JP3373069B2 - Non-aqueous secondary battery and method for producing positive electrode active material thereof - Google Patents

Non-aqueous secondary battery and method for producing positive electrode active material thereof

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Publication number
JP3373069B2
JP3373069B2 JP30787594A JP30787594A JP3373069B2 JP 3373069 B2 JP3373069 B2 JP 3373069B2 JP 30787594 A JP30787594 A JP 30787594A JP 30787594 A JP30787594 A JP 30787594A JP 3373069 B2 JP3373069 B2 JP 3373069B2
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Japan
Prior art keywords
lithium
positive electrode
active material
type
electrode active
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Japanese (ja)
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JPH07230802A (en
Inventor
武仁 見立
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Sharp Corp
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Sharp Corp
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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

Description

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

【０００１】[0001]

【産業上の利用分野】この発明は非水系二次電池及びそ
の正極活物質の製造方法に関する。さらに詳しくは、負
極の活物質がリチウムを含むか又はリチウムの挿入・脱
離の可能な物質からなり、正極の活物質がリチウム・マ
ンガンの複合酸化物からなる非水系二次電池及びリチウ
ム・マンガンの複合酸化物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous secondary battery and a method for producing a positive electrode active material thereof. More specifically, the non-aqueous secondary battery and the lithium-manganese in which the negative electrode active material contains lithium or is capable of inserting and releasing lithium and the positive electrode active material is a lithium-manganese composite oxide. Relates to a method for producing a composite oxide.

【０００２】[0002]

【従来の技術及び発明が解決しようとする課題】電子機
器等の小型、省電力化に伴って、リチウム等アルカリ金
属を利用した二次電池が注目されている。しかし、負極
にリチウムなどアルカリ金属を単体で用いた場合には、
充放電の繰り返し、つまりアルカリ金属の溶解−析出過
程により、金属の析出面上にデンドライト（樹枝状結
晶）が生成し、成長することとなる。その結果、このデ
ンドライトがセパレータを貫通し、正極と接すると、電
池内部の短絡を誘発するという問題があった。2. Description of the Related Art With the miniaturization and power saving of electronic devices and the like, secondary batteries using alkali metals such as lithium have attracted attention. However, when an alkali metal such as lithium is used alone for the negative electrode,
By repeating the charge and discharge, that is, the dissolution-precipitation process of the alkali metal, dendrites (dendritic crystals) are generated and grow on the metal deposition surface. As a result, when this dendrite penetrates the separator and comes into contact with the positive electrode, there is a problem that a short circuit inside the battery is induced.

【０００３】また、負極にアルカリ金属合金を用いる
と、アルカリ金属単体の時に比べ、デンドライトの発生
が抑制され、充放電サイクル特性が向上するが、金属の
析出面上のデンドライトの生成が完全になくなるわけで
なく、電池内部の短絡が起こることもある。近年になっ
て、負極に、金属の溶解−析出過程、或いは溶解−析出
−固体内拡散過程を利用するアルカリ金属やそれらの合
金の代りに、アルカリ金属イオンの吸収−放出過程を利
用した炭素や導電性高分子等の有機材料が使用されてい
る。これにより、アルカリ金属やそれらの合金を用いた
場合に起こるデンドライトの生成が原理上起こらなくな
り、電池内部の短絡の問題が激減するに至った。Further, when an alkali metal alloy is used for the negative electrode, dendrite generation is suppressed and charge / discharge cycle characteristics are improved as compared with the case of using an alkali metal alone, but dendrite formation on the metal deposition surface is completely eliminated. However, a short circuit inside the battery may occur. In recent years, in the negative electrode, instead of alkali metals or their alloys that utilize the dissolution-precipitation process of metals, or the dissolution-precipitation-diffusion process in solids, carbon that utilizes absorption-desorption processes of alkali metal ions or Organic materials such as conductive polymers are used. As a result, the generation of dendrite that occurs when an alkali metal or an alloy thereof is used does not occur in principle, and the problem of short circuit inside the battery is drastically reduced.

【０００４】一方、正極としては、五酸化バナジウム、
二硫化チタン、三酸化タングステン、二酸化マンガン、
リチウム・コバルト酸化物（ＬｉＣｏＯ2)、リチウム・
ニッケル酸化物（ＬｉＮｉＯ2)、スピネル型リチウム・
マンガン酸化物（ＬｉＭｎ2Ｏ4)等を用いることが検討
されている。五酸化バナジウムは、合成直後、充電状態
の活物質として働くものであり、特願昭６１−１１６７
８号、特願昭６１−１１６７５７号、特願平１−２４６
７６３号、特願平３−１０５８５８号等に開示されてい
る。これらにおいては、超急冷法等で作製できる非晶質
五酸化バナジウムを正極に用いることによって、高電圧
を有し、良好な充放電サイクル寿命を示すリチウム二次
電池が得られることが開示されている。On the other hand, as the positive electrode, vanadium pentoxide,
Titanium disulfide, tungsten trioxide, manganese dioxide,
Lithium cobalt oxide (LiCoO 2 ), lithium
Nickel oxide (LiNiO 2 ), spinel type lithium
The use of manganese oxide (LiMn 2 O 4 ) or the like has been studied. Vanadium pentoxide acts as an active material in a charged state immediately after synthesis, and is disclosed in Japanese Patent Application No. 61-1167.
No. 8, Japanese Patent Application No. 61-116757, Japanese Patent Application No. 1-246.
No. 763 and Japanese Patent Application No. 3-105858. In these, it is disclosed that by using amorphous vanadium pentoxide that can be produced by the ultraquenching method or the like for the positive electrode, a lithium secondary battery having a high voltage and exhibiting a good charge / discharge cycle life can be obtained. There is.

【０００５】さらに、高電位を有する正極活物質とし
て、リチウム・コバルト酸化物（ＬｉＣｏＯ2)、リチウ
ム・ニッケル酸化物（ＬｉＮｉＯ2)、これらの複合酸化
物、あるいはこれらの酸化物にさらに他の元素を添加し
た複合酸化物が、特開昭５５−１３６１３１号公報、特
開昭６２−９０８６３号公報、特開昭６２−２５６３７
１号公報、特開昭６２−２６４５６０号公報、特開平３
−６４８６０号公報、特開平４−２８１６２号公報、特
開平４−１５５７７５号公報等に開示されている。さら
に、これらの正極活物質を含む電極を用いることによ
り、高電圧を示すリチウム二次電池を得ることが提案さ
れている。しかしこれらの物質は原料が高価であるた
め、電池作製時のコスト面で問題がある。Further, as a positive electrode active material having a high potential, lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), a composite oxide of these, or other elements in addition to these oxides. The compound oxides added with are those disclosed in JP-A-55-136131, JP-A-62-90863, and JP-A-62-25637.
No. 1, JP-A-62-264560, JP-A-3.
-64860, JP-A-4-28162, JP-A-4-155775, and the like. Further, it has been proposed to obtain a lithium secondary battery exhibiting a high voltage by using an electrode containing these positive electrode active materials. However, since these materials are expensive as raw materials, there is a problem in terms of cost when manufacturing a battery.

【０００６】これに対して、原料が比較的安価である二
酸化マンガン、リチウム含有二酸化マンガン、あるいは
これらの酸化物に他の元素を添加した複合酸化物が、特
開昭６３−１１４０６４号公報、特開昭６３−１１４０
６５号公報、特開平１−２９４３６２号公報、特開平１
−３０７１５９号公報、特開平３−６７４６４号公報、
特開平３−１０８２６２号公報、特開平３−１１０７５
７号公報、特開平３−１１０７５８号公報等に開示され
ている。これら物質は、合成直後は充電状態の活物質と
して働く。このため、負極活物質として、初期に放電状
態にあるリチウムの挿入・脱離の可能な炭素や黒鉛等
を、上記正極活物質と組合せて用いた場合には、まず正
極を放電するかあるいは負極を充電する必要があり、電
池作製時に工程が増えるという問題点がある。On the other hand, manganese dioxide whose raw material is relatively inexpensive, lithium-containing manganese dioxide, or a composite oxide obtained by adding other elements to these oxides is disclosed in Japanese Patent Laid-Open No. 63-114064. Kai 63-1140
65, JP-A-1-294362, JP-A-1
-307159, JP-A-3-67464,
JP-A-3-108262, JP-A-3-11075
No. 7, Japanese Patent Laid-Open No. 3-110758, and the like. Immediately after synthesis, these substances act as active materials in a charged state. Therefore, when carbon or graphite capable of inserting / desorbing lithium in an initially discharged state is used as the negative electrode active material in combination with the positive electrode active material, first discharge the positive electrode or the negative electrode. Therefore, there is a problem in that the number of steps is increased when manufacturing a battery.

【０００７】また、スピネル型リチウム・マンガン酸化
物（ＬｉＭｎ2Ｏ4)、あるいはこの酸化物に他の元素を
添加した複合酸化物が、T.Ohzuku, M.tagawa, and T.Hi
rai,J.Electrochem.Soc., 137, 769(1990）及び特開平
２−２７０２６８号公報、特開平３−１０８２６１号公
報、特開平４−１４７５７号公報、特開平４−１４１９
５４号公報、特開平４−１４７５７３号公報等に開示さ
れている。これら複合酸化物を用いることにより上記問
題点が解決されるが、電位が高すぎ、電解液及び電解質
を分解しやすく、また充放電容量が小さい等という問題
がある。Further, spinel type lithium manganese oxide (LiMn 2 O 4 ) or a composite oxide obtained by adding other elements to this oxide is T.Ohzuku, M.tagawa, and T.Hi.
rai, J. Electrochem. Soc., 137 , 769 (1990) and JP-A-2-270268, JP-A-3-108261, JP-A-4-14757, and JP-A-4-1419.
No. 54, Japanese Patent Application Laid-Open No. 4-147573, and the like. Although the above problems can be solved by using these composite oxides, there are problems that the potential is too high, the electrolytic solution and the electrolyte are easily decomposed, and the charge / discharge capacity is small.

【０００８】このように、公知の正極活物質にはそれぞ
れに問題があり、新規な正極活物質を用いた非水系二次
電池、特にリチウム二次電池を提供することが望まれて
いた。本発明は上記課題に鑑みなされたものであり、安
価な原料を使用しながら、従来必要であった正極の放電
又は負極の充電工程を行う必要なく電池製造工程が比較
的簡素化され、さらに、リチウムの挿入・脱離の可能な
炭素や黒鉛等の負極と、リチウム・マンガンの複合酸化
物を含む正極との組合せにおいても繰返し充放電によっ
てデンドライトの発生しない良好な非水系二次電池及び
その正極活物質の製造方法を提供することを目的として
いる。As described above, each of the known positive electrode active materials has its own problems, and it has been desired to provide a non-aqueous secondary battery, particularly a lithium secondary battery, which uses the novel positive electrode active material. The present invention has been made in view of the above problems, while using an inexpensive raw material, the battery manufacturing process is relatively simplified without the need to perform a positive electrode discharging or negative electrode charging process that has been conventionally required. A good non-aqueous secondary battery and its positive electrode in which dendrite does not occur due to repeated charge and discharge even when a negative electrode such as carbon or graphite capable of inserting and removing lithium and a positive electrode containing a composite oxide of lithium and manganese are combined. It is intended to provide a method for producing an active material.

【０００９】[0009]

【課題を解決するための手段】本発明によれば、正極、
負極及び非水系のイオン伝導体からなる非水系二次電池
であって、負極がリチウムを含むか又はリチウムが挿入
・脱離可能な活物質からなり、正極がリチウム・マンガ
ンの複合酸化物を含む活物質からなり、かつその酸化物
のＣｕＫα線によるＸ線回折線が、少なくとも１５．２
〜１５．６゜、１８．６〜１８．８゜及び２４．５〜２
５．１゜の範囲にそれぞれピークを有しており、前記１
５．２〜１５．６゜の範囲のピーク強度に対する２７〜
３３゜の範囲のピーク強度の比が０．０２より小さい非
水系二次電池が提供される。According to the present invention, a positive electrode,
A non-aqueous secondary battery comprising a negative electrode and a non-aqueous ionic conductor, wherein the negative electrode contains lithium or an active material into which lithium can be inserted / removed, and the positive electrode contains a lithium-manganese composite oxide. An X-ray diffraction line of an oxide made of an active material and having CuKα rays of at least 15.2.
~ 15.6 °, 18.6 ~ 18.8 ° and 24.5 ~ 2
Each has a peak in the range of 5.1 °,
27-for peak intensities in the range of 5.2-15.6 °
A non-aqueous secondary battery having a peak intensity ratio of less than 0.02 in the 33 ° range is provided.

【００１０】また、α型、β型、γ型、δ型、ε型、η
型、λ型、電解型又はラムスデライト型のＭｎＯ2、Ｍ
ｎ5Ｏ8、Ｍｎ2Ｏ3、ＭｎＯＯＨ及びＬｉＭｎ2 Ｏ4から
なる群より選ばれた少なくとも１種のマンガン化合物
と、塩化リチウム、臭化リチウム、ヨウ化リチウム、水
酸化リチウム、酸化リチウム、硝酸リチウム、炭酸リチ
ウム、蟻酸リチウム、酢酸リチウム、安息香酸リチウ
ム、クエン酸リチウム、乳酸リチウム、シュウ酸リチウ
ム、ピルビン酸リチウム、ステアリン酸リチウム、酒石
酸リチウム及びＬｉ2ＭｎＯ3からなる群より選ばれた少
なくとも１種のリチウム化合物とを混合し、該混合物
を、 (i) ４００〜２０００℃の温度で、かつ酸素含有量が実
質的に０体積％より大きく１０体積％以下の範囲内の雰
囲気中、又は (ii)２５０℃以上の温度で、かつ還元性雰囲気中 で焼成してリチウム・マンガン複合酸化物を正極活物質
として形成する工程を含んでなる上記非水系二次電池の
製造方法が提供される。Further, α type, β type, γ type, δ type, ε type, η
Type, λ type, electrolytic type or ramsdellite type MnO 2 , M
at least one manganese compound selected from the group consisting of n 5 O 8 , Mn 2 O 3 , MnOOH, and LiMn 2 O 4 , and lithium chloride, lithium bromide, lithium iodide, lithium hydroxide, lithium oxide, nitric acid At least one selected from the group consisting of lithium, lithium carbonate, lithium formate, lithium acetate, lithium benzoate, lithium citrate, lithium lactate, lithium oxalate, lithium pyruvate, lithium stearate, lithium tartrate and Li 2 MnO 3. A lithium compound of a species, and the mixture is (i) at a temperature of 400 to 2000 ° C. and in an atmosphere in which the oxygen content is substantially more than 0% by volume and 10% by volume or less, or ( ii) Lithium-manganese composite oxide is formed as a positive electrode active material by firing in a reducing atmosphere at a temperature of 250 ° C. or higher. There is provided a method for manufacturing the non-aqueous secondary battery, which includes the step of:

【００１１】本願発明の非水系二次電池における正極
は、活物質としてリチウム・マンガン複合酸化物からな
る。このリチウム・マンガン複合酸化物は、第１群のマ
ンガン酸化物と第２群のリチウム化合物とを混合し、こ
の混合物を、約４００〜約２０００℃の温度範囲内、か
つ酸素含有量が実質的に０体積％より大きく１０体積％
以下の範囲内の雰囲気中で焼成することにより得られ
る。また、前記混合物を、約２５０℃以上の温度範囲
内、かつ還元性雰囲気中で焼成しても得ることもでき
る。このようにして得られたリチウム・マンガン複合酸
化物は、 Ｌｉx ＭｎＯy （０．８≦ｘ≦１．２、１．９≦ｙ≦
２．２） なる組成式を満たすものである。The positive electrode in the non-aqueous secondary battery of the present invention comprises a lithium-manganese composite oxide as an active material. This lithium-manganese composite oxide is a mixture of a manganese oxide of the first group and a lithium compound of the second group, and this mixture is mixed in a temperature range of about 400 to about 2000 ° C. and has an oxygen content substantially. Greater than 0% by volume and 10% by volume
It is obtained by firing in an atmosphere within the following range. It is also possible to obtain the mixture by firing the mixture in a temperature range of about 250 ° C. or higher and in a reducing atmosphere. The lithium-manganese composite oxide thus obtained has a composition of Li x MnO y (0.8 ≦ x ≦ 1.2, 1.9 ≦ y ≦
2.2) The following composition formula is satisfied.

