマグネシウム
と、ホウ素と硫黄とナトリウム及び／又はカルシウムと
を含むＬｉ１＋ａＭｎ２−ａＯ４＋ｆ（０＜ａ≦０．
２、０≦ｆ＜０．５）で示されるリチウムマンガン複合
酸化物粉末。11. Li 1 + a Mn 2 -a O 4 + f (0 <a ≦ 0.5) containing aluminum and / or magnesium, boron, sulfur, sodium and / or calcium.
2, lithium manganese composite oxide powder represented by 0 ≦ f <0.5). 【請求項１２】アルミニウム及び／又はマグネシウム
と、フッ素、塩素、臭素、ヨウ素から選ばれた少なくと
も一種類のハロゲン元素と、ホウ素と硫黄とナトリウム
及び／又はカルシウムとを含むＬｉ１＋ａＭｎ２−ａＯ
４＋ｆ（０＜ａ≦０．２、０≦ｆ＜０．５）で示される
リチウムマンガン複合酸化物粉末。12. Li 1 + a Mn 2-a O containing aluminum and / or magnesium, at least one halogen element selected from fluorine, chlorine, bromine and iodine, and boron, sulfur, sodium and / or calcium.
4 + f (0 <a ≦ 0.2, 0 ≦ f <0.5), a lithium manganese composite oxide powder. 【請求項１３】一般式Ｌｉ１＋ａＭｂＭｎ２−ａ−ｂＸ
ｃＢｄＳｅＡｇＯ４ ＋ｆ（Ｍはアルミニウム及び／又は
マグネシウム、Ｘはフッ素、塩素、臭素、ヨウ素から選
ばれた少なくとも一種類のハロゲン元素、Ｂはホウ素、
Ｓは硫黄、Ａはナトリウム及び／又はカルシウム、０＜
ａ≦０．２、０＜ｂ≦０．２、０≦ｃ≦０．０５、０＜
ｄ≦０．０２、０＜ｅ≦０．１、０≦ｆ＜０．５、０．
００００４≦ｇ≦０．０１５）で表されることを特徴と
する請求項１１又は１２に記載のリチウムマンガン複合
酸化物粉末。13. The general formula Li 1 + a M b Mn 2-a−b X.
c B d S e A g O 4 + f (M is aluminum and / or magnesium, X is at least one halogen element selected from fluorine, chlorine, bromine and iodine, B is boron,
S is sulfur, A is sodium and / or calcium, 0 <
a ≦ 0.2, 0 <b ≦ 0.2, 0 ≦ c ≦ 0.05, 0 <
d ≦ 0.02, 0 <e ≦ 0.1, 0 ≦ f <0.5, 0.
The lithium manganese composite oxide powder according to claim 11 or 12, characterized in that it is represented by 00004 ≤ g ≤ 0.015). 【請求項１４】前記リチウムマンガン複合酸化物粉末の
比表面積は０．２〜１．２ｍ２／ｇであることを特徴と
する請求項１３に記載のリチウムマンガン複合酸化物粉
末。14. The lithium manganese composite oxide powder according to claim 13, wherein the specific surface area of the lithium manganese composite oxide powder is 0.2 to 1.2 m 2 / g.
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WO2004049474A1 (en) * 2002-11-22 2004-06-10 Mitsui Mining & Smelting Co., Ltd. POSITIVE ELECTRODE MATERIAL FOR Li ION SECONDARY BATTERY
JP2005216651A (en) * 2004-01-29 2005-08-11 Nichia Chem Ind Ltd Positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode mixture for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
KR100591139B1 (en) 2005-11-08 2006-06-20 장상구 Lithium-ion-cell lithium-manganese-oxide powder and production
JP2009043546A (en) * 2007-08-08 2009-02-26 Hitachi Ltd Lithium secondary battery
WO2010114015A1 (en) * 2009-03-31 2010-10-07 三井金属鉱業株式会社 Positive electrode active material for lithium battery
JP2012096949A (en) * 2010-10-29 2012-05-24 Jgc Catalysts & Chemicals Ltd Production method and application of spinel-type lithium-manganese compound oxide particle
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KR102663027B1 (en) * 2021-12-23 2024-05-08 주식회사 지엘비이 Lithium manganese oxide spinel with high capacity as cathode material for lithium secondary battery and a method for producing the same

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004049474A1 (en) * 2002-11-22 2004-06-10 Mitsui Mining & Smelting Co., Ltd. POSITIVE ELECTRODE MATERIAL FOR Li ION SECONDARY BATTERY
JP2005216651A (en) * 2004-01-29 2005-08-11 Nichia Chem Ind Ltd Positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode mixture for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
KR100591139B1 (en) 2005-11-08 2006-06-20 장상구 Lithium-ion-cell lithium-manganese-oxide powder and production
JP2009043546A (en) * 2007-08-08 2009-02-26 Hitachi Ltd Lithium secondary battery
WO2010114015A1 (en) * 2009-03-31 2010-10-07 三井金属鉱業株式会社 Positive electrode active material for lithium battery
KR101129368B1 (en) * 2009-03-31 2012-03-26 미쓰이 긴조꾸 고교 가부시키가이샤 Positive electrode active material for lithium battery
US8703341B2 (en) 2009-03-31 2014-04-22 Mitsui Mining & Smelting Co., Ltd. Positive electrode active material for lithium battery
JP2012096949A (en) * 2010-10-29 2012-05-24 Jgc Catalysts & Chemicals Ltd Production method and application of spinel-type lithium-manganese compound oxide particle
CN109476504A (en) * 2016-08-25 2019-03-15 托普索公司 Active material of cathode for high-voltage secondary battery
KR102663027B1 (en) * 2021-12-23 2024-05-08 주식회사 지엘비이 Lithium manganese oxide spinel with high capacity as cathode material for lithium secondary battery and a method for producing the same

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