【００１２】第１群のマンガン酸化物には、α型、β
型、γ型、δ型、ε型、η型、λ型、電解型（ＥＭＤと
略）、ラムスデライト（Ramsdellite)型のＭｎＯ2 、Ｍ
ｎ5 Ｏ 8 、Ｍｎ2 Ｏ3 、ＭｎＯＯＨ及びＬｉＭｎ2Ｏ4
が含まれる。第１群のマンガン酸化物は、上記以外のマ
ンガン化合物であってもよいが、酸化物中において３価
以上のマンガンが多数占めていることを必須とする。こ
れは正極活物質としてのリチウム・マンガン複合酸化物
が良好な性能を示すためには、該酸化物中に３価以上の
マンガンが多数占めていることが必要だからである。第
１群のマンガン酸化物は、酸素含有量が０体積％より大
きく１０体積％以下の範囲内の雰囲気中で焼成されるた
め、２価以下のマンガンは酸化されて３価以上となるこ
とは困難である。従って、正極の活物質の原料において
３価以上のマンガンが多数を占めている必要がある。２
価以下のマンガン酸化物を上記条件で焼成しても、上記
のＸ線回折線におけるピーク値は得られ難い。第２群の
リチウム化合物には、塩化リチウム、臭化リチウム、ヨ
ウ化リチウム、水酸化リチウム、酸化リチウム、硝酸リ
チウム、炭酸リチウム、蟻酸リチウム、酢酸リチウム、
安息香酸リチウム、クエン酸リチウム、乳酸リチウム、
シュウ酸リチウム、ピルビン酸リチウム、ステアリン酸
リチウム、酒石酸リチウム及びＬｉ2ＭｎＯ3が含まれ
る。The first group of manganese oxides includes α type and β type.
Type, γ type, δ type, ε type, η type, λ type, electrolytic type (EMD and
Omitted), Ramsdellite type MnO2, M
nFiveO 8, Mn2O3, MnOOH and LiMn2OFour
Is included. Group 1 manganese oxides are
It may be an gangan compound, but it is trivalent in the oxide
It is essential that the above manganese occupies a large number. This
This is a lithium-manganese composite oxide as a positive electrode active material.
In order to exhibit good performance,
This is because it is necessary that a large amount of manganese is occupied. First
Group 1 manganese oxides have an oxygen content greater than 0% by volume.
It was fired in an atmosphere within the range of 10% by volume or less.
Therefore, manganese with a valency of 2 or less must be oxidized to a valency of 3 or more.
And is difficult. Therefore, in the raw material of the positive electrode active material
It is necessary that trivalent or higher manganese occupies the majority. Two
Even if a manganese oxide having a valency of less than or equal to the above is fired under the above conditions,
It is difficult to obtain a peak value in the X-ray diffraction line of. Of the second group
Lithium compounds include lithium chloride, lithium bromide, and iodine.
Lithium bromide, lithium hydroxide, lithium oxide, lithium nitrate
Titanium, lithium carbonate, lithium formate, lithium acetate,
Lithium benzoate, lithium citrate, lithium lactate,
Lithium oxalate, lithium pyruvate, stearic acid
Lithium, lithium tartrate and Li2MnO3Included
It

【００１３】第１群のマンガン酸化物より選ばれたマン
ガン化合物の少なくとも１種と第２群のリチウム化合物
より選ばれたリチウム化合物の少なくとも１種とを、焼
成後のリチウム・マンガン複合酸化物の組成比におい
て、Ｌｉ：Ｍｎ＝０．８：１〜１．２：１の範囲、Ｍ
ｎ：Ｏ＝１：２．２〜１：１．９の範囲になるよう混合
する。第１群のマンガン酸化物及び第２群のリチウム化
合物の混合量は、その組成比、焼成条件及び焼成容器等
から適宜決定される。この組成比の範囲外では、得られ
た複合酸化物は上記Ｘ線回折線の範囲にピーク強度を持
たないことがある。さらに、これを非水系二次電池の正
極活物質として適用させたとき、電極の抵抗及び分極が
大きくなり、その結果放電容量が小さくなり、実用的で
ない。At least one manganese compound selected from the manganese oxides of the first group and at least one lithium compound selected from the lithium compounds of the second group are mixed in a lithium-manganese composite oxide after firing. In the composition ratio, Li: Mn = 0.8: 1 to 1.2: 1, M
Mix so as to be in the range of n: O = 1: 2.2 to 1: 1.9. The mixing amounts of the first group of manganese oxides and the second group of lithium compounds are appropriately determined based on the composition ratio, firing conditions, firing container and the like. Outside the range of this composition ratio, the obtained composite oxide may not have a peak intensity in the range of the above X-ray diffraction line. Furthermore, when this is applied as a positive electrode active material of a non-aqueous secondary battery, the resistance and polarization of the electrode become large, resulting in a small discharge capacity, which is not practical.

【００１４】混合する方法は、乾式の方法及び湿式の方
法が適用できる。第１群のマンガン酸化物及び第２群の
リチウム化合物が粉体の場合は、これらをブレンダー等
で混合する方法、一方が水等の溶媒に可溶であるとき
は、その溶液中に不溶物を混合する方法、双方が可溶で
あるときは両溶液を混合して、蒸発や冷却などで溶媒を
除去し、混合する方法などが挙げられる。As the mixing method, a dry method and a wet method can be applied. When the manganese oxide of the first group and the lithium compound of the second group are powders, a method of mixing them with a blender or the like, and when one of them is soluble in a solvent such as water, an insoluble matter in the solution And a method of mixing both solutions when both are soluble and removing the solvent by evaporation or cooling to mix.

【００１５】焼成は、上記混合物を酸素含有量が実質的
に０体積％より大きく約１０体積％以下の範囲内、より
好ましくは０体積％より大きく約５体積％以下の範囲内
の雰囲気中で行われる。ここで、酸素含有量が実質的に
０体積とは、数ｐｐｂ以下の濃度をいう。酸素含有量を
約１０体積％以下にするために、雰囲気を減圧して真空
付近にしたり、アルゴン又は窒素等の不活性ガスで置換
したりすることが挙げられる。酸素含有量が約１０体積
％より大きな雰囲気で焼成すると、得られた複合酸化物
は前記Ｘ線回折線の範囲にピーク強度を持たないことが
ある。従って、これを非水系二次電池の正極活物質とし
て適用させたとき、正極の抵抗及び分極が大きくなり、
その結果放電容量が小さくなり、実用的でない。The calcination is performed by heating the mixture in an atmosphere having an oxygen content of substantially more than 0% by volume and about 10% by volume or less, more preferably more than 0% by volume and about 5% by volume or less. Done. Here, the oxygen content being substantially 0 volume means a concentration of several ppb or less. To reduce the oxygen content to about 10% by volume or less, the atmosphere may be depressurized to near vacuum or replaced with an inert gas such as argon or nitrogen. When baked in an atmosphere having an oxygen content of more than about 10% by volume, the obtained composite oxide may not have a peak intensity in the range of the X-ray diffraction line. Therefore, when this is applied as a positive electrode active material of a non-aqueous secondary battery, the resistance and polarization of the positive electrode increase,
As a result, the discharge capacity becomes small, which is not practical.

【００１６】このような雰囲気中で焼成する場合の焼成
温度は約４００〜約２０００℃の範囲が好ましい。焼成
温度が約４００℃より低い場合は、得られた複合酸化物
の結晶性が低く、前記Ｘ線回折線の範囲にピーク強度を
持たないため、上記と同様に非水系二次電池の正極活物
質としては実用的でない。また、約２０００℃より高い
温度での焼成は却って経済的でない。When firing in such an atmosphere, the firing temperature is preferably in the range of about 400 to about 2000 ° C. When the firing temperature is lower than about 400 ° C., the crystallinity of the obtained composite oxide is low and the X-ray diffraction line does not have a peak intensity. Therefore, the positive electrode active material of the non-aqueous secondary battery is the same as above. Not practical as a substance. Moreover, firing at a temperature higher than about 2000 ° C. is not economical on the contrary.

【００１７】また、上記混合物を還元性雰囲気中で焼成
してもよい。還元性雰囲気としては、水素又は炭化水素
類（例：メタン、エタン、プロパン、ブタン、エチレ
ン、プロピレン、２−ブチン、アセチレン、ビフェニ
ル、ビフェニルアセチレン、ベンゼン、トルエン、キシ
レン、ナフタレン、アントラセン、ヘキサメチルベンゼ
ン、シクロヘキサン、ピレン、ピリジン、アリルベンゼ
ン、アニリン、フェノール、１，２−ジブロモエチレ
ン、スチレン、アクリロニトリル、ピロール、チオフェ
ン、ブチルクロリド、ペンタノール、アニソール、アセ
トン、酪酸エチル等）の単独雰囲気、又は水素もしくは
炭化水素類と窒素、アルゴンもしくはヘリウム等との混
合気体による雰囲気が挙げられる。水素又は炭化水素類
は、常温で気体、液体又は固体と様々な状態で存在す
る。従って、使用する炭化水素類によって供給する方法
が異なる。例えば、ボンベで入手できる水素、エタン、
プロパン、アセチレン等はそのまま又はアルゴン、窒素
等のガスとともに供給することができる。ベンゼン、ト
ルエン、スチレン、アニリン、ピロール、ペンタノー
ル、アニソール、アセトン、酪酸エチル等の常温で液体
の物質、あるいはビフェニル等の常温では固体であるが
温度を上げて液体にした物質は、バブラー法、蒸発法等
によって供給することができる。常温で固体であるナフ
タレン、アントラセン等は、昇華法又は上記第１群のマ
ンガン酸化物及び第２群のリチウム化合物の混合物に混
合して供給することができる。The mixture may be fired in a reducing atmosphere. The reducing atmosphere is hydrogen or hydrocarbons (eg, methane, ethane, propane, butane, ethylene, propylene, 2-butyne, acetylene, biphenyl, biphenylacetylene, benzene, toluene, xylene, naphthalene, anthracene, hexamethylbenzene). , Cyclohexane, pyrene, pyridine, allylbenzene, aniline, phenol, 1,2-dibromoethylene, styrene, acrylonitrile, pyrrole, thiophene, butyl chloride, pentanol, anisole, acetone, ethyl butyrate, etc.) alone or hydrogen or Examples of the atmosphere include a mixed gas of hydrocarbons and nitrogen, argon, helium, or the like. Hydrogen or hydrocarbons exist in various states such as gas, liquid or solid at room temperature. Therefore, the method of supply differs depending on the hydrocarbons used. For example, hydrogen, ethane, available in cylinders,
Propane, acetylene and the like can be supplied as they are or together with gases such as argon and nitrogen. Substances that are liquid at room temperature, such as benzene, toluene, styrene, aniline, pyrrole, pentanol, anisole, acetone, ethyl butyrate, or substances that are solid at room temperature but are liquid at elevated temperatures, such as biphenyl, are the bubbler method, It can be supplied by an evaporation method or the like. Naphthalene, anthracene, etc., which are solid at room temperature, can be supplied by a sublimation method or by being mixed with a mixture of the first group manganese oxide and the second group lithium compound.

【００１８】特に、還元性雰囲気が水素である場合に
は、水素含有量が０体積％より大きく約３０体積％以下
の範囲内であることが好ましい。この場合の焼成温度は
２５０〜２０００℃が好ましい。水素含有量が約３０体
積％より大きな雰囲気で焼成すると、還元が進みすぎる
ため、得られた複合酸化物は前記Ｘ線回折線の範囲にピ
ーク強度を持たないことがある。従って、非水系二次電
池の正極活物質として適用させたとき、上記と同様に実
用的でない。焼成温度が２５０℃より低い場合には、結
晶性が低く、前記Ｘ線回折線の範囲にピーク強度を持た
ないことがあり、上記と同様実用的でない。また、約２
０００℃より高い温度での焼成は却って経済的でない。Particularly, when the reducing atmosphere is hydrogen, the hydrogen content is preferably in the range of more than 0% by volume and about 30% by volume or less. In this case, the firing temperature is preferably 250 to 2000 ° C. When firing in an atmosphere having a hydrogen content of more than about 30% by volume, reduction proceeds too much, and thus the obtained composite oxide may not have a peak intensity in the range of the X-ray diffraction line. Therefore, when it is applied as a positive electrode active material of a non-aqueous secondary battery, it is not practical like the above. When the firing temperature is lower than 250 ° C., the crystallinity is low and the X-ray diffraction line may have no peak intensity, which is not practical as in the above case. Also, about 2
On the contrary, firing at a temperature higher than 000 ° C is not economical.

【００１９】還元性雰囲気がプロパンである場合には、
プロパン含有量が０体積％より大きく約５０体積％以下
の範囲内であることが好ましい。この場合の焼成温度は
３００〜２０００℃が好ましい。プロパン含有量が約５
０体積％より大きな雰囲気で焼成すると、プロパンの気
相での熱分解合成により生成した炭素が、得られるリチ
ウム・マンガン複合酸化物に混合されるため好ましくな
い。焼成温度が３００℃より低い場合には、結晶性が低
く、前記Ｘ線回折線の範囲にピーク強度を持たないこと
があり、上記と同様実用的でない。また、約２０００℃
より高い温度での焼成は却って経済的でない。When the reducing atmosphere is propane,
It is preferred that the propane content be in the range of greater than 0% and less than or equal to about 50% by volume. In this case, the firing temperature is preferably 300 to 2000 ° C. Propane content is about 5
Firing in an atmosphere larger than 0% by volume is not preferable because the carbon produced by pyrolysis synthesis of propane in the gas phase is mixed with the obtained lithium-manganese composite oxide. If the firing temperature is lower than 300 ° C., the crystallinity is low and the X-ray diffraction line may have no peak intensity, which is not practical as in the above case. Also, about 2000 ℃
Baking at higher temperatures is rather uneconomical.

【００２０】また、リチウム・マンガン複合酸化物を、
上記第１群のマンガン酸化物、第２群のリチウム化合物
及び常温で固体であるナフタレン、アントラセン等を混
合して合成する場合には、焼成炉の雰囲気堆積、物質の
蒸気圧等の物性により、仕込み量、焼成温度は適宜変化
させることができる。上記リチウム・マンガン複合酸化
物について、Ｘ線源にＣｕＫα線を用いて、常法の粉末
Ｘ線回折法により回折線を求めた場合、１０〜５０゜に
おける回折角２θに存在する主な回折線のピークは、少
なくとも１５．２〜１５．６゜、１８．６〜１８．８
゜、２４．５〜２５．１゜の範囲にそれぞれ表れ、か
つ、１５．２〜１５．６゜の範囲のピーク強度に対する
２７〜３３゜の範囲のピーク強度の比は０．０２より小
さいことが必要である。１５．２〜１５．６゜のピーク
は、斜方晶系に属するＰｍｎｍであるＬｉＭｎＯ2 の
（０１０）と斜方晶系に属するＰｍ２ｍであるＬｉＭｎ
Ｏ2 の（０１０）とを示すものであり、１８．６〜１
８．８゜のピークは、スピネル型であるＬｉＭｎ2 Ｏ4
の（１１１）と単斜晶系に属するＬｉ2 ＭｎＯ3 の（０
０２）とを示すものであり、２４．５〜２５．１゜のピ
ークは、ＰｍｎｍであるＬｉＭｎＯ2 の（１１０）とＰ
ｍ２ｍであるＬｉＭｎＯ2 の（０１１）とを示すもので
あると考えられる。上記の範囲以外に、３５．６゜近
傍、３６．９゜近傍、３７．６゜近傍、３９．４゜近
傍、４０．８゜近傍、４２．６゜近傍、４５．１゜近傍
及び４７．４゜近傍の各範囲にもそれぞれピークを有し
ていてもよい。これら回折線にピークを有する場合に
は、１５．２〜１５．６゜の範囲に存在するピーク強度
（Ｉ0)に対する各々のピーク強度（Ｉ）の比（Ｉ／Ｉ0)
は、１８．６〜１８．８゜、２４．５〜２５．１゜、３
５．６゜近傍、３６．９゜近傍、３７．６゜近傍、３
９．４゜近傍、４０．８゜近傍、４２．６゜近傍、４
５．１゜近傍及び４７．４゜近傍において、それぞれ
０．０２〜１．５、０．７〜０．２、０．１５〜０．
３、０．０５〜０．２５、０．０５〜０．２、０．４５
〜０．７５、０．０５〜０．３、０〜０．１５、０．５
５〜１．１及び０〜０．０５であることが好ましい。上
記のＸ線回折線におけるピーク位置及び強度は、リチウ
ム・マンガン複合酸化物の原料である第１群のマンガン
酸化物及び第２群のリチウム化合物の種類、混合の割
合、焼成時の酸素含有量及び焼成温度によって変化す
る。これは、結晶性及び結晶の大きさが変化するためで
ある。しかし、いずれの条件においても、良好な正極活
物質としてのリチウム・マンガン複合酸化物は、Ｘ線回
折線の１５．２〜１５．６゜、１８．６〜１８．８゜及
び２４．５〜２５．１゜の範囲にそれぞれピークがあ
り、１５．２〜１５．６゜の範囲のピーク強度に対する
２７〜３３゜の範囲のピーク強度の比が０．０２より小
さいことを要する。Further, the lithium-manganese composite oxide is
When the first group of manganese oxides, the second group of lithium compounds and naphthalene, anthracene, etc. which are solid at room temperature are mixed and synthesized, due to physical properties such as atmosphere deposition in the firing furnace and vapor pressure of the substance, The charging amount and the firing temperature can be appropriately changed. When the diffraction line of the above-mentioned lithium-manganese composite oxide is obtained by a conventional powder X-ray diffraction method using CuKα ray as an X-ray source, the main diffraction lines existing at a diffraction angle 2θ of 10 to 50 °. Peaks of at least 15.2 to 15.6 ° and 18.6 to 18.8.
The peak intensity in the range of 27 to 33 ° with respect to the peak intensity in the range of 15.2 to 15.6 ° is less than 0.02. is necessary. The peaks at 15.2 to 15.6 ° are (010) of LiMnO 2 which is Pmnm belonging to the orthorhombic system and LiMn which is Pm2m belonging to the orthorhombic system.
(010) of O 2 and 18.6 to 1
The peak at 8.8 ° is the spinel type LiMn 2 O 4
(111) of Li 2 MnO 3 belonging to the monoclinic system (0
02) and the peak at 24.5 to 25.1 ° is (110) and P of LiMnO 2 which is Pmnm.
It is considered to be (011) of LiMnO 2 which is m2m. In addition to the above range, in the vicinity of 35.6 °, 36.9 °, 37.6 °, 39.4 °, 40.8 °, 42.6 °, 45.1 ° and 47. It may have a peak in each range near 4 °. When these diffraction lines have peaks, the ratio (I / I 0 ) of each peak intensity (I) to the peak intensity (I 0 ) existing in the range of 15.2 to 15.6 °.
Is 18.6 to 18.8 °, 24.5 to 25.1 °, 3
Near 5.6 °, 36.9 °, 37.6 °, 3
Near 9.4 °, near 40.8 °, near 42.6 °, 4
In the vicinity of 5.1 ° and in the vicinity of 47.4 °, 0.02-1.5, 0.7-0.2, 0.15-0.
3, 0.05-0.25, 0.05-0.2, 0.45
~ 0.75, 0.05-0.3, 0-0.15, 0.5
It is preferably 5 to 1.1 and 0 to 0.05. The peak positions and intensities in the above X-ray diffraction lines are the types of the manganese oxides of the first group and the lithium compounds of the second group, which are raw materials of the lithium-manganese composite oxide, the mixing ratio, and the oxygen content during firing. And the firing temperature. This is because the crystallinity and crystal size change. However, under any of the conditions, the lithium-manganese composite oxide as a good positive electrode active material has an X-ray diffraction line of 15.2-15.6 [deg.], 18.6-18.8 [deg.] And 24.5-. There is a peak in the range of 25.1 °, and it is necessary that the ratio of the peak intensity in the range of 27 to 33 ° to the peak intensity in the range of 15.2 to 15.6 ° is smaller than 0.02.

【００２１】ここで、Ｘ線回折線１５．２〜１５．６゜
のピーク強度に対する１８．６〜１８．８゜のピーク強
度の比は、０．０２〜１．５の範囲が好ましく、より好
ましくは０．０２〜１．０の範囲、さらに好ましくは
０．０２〜０．４の範囲である。前記ピーク強度の比が
０．０２より小さいリチウム・マンガン複合酸化物を得
ることは上記製造方法では困難であり、ピーク強度の比
が１．５より大きいと、上記と同様に、非水系二次電池
の正極活物質として適用させたとき、実用的でない。さ
らに、ピーク強度の比率が１．０より大きくなると、Ｘ
線回折線の２０．８゜、２１．８゜、２８．１゜、３
２．６゜、３６．２゜、３８．７゜、４４．０゜、４
４．７゜及び４９．０゜付近に微小強度のピークが出現
することがある。また、ごく稀に、ピーク強度の比が
０．４を越えると、多くの極微小強度のピークが出現す
ることがある。これらピークはいずれも、前記原料の第
１群のマンガン酸化物及び第２群のリチウム化合物の種
類、混合の割合、焼成時の酸素含有量及び焼成温度によ
って結晶性及び結晶の大きさが変化するため、出現した
り消滅したりする。The ratio of the peak intensity of 18.6 to 18.8 ° to the peak intensity of X-ray diffraction lines of 15.2 to 15.6 ° is preferably in the range of 0.02 to 1.5, more preferably The range is preferably 0.02 to 1.0, more preferably 0.02 to 0.4. It is difficult to obtain a lithium-manganese composite oxide having a peak intensity ratio of less than 0.02 by the above production method, and if the peak intensity ratio is greater than 1.5, a non-aqueous secondary oxide is obtained in the same manner as above. It is not practical when applied as a positive electrode active material of a battery. Furthermore, when the ratio of peak intensities exceeds 1.0, X
20.8 °, 21.8 °, 28.1 °, 3 of line diffraction line
2.6 °, 36.2 °, 38.7 °, 44.0 °, 4
Peaks of minute intensity may appear near 4.7 ° and 49.0 °. In rare cases, when the peak intensity ratio exceeds 0.4, many extremely small intensity peaks may appear. In all of these peaks, the crystallinity and crystal size change depending on the types of the first group manganese oxides and the second group lithium compounds as raw materials, the mixing ratio, the oxygen content during firing, and the firing temperature. Therefore, it appears and disappears.

【００２２】正極は、上記のように合成して得られるリ
チウム・マンガン複合酸化物を正極活物質として、これ
に導電材、結着材及び場合によっては、固体電解質等を
混合して形成することができる。導電材には、アセチレ
ンブラック、グラファイト粉末等の炭素類や、金属粉末
等を用いることができるが、これに限定されない。結着
材には、ポリテトラフルオロエチレン、ポリフッカビニ
リデン等のフッ素系ポリマー、ポリエチレン、ポリプロ
ピレン等のポリオレフィン系ポリマー等を用いることが
できるが、これに限定されない。これらの混合比は、活
物質１００重量部に対して、導電材を５〜５０重量部、
結着材を１〜３０重量部とすることができる。導電材が
５重量部より少ないと、電極の抵抗あるいは分極等が大
きくなり、放電容量が小さくなるため実用的なリチウム
二次電池が作製できない。導電材が５０重量部より多い
と（混合する導電材の種類により重量部は変わる）、電
極内に含まれる活物質量が減るため、正極としての放電
容量が小さくなり好ましくない。結着材が１重量部より
少ないと、結着能力がなくなってしまい、３０重量部よ
り多いと、導電材の場合と同様に、電極内に含まれる活
物質量が減り、さらに、電極の抵抗あるいは分極等が大
きくなって放電容量が小さくなるため実用的ではない。The positive electrode is formed by mixing the lithium-manganese composite oxide obtained by synthesizing as described above as a positive electrode active material, and mixing this with a conductive material, a binding material and, in some cases, a solid electrolyte. You can As the conductive material, carbons such as acetylene black and graphite powder, metal powder and the like can be used, but the conductive material is not limited thereto. The binder may be, but not limited to, a fluorine-based polymer such as polytetrafluoroethylene or polyfuccavinylidene, or a polyolefin-based polymer such as polyethylene or polypropylene. The mixing ratio of these is 5 to 50 parts by weight of the conductive material with respect to 100 parts by weight of the active material,
The binder may be 1 to 30 parts by weight. If the amount of the conductive material is less than 5 parts by weight, the resistance or polarization of the electrode increases and the discharge capacity decreases, so that a practical lithium secondary battery cannot be manufactured. When the amount of the conductive material is more than 50 parts by weight (the weight part changes depending on the type of the mixed conductive material), the amount of the active material contained in the electrode decreases, and the discharge capacity as the positive electrode becomes small, which is not preferable. If the amount of the binding material is less than 1 part by weight, the binding ability will be lost, and if it is more than 30 parts by weight, the amount of the active material contained in the electrode will be reduced as in the case of the conductive material, and the resistance of the electrode Alternatively, it is not practical because the polarization becomes large and the discharge capacity becomes small.

【００２３】また、本発明の非水系二次電池における負
極は、金属リチウム、リチウムアルミニウム等のリチウ
ム合金や、リチウムイオンをドープ・脱ドープできる物
質、例えば、導電性高分子（ポリアセチレン、ポリチオ
フェン、ポリパラフェニレン等）、熱分解炭素、触媒の
存在下で気相熱分解された熱分解炭素、ピッチ、コーク
ス、タール等から焼成した炭素、セルロース、フェノー
ル樹脂等の高分子より焼成した炭素などや、リチウムイ
オンのインターカレーション／デインターカレーション
の可能な黒鉛（天然黒鉛、人造黒鉛、膨脹黒鉛等）、リ
チウムイオンをインサーション・デサーションできる無
機化合物（ＷＯ2 、ＭｏＯ2 等）等の物質単独又はこれ
らの複合体を用いるこができる。これらの負極活物質の
うち、熱分解炭素、触媒の存在下で気相熱分解された熱
分解炭素、ピッチ、コークス、タール等から焼成した炭
素、高分子より焼成した炭素等、黒鉛（天然黒鉛、人造
黒鉛、膨脹黒鉛等）が電池特性及び安全性の面で好まし
い非水系二次電池を作製することができる。Further, the negative electrode in the non-aqueous secondary battery of the present invention is a lithium alloy such as metallic lithium or lithium aluminum, or a substance capable of being doped or dedoped with lithium ions, such as a conductive polymer (polyacetylene, polythiophene, poly). Paraphenylene, etc.), pyrolytic carbon, pyrolytic carbon vapor-decomposed in the presence of a catalyst, pitch, coke, carbon fired from tar, etc., cellulose, carbon fired from a polymer such as phenol resin, and the like, Lithium ion intercalation / deintercalation graphite (natural graphite, artificial graphite, expanded graphite, etc.), inorganic compound (WO 2 , MoO 2, etc.), which can insert / desert lithium ion, alone or These composites can be used. Of these negative electrode active materials, pyrolytic carbon, pyrolytic carbon vapor-decomposed in the presence of a catalyst, carbon fired from pitch, coke, tar, etc., carbon fired from a polymer, graphite (natural graphite , Artificial graphite, expanded graphite, etc.) can be used to produce a non-aqueous secondary battery that is preferable in terms of battery characteristics and safety.

【００２４】さらに、本発明の非水系二次電池における
イオン伝導体は、例えば有機電解液、高分子固体電解
質、無機固体電解質、溶融塩等を用いることができる
が、中でも有機電解液が好ましい。有機電解液は、溶媒
に電解質を溶解することによって調製することができ
る。溶媒としては、プロピレンカーボネート、エチレン
カーボネート、ブチレンカーボネート、ジエチルカーボ
ネート、ジメチルカーボネート、メチルエチルカーボネ
ート、γ−ブチロラクトン等のエステル類や、テトラヒ
ドロフラン、２−メチルテトラヒドロフランなどの置換
テトラヒドロフラン、ジオキソラン、ジエチルエーテ
ル、ジメトキシエタン、ジエトキシエタン、メトキシエ
トキシエタン等のエーテル類、ジメチルスルホキシド、
スルホラン、メチルスルホラン、アセトニトリル、ギ酸
メチル、酢酸メチル等が挙げられる。これら溶媒は、１
種あるいは２種以上の混合溶媒として使用することがで
きる。また電解質としては、過塩素酸リチウム、ホウフ
ッ化リチウム、ヘキサフルオロリン酸リチウム、６フッ
化砒素リチウム、トリフルオロメタンスルホン酸リチウ
ム、ハロゲン化リチウム、塩化アルミン酸リチウム等の
リチウム塩が挙げられる。これら電解質は、１種或いは
２種以上が混合して使用することができる。なお、溶
媒、電解質は、上記に掲げたものに限定されない。有機
電解液は、活性アルミ、金属リチウムなどにより脱水し
て用いることが好ましい。電解質中における水分量は１
０００ｐｐｍ以下がよく、５００ｐｐｍ以下が好まし
く、１００ｐｐｍ以下がさらに好ましい。また、この脱
水工程の代りに、脱水された溶質又は溶媒を使用しても
よく、さらにこれら脱水された溶質と溶媒とを組合せて
もよい。Further, as the ionic conductor in the non-aqueous secondary battery of the present invention, for example, an organic electrolytic solution, a polymer solid electrolyte, an inorganic solid electrolyte, a molten salt or the like can be used, and among them, the organic electrolytic solution is preferable. The organic electrolytic solution can be prepared by dissolving an electrolyte in a solvent. Examples of the solvent include esters such as propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, and tetrahydrofuran, substituted tetrahydrofuran such as 2-methyltetrahydrofuran, dioxolane, diethyl ether, dimethoxyethane. , Ethers such as diethoxyethane and methoxyethoxyethane, dimethyl sulfoxide,
Examples thereof include sulfolane, methyl sulfolane, acetonitrile, methyl formate and methyl acetate. These solvents are 1
It can be used as one kind or a mixed solvent of two or more kinds. Further, examples of the electrolyte include lithium salts such as lithium perchlorate, lithium borofluoride, lithium hexafluorophosphate, lithium arsenic hexafluoride, lithium trifluoromethanesulfonate, lithium halides and lithium chloroaluminate. These electrolytes can be used alone or in combination of two or more. The solvent and the electrolyte are not limited to those listed above. The organic electrolytic solution is preferably dehydrated with activated aluminum, metallic lithium or the like before use. The amount of water in the electrolyte is 1
000 ppm or less is preferable, 500 ppm or less is preferable, and 100 ppm or less is more preferable. Further, instead of this dehydration step, dehydrated solute or solvent may be used, and further, these dehydrated solute and solvent may be combined.

【００２５】本発明における非水系二次電池は、上記正
極及び負極に、必要に応じてニッケル網などの集電体を
接合させ、さらに外部電極に接合して構成される。ま
た、正極と負極との間に電解質を介在させ、必要に応じ
てポリプロピレン網などのセパレータを介在させてもよ
い。さらに、正極と負極とが接合された外部電極が互に
接触することがないよう、ポリプロピレンやポリエチレ
ンなどのパッキング又はハーメチックシールなどを行う
ことが好ましい。これら電池製造作業は、水分の侵入を
防止するため外部と切断して、アルゴンなどの不活性ガ
ス中又は極度に乾燥した空気中において行うのが好まし
い。The non-aqueous secondary battery in the present invention is constructed by joining a current collector such as a nickel net to the positive electrode and the negative electrode, if necessary, and further joining them to an external electrode. Further, an electrolyte may be interposed between the positive electrode and the negative electrode, and a separator such as a polypropylene net may be interposed if necessary. Further, it is preferable to carry out packing or hermetic sealing of polypropylene or polyethylene so that the external electrodes to which the positive electrode and the negative electrode are joined do not come into contact with each other. It is preferable that these battery manufacturing operations are performed in an inert gas such as argon or in extremely dry air by cutting off from the outside in order to prevent water from entering.

【００２６】[0026]

【作用】本発明による非水系二次電池によれば、負極と
してリチウムを含むか又はリチウムが挿入・脱離可能な
活物質、正極としてリチウム・マンガンの複合酸化物を
含む活物質を組み合わせて用いるため、安価な原料が使
用されるとともに、従来必要であった正極の放電又は負
極の充電工程を行う必要なく、電池製造工程が比較的簡
素化される。According to the non-aqueous secondary battery of the present invention, an active material containing lithium as a negative electrode or capable of inserting / releasing lithium and an active material containing a composite oxide of lithium / manganese as a positive electrode are used in combination. Therefore, an inexpensive raw material is used, and the battery manufacturing process is relatively simplified because it is not necessary to perform the positive electrode discharging process or the negative electrode charging process which is conventionally required.

【００２７】[0027]

【実施例】本発明の非水系二次電池及びその正極活物質
の製造方法の実施例を説明する。 実施例１ ・正極活物質の合成 炭酸リチウムと二酸化マンガン（ＩＣ Ｎｏ．５）と
を、リチウムとマンガンとの比で、Ｌｉ：Ｍｎ＝２．
３：１になるように秤量し、乳鉢で混合した。その後、
この混合物に１００kg／cm2 の圧力をかけてペレットを
作製した。これを８００℃で５時間、空気中で焼成し、
正極活物質の出発原料の１つであるＬｉ2.1ＭｎＯ3.0
を合成した。このＬｉ2.1 ＭｎＯ3.0 についてＸ線回折
を行った結果、Ｌｉ2 ＭｎＯ3 であることがわかった
（図１）。EXAMPLES Examples of the method for producing a non-aqueous secondary battery and its positive electrode active material of the present invention will be described. Example 1-Synthesis of Positive Electrode Active Material Lithium carbonate and manganese dioxide (IC No. 5) were used as Li: Mn = 2.
It was weighed to be 3: 1 and mixed in a mortar. afterwards,
A pressure of 100 kg / cm 2 was applied to this mixture to produce pellets. Bake this in air at 800 ° C for 5 hours,
Li 2.1 MnO 3.0, which is one of the starting materials for the positive electrode active material
Was synthesized. As a result of X-ray diffraction of this Li 2.1 MnO 3.0 , it was found to be Li 2 MnO 3 (FIG. 1).

【００２８】次に、市販のＭｎ2 Ｏ3 と上記で合成した
Ｌｉ2.1 ＭｎＯ3.0 とを、リチウムとマンガンとの比
で、Ｌｉ：Ｍｎ＝１．３：１になるように秤量し、乳鉢
で混合した。この混合粉末を錠剤成形機に入れ、１５０
kg／cm2 の圧力をかけてペレットに作製した。これを８
００℃で３時間、７体積％の酸素を混合した窒素雰囲気
中で焼成し、正極活物質Ｌｉ1.1 ＭｎＯ2.1 を得た。Ｘ
線源にＣｕＫα線を用いて、この活物質の粉末Ｘ線回折
を行なった。その結果を図２に示す。１０〜５０°の間
における回折角２θに存在するおもな回折線のピークは
１５．５°、１８．８°、２１．０°、２２．０°、２
５．０°、３５．７°、３６．４°、３７．１°、３
７．７°、３９．５°、４１．０°、４２．６°、４
５．３°、４７．６°、４８．２°に存在し、１５．５
°に対する強度比（Ｉ／Ｉ0）は、それぞれ１．０、
１．４、０．０６、０．０５、０．３４、０．２３、
０．１９、０．２０、０．１３、０．４７、０．１０、
０．０７、０．６０、０．０４、０．０４であった。Next, commercially available Mn 2 O 3 and Li 2.1 MnO 3.0 synthesized above were weighed so that the ratio of lithium to manganese was Li: Mn = 1.3: 1, and placed in a mortar. Mixed. Put this mixed powder in a tablet press and
Pellets were prepared by applying a pressure of kg / cm 2 . This 8
The positive electrode active material Li 1.1 MnO 2.1 was obtained by firing at 00 ° C. for 3 hours in a nitrogen atmosphere mixed with 7% by volume of oxygen. X
The powder X-ray diffraction of this active material was performed using CuKα ray as a radiation source. The result is shown in FIG. The peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.5 °, 18.8 °, 21.0 °, 22.0 °, 2
5.0 °, 35.7 °, 36.4 °, 37.1 °, 3
7.7 °, 39.5 °, 41.0 °, 42.6 °, 4
Present at 5.3 °, 47.6 °, 48.2 °, and 15.5 °
The intensity ratio (I / I 0 ) with respect to ° is 1.0,
1.4, 0.06, 0.05, 0.34, 0.23,
0.19, 0.20, 0.13, 0.47, 0.10,
The values were 0.07, 0.60, 0.04 and 0.04.

【００２９】・正極の作製 以上のようにして得られた正極活物質を、アセチレンブ
ラック及びポリテトラフルオロエチレンと共にそれぞれ
１００：１０：５の割合で乳鉢にて混合した。そして、
この混合物を加圧成形することにより、直径２０mm、重
量０．２５ｇのペレットを作製した。加圧成形時に、集
電体として作用するチタンメッシュも導入した。チタン
メッシュからチタン線をスポット溶接することにより集
電を取り、水分除去のために２００℃で減圧乾燥し、こ
れを評価用の電極とした。Preparation of Positive Electrode The positive electrode active material obtained as described above was mixed with acetylene black and polytetrafluoroethylene in a ratio of 100: 10: 5 in a mortar. And
The mixture was pressure-molded to prepare pellets having a diameter of 20 mm and a weight of 0.25 g. A titanium mesh that acts as a current collector was also introduced during pressure molding. A titanium wire was spot-welded from a titanium mesh to collect current, which was dried under reduced pressure at 200 ° C. to remove water and used as an electrode for evaluation.

【００３０】・正極の評価 評価は３極法を用い、対極及び参照極にリチウムを用い
た。電解液には、１mol/lの過塩素酸リチウムを溶解し
たプロピレンカーボネートを用いた。５mA/gの電流密度
で、初めに４．１Ｖまで充電を行い、続いて同じ電流で
２．０Ｖまで放電を行った。２回目以降も同じ電位の範
囲、電流密度で充放電を繰り返した。Evaluation of the positive electrode A three-pole method was used for evaluation, and lithium was used for the counter electrode and the reference electrode. As the electrolytic solution, propylene carbonate in which 1 mol / l lithium perchlorate was dissolved was used. At a current density of 5 mA / g, the battery was first charged to 4.1 V and then discharged to 2.0 V at the same current. Charge and discharge were repeated in the same potential range and current density after the second time.

【００３１】その結果、前記のごとく作製したＬｉ1.1
ＭｎＯ2.1 正極の２回目の放電容量は１０８mAh/g、平
均電位は２．８６Ｖであった。 実施例２ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と水酸化リチウムと
を、リチウムとマンガンの比で、Ｌｉ：Ｍｎ＝１：１に
なるように秤量し、実施例１と同様にペレットに作製し
た。これを７００℃で３時間、窒素雰囲気中で焼成し、
正極活物質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を
用いて、この活物質の粉末Ｘ線回折を行なった。その結
果を図３に示す。１０〜５０°の間における回折角２θ
に存在するおもな回折線のピークは、１５．４°、１
８．７°、２４．６°、３５．６°、３６．９°、３
７．６°、３９．４°、４０．８°、４２．５°、４
５．１°、４７．４°に存在し、１５．４°に対する強
度比（Ｉ／Ｉ0）は、それぞれ１．０、０．１５、０．
２５、０．２２、０．１４、０．１６、０．５１、０．
０７、０．０５、０．６７、０．０５であった。As a result, Li 1.1 prepared as described above was used.
The second-time discharge capacity of the MnO 2.1 positive electrode was 108 mAh / g, and the average potential was 2.86 V. Example 2 Synthesis of Positive Electrode Active Material Electrolytic manganese dioxide (IC No. 1) and lithium hydroxide were weighed so that the ratio of lithium to manganese was Li: Mn = 1: 1. Similarly, pellets were prepared. This was baked at 700 ° C. for 3 hours in a nitrogen atmosphere,
A positive electrode active material LiMnO 2 was obtained. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. The result is shown in FIG. Diffraction angle 2θ between 10 and 50 °
The main peaks of the diffraction lines existing in are 15.4 °, 1
8.7 °, 24.6 °, 35.6 °, 36.9 °, 3
7.6 °, 39.4 °, 40.8 °, 42.5 °, 4
It exists at 5.1 ° and 47.4 °, and the intensity ratio (I / I 0 ) with respect to 15.4 ° is 1.0, 0.15, 0 .
25, 0.22, 0.14, 0.16, 0.51, 0.
It was 07, 0.05, 0.67, and 0.05.

【００３２】・正極の作製 以上のようにして得られた正極活物質をアセチレンブラ
ック及びポリテトラフルオロエチレンと共にそれぞれ１
００：２０：１５の割合で混合した以外は、実施例１と
同様にして、直径２０mm、重量０．２５ｇのペレットを
得た。 ・正極の評価 γ−ブチロラクトンとジメトキシエタンとの１：１混合
溶媒に、０．５mol/lのトリフルオロメタンスルホン酸
リチウムを溶解した電解液を用いた以外は、実施例１と
同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was used together with acetylene black and polytetrafluoroethylene to prepare 1
Pellets having a diameter of 20 mm and a weight of 0.25 g were obtained in the same manner as in Example 1, except that the pellets were mixed at a ratio of 00:20:15. Evaluation of Positive Electrode Evaluation was performed in the same manner as in Example 1 except that an electrolytic solution in which 0.5 mol / l lithium trifluoromethanesulfonate was dissolved in a 1: 1 mixed solvent of γ-butyrolactone and dimethoxyethane was used. went.

【００３３】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１２１mAh/g、平均電位
は２．７２Ｖであった。 実施例３ ・正極活物質の合成 ５％の酢酸リチウムを溶かした水溶液に電解二酸化マン
ガン（ＩＣ No.1）を、リチウムとマンガンの比で、Ｌ
ｉ：Ｍｎ＝１：１になるように加え、８０〜１００℃に
て水を蒸発させ、次いで乳鉢で粉砕、混合した。この混
合粉末を実施例１と同様にペレットに作製した。これを
４５０℃で７２時間、窒素雰囲気中で焼成し、正極活物
質ＬｉＭｎＯ1.9を得た。Ｘ線源にＣｕＫα線を用い
て、この活物質の粉末Ｘ線回折を行なった。その結果を
図４に示す。１０〜５０°の間における回折角２θに存
在するおもな回折線のピークは、１５．４°、１８．６
°、２４．９°、３５．６°、３６．１°、３６．９
゜、３７．６°、３９．３°、４０．９°、４２．４
°、４３．７゜、４５．１°、４７．４°に存在し、１
５．４°に対する強度比（Ｉ／Ｉ0）は、それぞれ１．
０、０．４４、０．２４、０．２３、０．０８、０．２
２、０．１８、０．６３、０．０７、０．０５、０．０
４、０．９９、０．０６であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 121 mAh / g, and the average potential was 2.72V. Example 3 Synthesis of Positive Electrode Active Material Electrolytic manganese dioxide (IC No. 1) was added to an aqueous solution in which 5% lithium acetate was dissolved, and the ratio of lithium to manganese was L.
i: Mn = 1: 1, water was evaporated at 80 to 100 ° C., and then crushed and mixed in a mortar. This mixed powder was made into pellets in the same manner as in Example 1. This was baked at 450 ° C. for 72 hours in a nitrogen atmosphere to obtain a positive electrode active material LiMnO 1.9 . This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. The result is shown in FIG. The peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.4 ° and 18.6.
°, 24.9 °, 35.6 °, 36.1 °, 36.9
°, 37.6 °, 39.3 °, 40.9 °, 42.4
Exist at °, 43.7 °, 45.1 °, 47.4 ° and 1
The intensity ratio (I / I 0 ) for 5.4 ° is 1.
0, 0.44, 0.24, 0.23, 0.08, 0.2
2, 0.18, 0.63, 0.07, 0.05, 0.0
It was 4, 0.99 and 0.06.

【００３４】・正極の作製 以上のようにして得られた正極活物質をアセチレンブラ
ック及びポリテトラフルオロエチレンと共にそれぞれ１
００：１０：８の割合で混合した以外は、実施例１と同
様にして、直径２０mm、重量０．２５ｇのペレットを作
製した。 ・正極の評価 プロピレンカーボネートとジエチルカーボネートとの
２：１混合溶媒に１mol/lのヘキサフルオロリン酸リチ
ウムを溶解した電解液を用いた以外は、実施例１と同様
にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was used together with acetylene black and polytetrafluoroethylene to prepare 1
Pellets having a diameter of 20 mm and a weight of 0.25 g were prepared in the same manner as in Example 1 except that the mixture was mixed at a ratio of 00: 10: 8. -Evaluation of positive electrode Evaluation was performed in the same manner as in Example 1 except that an electrolytic solution in which 1 mol / l lithium hexafluorophosphate was dissolved in a 2: 1 mixed solvent of propylene carbonate and diethyl carbonate was used.

【００３５】その結果、前記のごとく作製したＬｉＭｎ
Ｏ1.9正極の２回目の放電容量は、１１３mAh/g、平均電
位は２．６８Ｖであった。 実施例４ ・正極活物質の合成 ＭｎＯＯＨと酸化リチウムとを、リチウムとマンガンと
の比で、Ｌｉ：Ｍｎ＝１．３：１になるように秤量し、
実施例１と同様にペレットを作った。これを４００℃で
９６時間、窒素雰囲気中で焼成し、正極活物質Ｌｉ1.2
ＭｎＯ2.2 を得た。Ｘ線源にＣｕＫα線を用いて、この
活物質の粉末Ｘ線回折を行なった。その結果、１０〜５
０°の間における回折角２θに存在するおもな回折線の
ピークは、１５．６°、１８．８°、２５．１°、３
５．７°、３６．２°、３６．９゜、３７．８°、３
９．５°、４０．９°、４２．４°、４３．８゜、４
５．１°、４７．５°に存在し、１５．６°に対する強
度比（Ｉ／Ｉ0)は、それぞれ１．０、０．３４、０．２
４、０．２２、０．０４、０．１７、０．１５、０．５
８、０．０４、０．０２、０．０３、０．７７、０．０
４であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 1.9 positive electrode was 113 mAh / g, and the average potential was 2.68 V. Example 4 Synthesis of Positive Electrode Active Material MnOOH and lithium oxide were weighed so that the ratio of lithium to manganese was Li: Mn = 1.3: 1,
Pellets were made as in Example 1. This was baked at 400 ° C. for 96 hours in a nitrogen atmosphere to obtain a positive electrode active material Li 1.2.
MnO 2.2 was obtained. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. As a result, 10-5
The peaks of the main diffraction lines existing at the diffraction angle 2θ between 0 ° are 15.6 °, 18.8 °, 25.1 °, 3
5.7 °, 36.2 °, 36.9 °, 37.8 °, 3
9.5 °, 40.9 °, 42.4 °, 43.8 °, 4
It exists at 5.1 ° and 47.5 °, and the intensity ratio (I / I 0 ) for 15.6 ° is 1.0, 0.34, and 0.2, respectively.
4, 0.22, 0.04, 0.17, 0.15, 0.5
8, 0.04, 0.02, 0.03, 0.77, 0.0
It was 4.

【００３６】・正極の作製 ここでは、一般的な方法により正極を作製した。つま
り、結着剤の溶液又は結着剤を分散させた懸濁液に、活
物質粉末を分散し、混練しペーストを作製した。次い
で、このペーストを集電体箔上に塗布するか、又は金属
三次元多孔質集電体の孔中に塗り込み、上記溶液又は懸
濁液の溶媒の沸点以上の温度、かつ結着剤の融点あるい
は軟化点付近の温度で、不活性雰囲気下、空気中あるい
は減圧下で熱処理した。Preparation of Positive Electrode Here, a positive electrode was prepared by a general method. That is, the active material powder was dispersed and kneaded in a binder solution or a suspension in which the binder was dispersed to prepare a paste. Then, the paste is applied onto a current collector foil, or is applied to the holes of the metal three-dimensional porous current collector, at a temperature equal to or higher than the boiling point of the solvent of the solution or suspension, and a binder. The heat treatment was carried out at a temperature near the melting point or the softening point in air or under reduced pressure in an inert atmosphere.

【００３７】具体的には、上記のようにして得られた正
極活物質とアセチレンブラックとを、結着剤であるポリ
フッ化ビニリデンを溶剤Ｎ−メチル−２−ピロリドンに
溶かした溶液に分散させ、正極活物質のペーストを調製
した。このペーストをアルミ箔集電体上片面に塗布し、
空気中６０℃で仮乾燥した。その後、溶剤であるＮ−メ
チル−２−ピロリドンを完全に除去するために２５０℃
で真空乾燥して正極シート電極を作製した。さらに水分
除去のために２００℃で減圧乾燥したものを正極として
用いた。この正極は、見かけ上の表面積４ｃｍ2 、電極
厚み７８μｍ（集電体の厚みが２０μｍ）であった。Specifically, the positive electrode active material and acetylene black obtained as described above are dispersed in a solution in which polyvinylidene fluoride as a binder is dissolved in a solvent N-methyl-2-pyrrolidone, A positive electrode active material paste was prepared. Apply this paste on one side of the aluminum foil current collector,
It was temporarily dried in air at 60 ° C. After that, in order to completely remove the solvent N-methyl-2-pyrrolidone, 250 ° C.
Was vacuum dried to produce a positive electrode sheet electrode. Further, in order to remove water, one dried under reduced pressure at 200 ° C. was used as a positive electrode. This positive electrode had an apparent surface area of 4 cm 2 and an electrode thickness of 78 μm (current collector thickness was 20 μm).

【００３８】・正極の評価 プロピレンカーボネートとジメチルカーボネートの１：
１混合溶媒に、１mol/lの過塩素酸リチウムを溶解した
電解液を用いた以外は、実施例１と同様にして評価を行
った。その結果、前記のごとく作製したＬｉ1.3 ＭｎＯ
3.2正極の２回目の放電容量は、１１８mAh/g、平均電位
は２．９５Ｖであった。 実施例５ ・正極活物質の合成 二酸化マンガン（ＩＣ No.5）と硝酸リチウムとを、リ
チウムとマンガンの比で、Ｌｉ：Ｍｎ＝１：１になるよ
うに秤量し、実施例１と同様にペレットを作った。これ
を１１００℃で４時間、２体積％の酸素を混合した窒素
雰囲気中で焼成し、正極活物質ＬｉＭｎＯ2を得た。Ｘ
線源にＣｕＫα線を用いて、この活物質の粉末Ｘ線回折
を行なった。その結果、１０〜５０°の間における回折
角２θに存在するおもな回折線のピークは、１５．３
°、１８．７°、２４．６°、３５．６°、３６．８
°、３７．５゜、３９．２°、４０．７°、４２．４
°、４５．０°、４７．３°に存在し、１５．３°に対
する強度比（Ｉ／Ｉ0）は、それぞれ１．０、０．０
２、０．５８、０．１８、０．１８、０．０９、０．５
３、０．２１、０．０８、０．７５、０．０３であっ
た。Evaluation of positive electrode 1: Propylene carbonate and dimethyl carbonate 1:
Evaluation was performed in the same manner as in Example 1 except that an electrolytic solution in which 1 mol / l lithium perchlorate was dissolved in 1 mixed solvent was used. As a result, Li 1.3 MnO prepared as described above
3.2 The second discharge capacity of the positive electrode was 118 mAh / g, and the average potential was 2.95V. Example 5-Synthesis of positive electrode active material Manganese dioxide (IC No. 5) and lithium nitrate were weighed so that the ratio of lithium to manganese was Li: Mn = 1: 1, and the same as in Example 1. Made pellets. This was baked at 1100 ° C. for 4 hours in a nitrogen atmosphere mixed with 2% by volume of oxygen to obtain a positive electrode active material LiMnO 2 . X
The powder X-ray diffraction of this active material was performed using CuKα ray as a radiation source. As a result, the peak of the main diffraction line existing at the diffraction angle 2θ between 10 and 50 ° was 15.3
°, 18.7 °, 24.6 °, 35.6 °, 36.8
°, 37.5 °, 39.2 °, 40.7 °, 42.4
At 4 °, 45.0 °, and 47.3 °, and the intensity ratio (I / I 0 ) for 15.3 ° is 1.0 and 0.0, respectively.
2, 0.58, 0.18, 0.18, 0.09, 0.5
The values were 3, 0.21, 0.08, 0.75 and 0.03.

【００３９】・正極の作製 以上のようにして得られた正極活物質を、Ｎ−メチル−
２−ピロリドンを除去するために２３０℃で真空乾燥し
た以外は実施例４と同様にして正極を作製した。この正
極は、見かけ上の表面積４ｃｍ2 、電極厚み８３μｍ
（集電体の厚みが２０μｍ）であった。 ・正極の評価 実施例４と同様に評価した。Preparation of Positive Electrode The positive electrode active material obtained as described above was treated with N-methyl-
A positive electrode was produced in the same manner as in Example 4 except that it was vacuum dried at 230 ° C. to remove 2-pyrrolidone. This positive electrode has an apparent surface area of 4 cm 2 and an electrode thickness of 83 μm.
(The thickness of the current collector was 20 μm). Evaluation of positive electrode Evaluation was performed in the same manner as in Example 4.

【００４０】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１３１mAh/g、平均電位
は２．７８Ｖであった。 実施例６ ・正極活物質の合成 三二酸化マンガン（Ｍｎ2 Ｏ3 ）と硝酸リチウムとを、
リチウムとマンガンとの比で、Ｌｉ：Ｍｎ＝０．９：１
になるように秤量し、実施例１と同様にペレットを作っ
た。これを６００℃で１８時間、１０体積％の酸素を混
合した窒素雰囲気中で焼成し、正極活物質Ｌｉ0.8 Ｍｎ
Ｏ1.9を得た。Ｘ線源にＣｕＫα線を用いて、この活物
質の粉末Ｘ線回折を行なった。その結果、１０〜５０°
の間における回折角２θに存在するおもな回折線のピー
クは、１５．５°、１８．７°、２４．８°、３５．６
°、３６．３°、３６．８°、３７．６゜、３９．３
°、４０．８°、４２．６°、４４．０°、４５．２
°、４７．３°に存在し、１５．５°に対する強度比
（Ｉ／Ｉ0）は、それぞれ１．０、１．５、０．５９、
０．１８、０．３２、０．０８、０．１１、０．５７、
０．２８、０．１０、０．３７、０．５８、０．１０で
あった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 131 mAh / g, and the average potential was 2.78V. Example 6 Synthesis of Positive Electrode Active Material Manganese trioxide (Mn 2 O 3 ) and lithium nitrate,
The ratio of lithium to manganese is Li: Mn = 0.9: 1.
Were weighed so that pellets were prepared in the same manner as in Example 1. This was baked at 600 ° C. for 18 hours in a nitrogen atmosphere mixed with 10% by volume of oxygen to obtain a positive electrode active material Li 0.8 Mn.
O1.9 was obtained. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. As a result, 10 to 50 °
The peaks of the main diffraction lines existing at the diffraction angle 2θ between 15.5 °, 18.7 °, 24.8 °, and 35.6.
°, 36.3 °, 36.8 °, 37.6 °, 39.3
°, 40.8 °, 42.6 °, 44.0 °, 45.2
And the intensity ratio (I / I 0 ) to 15.5 ° is 1.0, 1.5, 0.59, and respectively.
0.18, 0.32, 0.08, 0.11, 0.57,
The values were 0.28, 0.10, 0.37, 0.58 and 0.10.

【００４１】・正極の作製 以上のようにして得られた正極活物質を、Ｎ−メチル−
２−ピロリドンを除去するために２００℃で真空乾燥し
た以外は実施例４と同様にして正極を作製した。この正
極は、見かけ上の表面積４ｃｍ2 、電極厚み７６μｍ
（集電体の厚みが２０μｍ）であった。Preparation of Positive Electrode The positive electrode active material obtained as described above was treated with N-methyl-
A positive electrode was produced in the same manner as in Example 4 except that the product was vacuum dried at 200 ° C. to remove 2-pyrrolidone. This positive electrode has an apparent surface area of 4 cm 2 and an electrode thickness of 76 μm.
(The thickness of the current collector was 20 μm).

【００４２】・正極の評価 実施例４と同様に評価した。その結果、前記のごとく作
製したＬｉ0.9 ＭｎＯ1.9 正極の２回目の放電容量は、
９８mAh/g、平均電位は３．２６Ｖであった。 実施例７ ・正極活物質の合成 二酸化マンガン（ＩＣ No.5）と酸化リチウムとを、リ
チウムとマンガンとの比で、Ｌｉ：Ｍｎ＝１．２：１に
なるように秤量し、実施例１と同様にペレットを作っ
た。これを３００℃で２４時間、５０体積％のプロパン
を混合した窒素雰囲気中（ガスボンベからガスフローで
供給した）で焼成し、正極活物質Ｌｉ1.1ＭｎＯ2を得
た。Ｘ線源にＣｕＫα線を用いて、この活物質の粉末Ｘ
線回折を行なった。その結果、１０〜５０°の間におけ
る回折角２θに存在するおもな回折線のピークは、１
５．５°、１８．８°、２４．９°、３５．７°、３
６．２°、３６．９゜、３７．７゜、３９．５°、４
０．８°、４２．５°、４３．８°、４５．１°、４
７．５°に存在し、１５．５°に対する強度比（Ｉ／Ｉ
0）は、それぞれ１．０、０．８８、０．６４、０．１
８、０．２２、０．１４、０．１１、０．５４、０．２
１、０．１０、０．１３、０．５７、０．０４であっ
た。Evaluation of Positive Electrode Evaluation was carried out in the same manner as in Example 4. As a result, the second discharge capacity of the Li 0.9 MnO 1.9 positive electrode prepared as described above was
It was 98 mAh / g, and the average potential was 3.26V. Example 7-Synthesis of positive electrode active material Manganese dioxide (IC No. 5) and lithium oxide were weighed so that the ratio of lithium and manganese was Li: Mn = 1.2: 1, and Example 1 was used. And made pellets as well. This was baked at 300 ° C. for 24 hours in a nitrogen atmosphere mixed with 50% by volume of propane (supplied by a gas flow from a gas cylinder) to obtain a positive electrode active material Li 1.1 MnO 2 . Using CuKα rays as an X-ray source, powder X of this active material
Line diffraction was performed. As a result, the peak of the main diffraction line existing at the diffraction angle 2θ between 10 and 50 ° is 1
5.5 °, 18.8 °, 24.9 °, 35.7 °, 3
6.2 °, 36.9 °, 37.7 °, 39.5 °, 4
0.8 °, 42.5 °, 43.8 °, 45.1 °, 4
Exists at 7.5 ° and has an intensity ratio (I / I
0 ) are 1.0, 0.88, 0.64, and 0.1, respectively.
8, 0.22, 0.14, 0.11, 0.54, 0.2
The values were 1, 0.10, 0.13, 0.57 and 0.04.

【００４３】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み８５μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 エチレンカーボネートとジメチルカーボネートの１：１
混合溶媒に、１mol/lの過塩素酸リチウムを溶解した電
解液を用いた以外は、実施例１と同様にして評価を行っ
た。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 85 μm (current collector thickness 20 μm)
Met.・ Evaluation of positive electrode 1: 1 of ethylene carbonate and dimethyl carbonate
Evaluation was performed in the same manner as in Example 1 except that an electrolytic solution in which 1 mol / l lithium perchlorate was dissolved was used as the mixed solvent.

【００４４】その結果、前記のごとく作製したＬｉ1.1
ＭｎＯ2正極の２回目の放電容量は、１２３mAh/g、平均
電位は２．９３Ｖであった。 実施例８ ・正極活物質の合成 ＭｎＯＯＨと酸化リチウムとを、リチウムとマンガンと
の比で、Ｌｉ：Ｍｎ＝１．１：１になるように秤量し、
実施例１と同様にペレットを作った。これを６００℃で
８時間、５体積％のプロパンを混合した窒素雰囲気中
（ガスボンベからガスフローで供給した）で焼成し、正
極活物質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を用
いて、この活物質の粉末Ｘ線回折を行なった。その結
果、１０〜５０°の間における回折角２θに存在するお
もな回折線のピークは、１５．５°、１８．７°、２
４．９°、３５．７°、３６．２°、３６．９゜、３
７．６゜、３９．４°、４０．７°、４２．５°、４
３．９°、４５．０°、４７．４°に存在し、１５．５
°に対する強度比（Ｉ／Ｉ0）は、それぞれ１．０、
０．５１、０．５８、０．１８、０．０８、０．１０、
０．１０、０．６３、０．２３、０．１２、０．０５、
０．５７、０．０３であった。As a result, Li 1.1 prepared as described above was used.
The second-time discharge capacity of the MnO 2 positive electrode was 123 mAh / g, and the average potential was 2.93V. Example 8 Synthesis of Positive Electrode Active Material MnOOH and lithium oxide were weighed so that the ratio of lithium to manganese was Li: Mn = 1.1: 1,
Pellets were made as in Example 1. This was baked at 600 ° C. for 8 hours in a nitrogen atmosphere mixed with 5% by volume of propane (supplied by a gas flow from a gas cylinder) to obtain a positive electrode active material LiMnO 2 . This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. As a result, the peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.5 °, 18.7 °, and 2
4.9 °, 35.7 °, 36.2 °, 36.9 °, 3
7.6 °, 39.4 °, 40.7 °, 42.5 °, 4
Present at 3.9 °, 45.0 °, 47.4 °, 15.5
The intensity ratio (I / I 0 ) with respect to ° is 1.0,
0.51, 0.58, 0.18, 0.08, 0.10,
0.10, 0.63, 0.23, 0.12, 0.05,
It was 0.57 and 0.03.

【００４５】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み７３μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 73 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００４６】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１２５mAh/g、平均電位
は２．８３Ｖであった。 実施例９ ・正極活物質の合成 ４００℃で１０時間、３０体積％のプロパンを混合した
窒素雰囲気中で焼成した以外は、実施例８と同様に正極
活物質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を用い
て、この活物質の粉末Ｘ線回折を行なった。その結果、
１０〜５０°の間における回折角２θに存在するおもな
回折線のピークは、１５．５°、１８．８°、２４．７
°、３５．６°、３６．３°、３６．９゜、３７．５
゜、３９．４°、４０．８°、４２．５°、４４．０
°、４５．０°、４７．４°に存在し、１５．５°に対
する強度比（Ｉ／Ｉ0）は、それぞれ１．０、０．６
５、０．６６、０．１６、０．１５、０．１２、０．０
８、０．４９、０．２４、０．１４、０．１１、０．６
１、０．０４であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 125 mAh / g, and the average potential was 2.83 V. Example 9-Synthesis of Positive Electrode Active Material A positive electrode active material LiMnO 2 was obtained in the same manner as in Example 8 except that firing was performed at 400 ° C. for 10 hours in a nitrogen atmosphere mixed with 30% by volume of propane. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. as a result,
The peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.5 °, 18.8 °, and 24.7.
°, 35.6 °, 36.3 °, 36.9 °, 37.5
°, 39.4 °, 40.8 °, 42.5 °, 44.0
At 4 °, 45.0 °, and 47.4 °, and the intensity ratio (I / I 0 ) for 15.5 ° is 1.0 and 0.6, respectively.
5, 0.66, 0.16, 0.15, 0.12, 0.0
8, 0.49, 0.24, 0.14, 0.11, 0.6
It was 1, 0.04.

【００４７】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み８１μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 81 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００４８】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１１５mAh/g、平均電位
は２．９０Ｖであった。 実施例１０ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と酸化リチウムと
を、リチウムとマンガンとの比で、Ｌｉ：Ｍｎ＝１．
１：１になるように秤量し、実施例１と同様にペレット
を作った。これを１１００℃で５時間、０．０１体積％
のプロパンを混合したアルゴン雰囲気中（ガスボンベか
らガスフローで供給した）で焼成し、正極活物質ＬｉＭ
ｎＯ2を得た。Ｘ線源にＣｕＫα線を用いて、この活物
質の粉末Ｘ線回折を行なった。その結果、１０〜５０°
の間における回折角２θに存在するおもな回折線のピー
クは、１５．３°、１８．７°、２４．６°、３５．５
°、３６．３°、３６．９゜、３７．５゜、３９．３
°、４０．７°、４２．５°、４４．０°、４５．１
°、４７．４°に存在し、１５．３°に対する強度比
（Ｉ／Ｉ0）は、それぞれ１．０、０．３３、０．６
２、０．１８、０．１０、０．１３、０．０８、０．５
８、０．２５、０．１２、０．０９、０．６６、０．０
４であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 115 mAh / g, and the average potential was 2.90 V. Example 10-Synthesis of positive electrode active material Electrolytic manganese dioxide (IC No. 1) and lithium oxide were used in a ratio of lithium to manganese, Li: Mn = 1.
Weighed to be 1: 1 and pelletized in the same manner as in Example 1. This is 5 hours at 1100 ℃, 0.01% by volume
Of the positive electrode active material LiM, which was baked in an argon atmosphere mixed with propane (supplied by gas flow from a gas cylinder).
nO 2 was obtained. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. As a result, 10 to 50 °
The peaks of the main diffraction lines existing at the diffraction angle 2θ between 15.3 °, 18.7 °, 24.6 °, and 35.5 °
°, 36.3 °, 36.9 °, 37.5 °, 39.3
°, 40.7 °, 42.5 °, 44.0 °, 45.1
And the intensity ratio (I / I 0 ) to 15.3 ° are 1.0, 0.33, and 0.6, respectively.
2, 0.18, 0.10, 0.13, 0.08, 0.5
8, 0.25, 0.12, 0.09, 0.66, 0.0
It was 4.

【００４９】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み７５μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 75 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００５０】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１２９mAh/g、平均電位
は２．８５Ｖであった。 実施例１１ ・正極活物質の合成 ２５０℃で５時間、３０体積％の水素を混合した窒素雰
囲気中で焼成した以外は、実施例１０と同様に正極活物
質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を用いて、
この活物質の粉末Ｘ線回折を行なった。その結果、１０
〜５０°の間における回折角２θに存在するおもな回折
線のピークは、１５．４°、１８．８°、２４．７°、
３５．６°、３６．３°、３６．９゜、３７．６゜、３
９．４°、４０．７°、４２．６°、４４．１°、４
５．１°、４７．３°に存在し、１５．４°に対する強
度比（Ｉ／Ｉ0）は、それぞれ１．０、０．３５、０．
５９、０．１７、０．０９、０．１７、０．０８、０．
５１、０．２２、０．１５、０．０８、０．５８、０．
０３であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 129 mAh / g, and the average potential was 2.85 V. 5 hours at synthesis 250 ° C. Example 11 positive-electrode active material, except that firing in a nitrogen atmosphere a mixture of 30 vol% hydrogen was obtained in the same manner as the positive electrode active material LiMnO 2 as in Example 10. Using CuKα rays as the X-ray source,
This active material was subjected to powder X-ray diffraction. As a result, 10
The peaks of the main diffraction lines existing at the diffraction angle 2θ between ˜50 ° are 15.4 °, 18.8 °, 24.7 °,
35.6 °, 36.3 °, 36.9 °, 37.6 °, 3
9.4 °, 40.7 °, 42.6 °, 44.1 °, 4
It exists at 5.1 ° and 47.3 °, and the intensity ratio (I / I 0 ) with respect to 15.4 ° is 1.0, 0.35, 0 .
59, 0.17, 0.09, 0.17, 0.08, 0.
51, 0.22, 0.15, 0.08, 0.58, 0.
It was 03.

【００５１】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み７０μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 70 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００５２】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１２６mAh/g、平均電位
は２．７７Ｖであった。 実施例１２ ・正極活物質の合成 ３００℃で５時間、５体積％の水素を混合した窒素雰囲
気中で焼成した以外は、実施例１０と同様に正極活物質
ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を用いて、こ
の活物質の粉末Ｘ線回折を行なった。その結果、１０〜
５０°の間における回折角２θに存在するおもな回折線
のピークは、１５．５°、１８．８°、２４．８°、３
５．６°、３６．４°、３７．０゜、３７．６゜、３
９．４°、４０．８°、４２．６°、４４．１°、４
５．１°、４７．４°に存在し、１５．５°に対する強
度比（Ｉ／Ｉ0）は、それぞれ１．０、０．２４、０．
４８、０．１７、０．０４、０．１１、０．０７、０．
６１、０．２８、０．１４、０．０３、０．５７、０．
０２であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 126 mAh / g, and the average potential was 2.77V. 5 hours at synthesis 300 ° C. Example 12 positive-electrode active material, except that firing in a nitrogen atmosphere a mixture of hydrogen 5 vol%, was obtained in the same manner as the positive electrode active material LiMnO 2 as in Example 10. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. As a result, 10
The peaks of the main diffraction lines existing at the diffraction angle 2θ between 50 ° are 15.5 °, 18.8 °, 24.8 °, 3
5.6 °, 36.4 °, 37.0 °, 37.6 °, 3
9.4 °, 40.8 °, 42.6 °, 44.1 °, 4
It exists at 5.1 ° and 47.4 °, and the intensity ratio (I / I 0 ) with respect to 15.5 ° is 1.0, 0.24, 0 .
48, 0.17, 0.04, 0.11, 0.07, 0.
61, 0.28, 0.14, 0.03, 0.57, 0.
It was 02.

【００５３】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み８８μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 88 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００５４】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１１７mAh/g、平均電位
は２．７５Ｖであった。 実施例１３ ・正極活物質の合成 ４００℃で５時間、０．１体積％の水素を混合した窒素
雰囲気中で焼成した以外は、実施例１０と同様に正極活
物質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を用い
て、この活物質の粉末Ｘ線回折を行なった。その結果、
１０〜５０°の間における回折角２θに存在するおもな
回折線のピークは、１５．４°、１８．７°、２４．７
°、３５．５°、３６．９°、３７．５゜、３９．３
°、４０．７°、４２．５°、４５．１°、４７．３°
に存在し、１５．４°に対する強度比（Ｉ／Ｉ0）は、
それぞれ１．０、０．０９、０．６２、０．１９、０．
１０、０．０８、０．５１、０．２６、０．１５、０．
６６、０．０３であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 117 mAh / g, and the average potential was 2.75 V. 5 hours at synthesis 400 ° C. Example 13 positive-electrode active material, except that firing in a nitrogen atmosphere a mixture of 0.1% hydrogen by volume, to give the same positive electrode active material LiMnO 2 as in Example 10. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. as a result,
The peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.4 °, 18.7 °, and 24.7.
°, 35.5 °, 36.9 °, 37.5 °, 39.3
°, 40.7 °, 42.5 °, 45.1 °, 47.3 °
And the intensity ratio (I / I 0 ) for 15.4 ° is
1.0, 0.09, 0.62, 0.19, 0.
10, 0.08, 0.51, 0.26, 0.15, 0.
It was 66 and 0.03.

【００５５】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み８２μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 82 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００５６】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１３０mAh/g、平均電位
は２．８１Ｖであった。 実施例１４ ・正極活物質の合成 ８００℃で５時間、２５℃の一定温度に保たれたベンゼ
ンにアルゴンをバブルさせ、ベンゼンを含有したアルゴ
ンを焼成容器にフローさせながら焼成した以外は、実施
例１０と同様に正極活物質ＬｉＭｎＯ2を得た。Ｘ線源
にＣｕＫα線を用いて、この活物質の粉末Ｘ線回折を行
なった。その結果、１０〜５０°の間における回折角２
θに存在するおもな回折線のピークは、１５．４°、１
８．８°、２４．７°、３５．６°、３６．９°、３
７．５゜、３９．３°、４０．７°、４２．５°、４
５．０°、４７．３°に存在し、１５．４°に対する強
度比（Ｉ／Ｉ0）は、それぞれ１．０、０．１５、０．
６１、０．１５、０．１３、０．０９、０．５８、０．
２８、０．１０、０．５５、０．０４であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 130 mAh / g, and the average potential was 2.81 V. Example 14 Synthesis of Positive Electrode Active Material Example except that benzene which was kept at a constant temperature of 25 ° C. for 5 hours at 800 ° C. was bubbled with argon, and the benzene-containing argon was baked while flowing in a baking container. A positive electrode active material LiMnO 2 was obtained in the same manner as in 10. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. As a result, the diffraction angle 2 between 10 and 50 °
The main diffraction peaks at θ are 15.4 ° and 1
8.8 °, 24.7 °, 35.6 °, 36.9 °, 3
7.5 °, 39.3 °, 40.7 °, 42.5 °, 4
It exists at 5.0 ° and 47.3 °, and the intensity ratio (I / I 0 ) with respect to 15.4 ° is 1.0, 0.15, 0 .
61, 0.15, 0.13, 0.09, 0.58, 0.
The values were 28, 0.10, 0.55 and 0.04.

【００５７】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み８１μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 81 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００５８】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１２２mAh/g、平均電位
は２．９３Ｖであった。 実施例１５ ・正極活物質の合成 ５０℃の一定温度に保たれた１−ペンタノールにアルゴ
ンをバブルさせ、１−ペンタノールを含んだアルゴンを
焼成容器にフローさせた以外は実施例１０と同様に焼成
し、正極活物質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα
線を用いて、この活物質の粉末Ｘ線回折を行なった。そ
の結果、１０〜５０°の間における回折角２θに存在す
るおもな回折線のピークは、１５．５°、１８．７°、
２４．７°、３５．６°、３６．３°、３６．９°、３
７．５゜、３９．３°、４０．８°、４２．６°、４
４．１°、４５．１°、４７．４°に存在し、１５．５
°に対する強度比（Ｉ／Ｉ0）は、それぞれ１．０、
０．２１、０．５６、０．１７、０．０８、０．１４、
０．０４、０．５１、０．２６、０．１１、０．０９、
０．７１、０．０５であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 122 mAh / g, and the average potential was 2.93 V. Example 15-Synthesis of Positive Electrode Active Material Same as Example 10 except that 1-pentanol kept at a constant temperature of 50 ° C. was bubbled with argon and the argon containing 1-pentanol was flown into the firing container. Then, the positive electrode active material LiMnO 2 was obtained. CuKα for X-ray source
The active material was subjected to powder X-ray diffraction using a line. As a result, the peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.5 °, 18.7 °,
24.7 °, 35.6 °, 36.3 °, 36.9 °, 3
7.5 °, 39.3 °, 40.8 °, 42.6 °, 4
Existing at 4.1 °, 45.1 °, 47.4 °, and 15.5 °
The intensity ratio (I / I 0 ) with respect to ° is 1.0,
0.21, 0.56, 0.17, 0.08, 0.14,
0.04, 0.51, 0.26, 0.11, 0.09,
It was 0.71 and 0.05.

【００５９】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み７７μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 77 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００６０】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１１６mAh/g、平均電位
は２．８５Ｖであった。 実施例１６ ・正極活物質の合成 ２５℃の一定温度に保たれた酪酸エチルにアルゴンをバ
ブルさせ、酪酸エチルを含んだアルゴンを焼成容器にフ
ローさせた以外は実施例１０と同様に焼成し、正極活物
質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を用いて、
この活物質の粉末Ｘ線回折を行なった。その結果、１０
〜５０°の間における回折角２θに存在するおもな回折
線のピークは、１５．５°、１８．７°、２４．９°、
３５．６°、３６．３°、３６．９°、３７．６゜、３
９．３°、４０．８°、４２．６°、４４．１°、４
５．１°、４７．４°に存在し、１５．５°に対する強
度比（Ｉ／Ｉ0）は、それぞれ１．０、０．１９、０．
５２、０．１６、０．０６、０．１３、０．０５、０．
５３、０．２５、０．１２、０．０７、０．６２、０．
０３であった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 2 positive electrode was 116 mAh / g, and the average potential was 2.85V. Example 16-Synthesis of Positive Electrode Active Material Firing was performed in the same manner as in Example 10 except that ethyl butyrate kept at a constant temperature of 25 ° C was bubbled with argon and argon containing ethyl butyrate was flown into the firing container. A positive electrode active material LiMnO 2 was obtained. Using CuKα rays as the X-ray source,
This active material was subjected to powder X-ray diffraction. As a result, 10
The peaks of the main diffraction lines existing at the diffraction angle 2θ between ˜50 ° are 15.5 °, 18.7 °, 24.9 °,
35.6 °, 36.3 °, 36.9 °, 37.6 °, 3
9.3 °, 40.8 °, 42.6 °, 44.1 °, 4
It exists at 5.1 ° and 47.4 °, and the intensity ratio (I / I 0 ) with respect to 15.5 ° is 1.0, 0.19, 0 .
52, 0.16, 0.06, 0.13, 0.05, 0.
53, 0.25, 0.12, 0.07, 0.62, 0.
It was 03.

【００６１】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み７９μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 79 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００６２】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、１１１mAh/g、平均電位
は２．８９Ｖであった。 実施例１７〜１９ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と酸化リチウムと
を、リチウムとマンガンとの比で、Ｌｉ：Ｍｎ＝１．
１：１になるように秤量し、さらにナフタレンをマンガ
ンと炭素との比で、Ｍｎ：Ｃ＝１：３、１：５、１：１
０となるように、それぞれ秤量し、実施例１と同様にペ
レットを作った。これらを直径３ｃｍ、長さ１ｍの焼成
管に入れ、７００℃で５時間、窒素中で焼成し、正極活
物質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を用い
て、これら活物質の粉末Ｘ線回折を行なった。その結
果、１０〜５０°の間における回折角２θに存在するお
もな回折線のピークは、１５．４°近傍、１８．８°近
傍、２４．７°近傍、３５．６°近傍、３６．２°近
傍、３６．９°近傍、３７．５゜近傍、３９．３°近
傍、４０．７°近傍、４２．５°近傍、４４．０°近
傍、４５．０°近傍、４７．３°近傍に存在し、１５．
４°近傍に対する１８．８°近傍の強度比（Ｉ／Ｉ0）
は、それぞれ０．８５、０．６５、０．５９であった。As a result, the LiMn prepared as described above was
The second discharge capacity of the O 2 positive electrode was 111 mAh / g, and the average potential was 2.89V. Examples 17 to 19-Synthesis of positive electrode active material Electrolytic manganese dioxide (IC No. 1) and lithium oxide were used as Li: Mn = 1.
Weigh it to be 1: 1 and further add naphthalene in the ratio of manganese and carbon to Mn: C = 1: 3, 1: 5, 1: 1.
Each was weighed so as to be 0, and pellets were prepared in the same manner as in Example 1. These were put in a firing tube having a diameter of 3 cm and a length of 1 m, and fired in nitrogen at 700 ° C. for 5 hours to obtain a positive electrode active material LiMnO 2 . The powder X-ray diffraction of these active materials was performed using CuKα ray as an X-ray source. As a result, the peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.4 °, 18.8 °, 24.7 °, 35.6 °, 36. Near 2 °, Near 36.9 °, Near 37.5 °, Near 39.3 °, Near 40.7 °, Near 42.5 °, Near 44.0 °, Near 45.0 °, 47.3 It exists in the vicinity of 15.
Intensity ratio (I / I 0 ) near 18.8 ° to around 4 °
Were 0.85, 0.65, and 0.59, respectively.

【００６３】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。これら正極は、見かけ上の表面積
４ｃｍ2 、電極厚み８５μｍ、７３μｍ、８２μｍ（集
電体の厚みが２０μｍ）であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. These positive electrodes had an apparent surface area of 4 cm 2 and electrode thicknesses of 85 μm, 73 μm, and 82 μm (current collector thickness was 20 μm). Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００６４】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、それぞれ１１２mAh/g、
１１９mAh/g、１１６mAh/g、平均電位は２．９５Ｖ、
２．８８Ｖ、２．７９Ｖであった。 実施例２０〜２２ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）、酸化リチウム及び
ナフタレンを用いて、実施例１７〜１９と同様にペレッ
トを作った。これらを直径１０ｃｍ、長さ１ｍの焼成管
にいれ、７００℃で５時間、窒素雰囲気中で焼成し、正
極活物質ＬｉＭｎＯ2を得た。Ｘ線源にＣｕＫα線を用
いて、これら活物質の粉末Ｘ線回折を行なった。その結
果、１０〜５０°の間における回折角２θに存在するお
もな回折線のピークは、１５．４°近傍、１８．８°近
傍、２４．７°近傍、３５．６°近傍、３６．２°近
傍、３６．９°近傍、３７．５゜近傍、３９．３°近
傍、４０．７°近傍、４２．５°近傍、４４．０°近
傍、４５．０°近傍、４７．３°近傍に存在し、１５．
４°近傍に対する１８．８°近傍の強度比（Ｉ／Ｉ0）
は、それぞれ１．１、０．８４、０．８２であった。As a result, the LiMn prepared as described above was
The second discharge capacity of the O 2 positive electrode was 112 mAh / g,
119mAh / g, 116mAh / g, average potential 2.95V,
It was 2.88V and 2.79V. Examples 20 to 22-Synthesis of positive electrode active material Electrolytic manganese dioxide (IC No. 1), lithium oxide and naphthalene were used to form pellets in the same manner as in Examples 17 to 19. These were put into a firing tube having a diameter of 10 cm and a length of 1 m, and fired at 700 ° C. for 5 hours in a nitrogen atmosphere to obtain a positive electrode active material LiMnO 2 . The powder X-ray diffraction of these active materials was performed using CuKα ray as an X-ray source. As a result, the peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.4 °, 18.8 °, 24.7 °, 35.6 °, 36. Near 2 °, Near 36.9 °, Near 37.5 °, Near 39.3 °, Near 40.7 °, Near 42.5 °, Near 44.0 °, Near 45.0 °, 47.3 It exists in the vicinity of 15.
Intensity ratio (I / I 0 ) near 18.8 ° to around 4 °
Were 1.1, 0.84, and 0.82, respectively.

【００６５】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。これら正極は、見かけ上の表面積
４ｃｍ2 、電極厚み８５μｍ、７３μｍ、８２μｍ（集
電体の厚みが２０μｍ）であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. These positive electrodes had an apparent surface area of 4 cm 2 and electrode thicknesses of 85 μm, 73 μm, and 82 μm (current collector thickness was 20 μm). Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００６６】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2正極の２回目の放電容量は、それぞれ１０１mAh/g、
１１３mAh/g、１０９mAh/g、平均電位は３．１５Ｖ、
３．０１Ｖ、２．９５Ｖであった。 実施例２３ ・正極活物質の合成及び正極の作製 実施例２と同様にして、正極活物質の合成及び正極の作
製を行い、直径１５mm、重量５０mgのペレットを作製し
た。As a result, the LiMn prepared as described above was
The second discharge capacity of the O 2 positive electrode was 101 mAh / g,
113mAh / g, 109mAh / g, average potential 3.15V,
It was 3.01V and 2.95V. Example 23-Synthesis of Positive Electrode Active Material and Production of Positive Electrode Synthesis of a positive electrode active material and production of a positive electrode were carried out in the same manner as in Example 2 to produce pellets having a diameter of 15 mm and a weight of 50 mg.

【００６７】・負極の作製 負極の活物質は、熱分解によって得られた炭素を用い
た。その合成方法は、プロパンを出発原料とし、常圧下
の気相熱分解法によって、基板としてニッケル箔（４cm
2）を用いて炭素を堆積させた。このときの熱分解温度
は約７５０℃、熱分解時間は約２時間であった。このよ
うにして得られた熱分解炭素を、常法のＸ線回折法で測
定すると、（００２）面の面間隔ｄ002は０．３３７ｎ
ｍ、（００２）面方向の結晶子厚さＬｃは１５ｎｍであ
った。また、アルゴンレーザーラマン法による測定で
は、１５８０ｃｍ-1付近のピーク強度に対する１３６０
ｃｍ-1付近のピーク強度の比（Ｒ値）が０．４６であっ
た。Preparation of Negative Electrode As the active material of the negative electrode, carbon obtained by thermal decomposition was used. The synthesis method was propane as a starting material and vapor phase pyrolysis under normal pressure, and nickel foil (4 cm
2 ) was used to deposit carbon. At this time, the thermal decomposition temperature was about 750 ° C., and the thermal decomposition time was about 2 hours. When the pyrolytic carbon thus obtained is measured by a conventional X-ray diffraction method, the interplanar spacing d 002 of the (002) plane is 0.337 n.
The crystallite thickness Lc in the m, (002) plane direction was 15 nm. Further, in the measurement by the Argon laser Raman method, 1360 with respect to the peak intensity near 1580 cm -1
The ratio of peak intensities (R value) near cm −1 was 0.46.

【００６８】上記の方法により熱分解炭素を堆積したニ
ッケル箔にニッケル金属線をスポット溶接し、ターミナ
ルを取った。さらに、これを２００℃で減圧乾燥して、
水分除去し、負極として用いた。この負極においては、
活物質量は１６ｍｇであった。 ・電池の評価 電池はビーカー型セルを用い、正極及び負極を上記で作
製したものを用いて評価した。電解液としては、プロピ
レンカーボネートとジエチルカーボネートとの１：１混
合溶媒に１mol/lの過塩素酸リチウムを溶解したものを
用いた。A nickel metal wire was spot-welded to the nickel foil on which pyrolytic carbon was deposited by the above method, and a terminal was taken. Furthermore, this is dried under reduced pressure at 200 ° C.,
Water was removed and used as a negative electrode. In this negative electrode,
The amount of active material was 16 mg. -Evaluation of Battery A beaker type cell was used as the battery, and the positive electrode and the negative electrode prepared as described above were used for the evaluation. The electrolyte used was a 1: 1 mixed solvent of propylene carbonate and diethyl carbonate in which 1 mol / l of lithium perchlorate was dissolved.

【００６９】充放電試験は、０．２mAの一定電流で、初
めに４．１Ｖまで充電を行い、続いて同じ電流で１．０
Ｖまで放電を行った。２回目以降も同じ電流で、同じ電
位の範囲の充放電を繰返し、電池の評価を行った。その
結果、前記のごとく作製した電池の２回目の放電容量は
４mAh 、平均電位は２．４Ｖであった。 実施例２４ ・正極活物質の合成及び正極の作製 実施例２と同様にして、正極活物質の合成及び正極の作
製を行い、直径２０mm、重量０．２５gのペレットを作
製した。In the charge / discharge test, a constant current of 0.2 mA was first charged to 4.1 V, and then 1.0 mA was applied at the same current.
Discharged to V. The battery was evaluated by repeating charge and discharge in the same potential range at the same current after the second time. As a result, the battery manufactured as described above had a second discharge capacity of 4 mAh and an average potential of 2.4V. Example 24 Synthesis of Positive Electrode Active Material and Production of Positive Electrode Synthesis of a positive electrode active material and production of a positive electrode were performed in the same manner as in Example 2 to produce pellets having a diameter of 20 mm and a weight of 0.25 g.

【００７０】・負極の作製 マダガスカル産の天然黒鉛（鱗片状、粒径１１μｍ、ｄ
002は０．３３７ｎｍ、Ｌｃは２７ｎｍ、Ｌａは１７ｎ
ｍ、Ｒ値は０、比表面積８ｍ2／ｇ）にノニオン系の分
散剤を添加し、ポリテトラフルオロエチレン（乾燥後、
酸化銅付着黒鉛複合体とポリテトラフルオロエチレンと
の重量比は、８７：１３である。）のディスパージョン
液を加えてペースト状にした。これを、銅箔よりなる集
電体の両面に塗布した。６０℃で乾燥した後、２４０℃
の温度で熱処理し、プレスした。その後さらに２００℃
の温度で減圧乾燥して水分除去したものを、負極活物質
として用いた。この負極活物質は表面積８ｃｍ2、重量
は７８ｍｇであった。Preparation of negative electrode Natural graphite from Madagascar (scale, particle size 11 μm, d
002 is 0.337 nm, Lc is 27 nm, La is 17 n
m, R value is 0, specific surface area is 8 m 2 / g, and a nonionic dispersant is added to polytetrafluoroethylene (after drying,
The weight ratio of the copper oxide-adhered graphite composite and polytetrafluoroethylene was 87:13. ) Dispersion liquid was added to form a paste. This was applied to both sides of a collector made of copper foil. After drying at 60 ℃, 240 ℃
It heat-processed at the temperature of and was pressed. After that, 200 ℃
The product obtained by drying under reduced pressure at the temperature of 10 to remove water was used as the negative electrode active material. This negative electrode active material had a surface area of 8 cm 2 and a weight of 78 mg.

【００７１】・電池の評価 電池はビーカー型セルを用い、正極及び負極を上記で作
製したものを用いて評価した。電解液としては、エチレ
ンカーボネートとジエチルカーボネートとの１：１混合
溶媒に、１mol/lの過塩素酸リチウムを溶解したものを
用いた。充放電試験は、２mAの一定電流で、初めに４．
１Ｖまで充電を行い、続いて同じ電流で２．０Ｖまで放
電を行った。２回目以降も同じ電流で、同じ電位の範囲
の充放電を繰返し、電池の評価を行った。Evaluation of Battery A beaker type cell was used as the battery, and the positive electrode and the negative electrode prepared as described above were evaluated. The electrolyte used was a 1: 1 mixed solvent of ethylene carbonate and diethyl carbonate in which 1 mol / l of lithium perchlorate was dissolved. In the charge / discharge test, a constant current of 2 mA was used, and 4.
The battery was charged to 1V and then discharged to 2.0V with the same current. The battery was evaluated by repeating charge and discharge in the same potential range at the same current after the second time.

【００７２】その結果、前記のごとく作製した電池の２
回目の放電容量は、２１mAh、平均電位は２．５Ｖであ
った。 実施例２５ ・正極活物質の合成及び正極の作製 実施例５と同様にして、正極活物質の合成を行い、実施
例１と同様にして、正極の作製を行い、直径１５mm、厚
み０．７７ｍｍのペレットを作製した。As a result, 2 of the batteries prepared as described above
The discharge capacity for the first time was 21 mAh, and the average potential was 2.5V. Example 25-Synthesis of Positive Electrode Active Material and Production of Positive Electrode A positive electrode active material was synthesized in the same manner as in Example 5, and a positive electrode was produced in the same manner as in Example 1, with a diameter of 15 mm and a thickness of 0.77 mm. Pellets were prepared.

【００７３】・負極の作製 実施例８の負極活性物質（マダガスカル産の天然黒鉛）
を用い、ポリテトラフルオロエチレンと共にそれぞれ１
０：１の割合で混合し、加圧成形を行って直径１４ｍ
ｍ、厚み０．５７ｍｍのペレットを作製した。その際、
集電体として作用するニッケルメッシュも一体的になる
ように加圧成形した。水分除去のために２００℃で減圧
乾燥したものを負極として用いた。Preparation of Negative Electrode Negative electrode active material of Example 8 (natural graphite from Madagascar)
1 with polytetrafluoroethylene
Mix at a ratio of 0: 1 and press mold to obtain a diameter of 14m
m and a thickness of 0.57 mm were produced. that time,
The nickel mesh acting as a current collector was also pressure-molded so as to be integrated. What was dried under reduced pressure at 200 ° C. to remove water was used as a negative electrode.

【００７４】・電池の組み立て 図５に示すように、電池は、主として正極缶１、正極
３、負極缶４及び負極６からなる。まず、正極缶１の内
底面に、正極集電体２を溶接によって取り付け、その外
周部に、絶縁パッキング８を配設した。さらに、正極集
電体２上に正極３を圧着した。次いで、正極３の上にポ
リプロピレン不織布のセパレータ７を載置し、このセパ
レータ７に、エチレンカーボネート、プロピレンカーボ
ネート、ジエチレンカーボネートの体積比が２：１：３
の混合溶液に電解質ＬｉＰＦ6 を１ｍｏｌ／リットルに
なるように溶解した電解液を含浸させる。一方、負極缶
４の内面に負極集電体５を溶接し、この負極集電体５上
に負極６を圧着した。次いで、セパレータ７の上に負極
６を重ね、正極缶１と負極缶４とを絶縁パッキング８を
介在させてかしめ、密封し、コイン型電池を作製した。
なお、電池の容量は全て負極に基づいて規定した。Assembling of Battery As shown in FIG. 5, the battery mainly comprises a positive electrode can 1, a positive electrode 3, a negative electrode can 4 and a negative electrode 6. First, the positive electrode current collector 2 was attached to the inner bottom surface of the positive electrode can 1 by welding, and the insulating packing 8 was arranged on the outer peripheral portion thereof. Further, the positive electrode 3 was pressure-bonded onto the positive electrode current collector 2. Next, a polypropylene non-woven fabric separator 7 is placed on the positive electrode 3, and the volume ratio of ethylene carbonate, propylene carbonate, and diethylene carbonate is 2: 1: 3.
The mixed solution (1) is impregnated with an electrolytic solution in which the electrolyte LiPF 6 is dissolved to 1 mol / liter. On the other hand, the negative electrode current collector 5 was welded to the inner surface of the negative electrode can 4, and the negative electrode 6 was pressure-bonded onto the negative electrode current collector 5. Next, the negative electrode 6 was placed on the separator 7, and the positive electrode can 1 and the negative electrode can 4 were caulked with the insulating packing 8 interposed therebetween and sealed to manufacture a coin-type battery.
All battery capacities were defined based on the negative electrode.

【００７５】・電池の評価 作製したコイン型電池はすべて充放電電流１ｍＡ、充電
上限電圧４．２Ｖに達した後、４．０Ｖの定電圧充電を
行い、充電時間を３０時間とし、放電の下限電圧を２．
０Ｖとして充放電試験を行った。評価には、電池の放電
容量測定を行った。Evaluation of Battery All the coin-type batteries manufactured were charged and discharged at a current of 1 mA and reached a charging upper limit voltage of 4.2 V, and then were subjected to constant voltage charging of 4.0 V, charging time was 30 hours, and discharging lower limit was set. The voltage is 2.
A charge / discharge test was performed at 0V. For evaluation, the discharge capacity of the battery was measured.

【００７６】その結果、放電における平均電圧が２．７
Ｖであり、２サイクル目の放電容量は２０ｍＡｈ、２０
サイクル目の放電容量の平均値は１７ｍＡｈであった。 比較例１ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と炭酸リチウムと
を、リチウムとマンガンの比でＬｉ:Ｍｎ＝１．１：２
になるように秤量し、実施例１と同様にペレットを作っ
た。これを７００℃で５時間、空気雰囲気中で焼成し、
正極活物質ＬｉＭｎ2 Ｏ3.9 （Ｌｉ0.5 ＭｎＯ1.95）を
得た。Ｘ線源にＣｕＫα線を用いて、この活物質の粉末
Ｘ線回折を行なった。その結果を図６に示す。図６か
ら、この活物質は、ＬｉＭｎ2Ｏ4であることが確認され
た。As a result, the average voltage during discharge was 2.7.
V, the discharge capacity in the second cycle is 20 mAh, 20
The average value of the discharge capacity at the cycle was 17 mAh. Comparative Example 1-Synthetic Electrolytic Manganese Dioxide (IC No. 1) of Positive Electrode Active Material and Lithium Carbonate in the ratio of lithium to manganese, Li: Mn = 1.1: 2.
Were weighed so that pellets were prepared in the same manner as in Example 1. This is baked at 700 ° C. for 5 hours in an air atmosphere,
A positive electrode active material LiMn 2 O 3.9 (Li 0.5 MnO 1.95 ) was obtained. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. The result is shown in FIG. From FIG. 6, it was confirmed that this active material was LiMn 2 O 4 .

【００７７】・正極の作製 以上のようにして得られた正極活物質を、アセチレンブ
ラック及びポリテトラフルオロエチレンと共にそれぞれ
１００：１５：５の割合で混合した以外は、実施例１と
同様にして、直径２０mm、重量０．２５ｇのペレットを
作製した。 ・正極の評価 実施例１と同様にして評価を行った。Preparation of Positive Electrode The procedure of Example 1 was repeated except that the positive electrode active material obtained as described above was mixed with acetylene black and polytetrafluoroethylene at a ratio of 100: 15: 5, respectively. Pellets having a diameter of 20 mm and a weight of 0.25 g were prepared. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 1.

【００７８】その結果、前記のごとく作製したＬｉＭｎ
2Ｏ4正極の２回目の放電容量は、８５mAh/g、平均電位
は３．８７Ｖであった。 比較例２ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と炭酸リチウムと
を、リチウムとマンガンとの比で、Ｌｉ:Ｍｎ＝１：１
になるように秤量し、実施例１と同様にペレットを作っ
た。これを７００℃で３時間、空気雰囲気中で焼成し、
正極活物質Ｌｉ1. 9 Ｍｎ2 Ｏ4.5 （Ｌｉ0.95Ｍｎ
Ｏ2.25）を得た。Ｘ線源にＣｕＫα線を用いて、この活
物質の粉末Ｘ線回折を行なった。その結果を図７に示
す。図７から、この活物質は、ＬｉＭｎ2Ｏ4とＬｉ2Ｍ
ｎＯ3との混合物であることが確認され、１５．５°付
近にピークがないことが確認された。As a result, the LiMn prepared as described above was
The second discharge capacity of the 2 O 4 positive electrode was 85 mAh / g, and the average potential was 3.87 V. Comparative Example 2 ・ Synthetic Electrolytic Manganese Dioxide (IC No. 1) of Positive Electrode Active Material and Lithium Carbonate in the ratio of lithium to manganese, Li: Mn = 1: 1.
Were weighed so that pellets were prepared in the same manner as in Example 1. This is baked at 700 ° C. for 3 hours in an air atmosphere,
The positive electrode active material Li 1. 9 Mn 2 O 4.5 ( Li 0.95 Mn
O 2.25 ) was obtained. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. The result is shown in FIG. 7. As shown in FIG. 7, the active material is LiMn 2 O 4 and Li 2 M.
It was confirmed to be a mixture with nO 3, and it was confirmed that there was no peak near 15.5 °.

【００７９】・正極の作製 以上のようにして得られた正極活物質をアセチレンブラ
ック及びポリテトラフルオロエチレンと共にそれぞれ１
００：１５：５の割合で混合した以外は、実施例１と同
様にして、直径２０mm、重量０．２５ｇのペレットを作
製した。 ・正極の評価 実施例１と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was used together with acetylene black and polytetrafluoroethylene to prepare 1
Pellets having a diameter of 20 mm and a weight of 0.25 g were prepared in the same manner as in Example 1 except that the pellets were mixed at a ratio of 00: 15: 5. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 1.

【００８０】その結果、前記のごとく作製した正極の２
回目の放電容量は、５１mAh/g、平均電位は３．７９Ｖ
であった。 比較例３ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と炭酸リチウムとを
リチウムとマンガンとの比で、Ｌｉ:Ｍｎ＝１．５：１
になるように秤量し、実施例１と同様にペレットを作っ
た。これを８００℃で３時間、空気雰囲気中で焼成し、
正極活物質Ｌｉ 1.3ＭｎＯ2.3を得た。Ｘ線源にＣｕＫα
線を用いて、この活物質の粉末Ｘ線回折を行なった。そ
の結果を図８に示す。図８から、この活物質は、ＬｉＭ
ｎ2ＯとＬｉ2ＭｎＯ3の混合物であることが確認され
た。また、１５．５°付近のピーク強度に対する１８．
８°付近のピーク強度の比は３．８であった。As a result, the positive electrode 2 produced as described above was
The discharge capacity of the first time is 51mAh / g, the average potential is 3.79V.
Met. Comparative Example 3 ・ Synthesis of positive electrode active material Electrolytic manganese dioxide (IC No.1) and lithium carbonate
The ratio of lithium to manganese is Li: Mn = 1.5: 1.
To make pellets in the same manner as in Example 1.
It was Baking this at 800 ℃ for 3 hours in air atmosphere,
Positive electrode active material Li 1.3MnO2.3Got CuKα for X-ray source
The active material was subjected to powder X-ray diffraction using a line. So
The results are shown in FIG. From FIG. 8, this active material is LiM
n2O and Li2MnO3Confirmed to be a mixture of
It was In addition, the peak intensity near 15.5 ° is 18.
The ratio of peak intensities near 8 ° was 3.8.

【００８１】・正極の作製 以上のようにして得られた正極活物質をアセチレンブラ
ック及びポリテトラフルオロエチレンと共にそれぞれ１
００：１５：５の割合で混合した以外は、実施例１と同
様にして、直径２０mm、重量０．２５ｇのペレットを作
製した。 ・正極の評価 実施例１と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was used together with acetylene black and polytetrafluoroethylene to prepare 1
Pellets having a diameter of 20 mm and a weight of 0.25 g were prepared in the same manner as in Example 1 except that the pellets were mixed at a ratio of 00: 15: 5. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 1.

【００８２】その結果、前記のごとく作製した正極の２
回目の放電容量は、８９mAh/g、平均電位は２．７１Ｖ
であった。 比較例４ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と水酸化リチウムと
を、リチウムとマンガンとの比でＬｉ:Ｍｎ＝１．１：
１になるように秤量し、実施例１と同様にペレットを作
った。これを７００℃で５時間、１５体積％の酸素を混
合した窒素雰囲気中で焼成し、正極活物質Ｌｉ0.9 Ｍｎ
Ｏ2.1を得た。Ｘ線源にＣｕＫα線を用いて、この活物
質の粉末Ｘ線回折を行なった。その結果、１０〜５０°
の間における回折角２θに存在するおもな回折線のピー
クは、１５．３°、１８．８°、２１．０°、２１．９
°、２４．７°、２８．３°、３３．０°、３５．６
°、３６．３°、３７．０°、３７．５°、３８．０
°、３８．７°、３９．３°４０．８°、４２．４°、
４２．９°、４３．９°、４５．１°、４６．９°、４
７．４°、４８．２°、４９．１°に存在し、１５．３
°に対する強度比（Ｉ／Ｉ0）は、それぞれ１．０、
０．７、０．０５、０．０８、０．７０、０．０５、
０．２０、０．２０、０．１９、０．２１、０．１０、
０．０６、０．０３、０．６０、０．８０、０．１６、
０．０２、０．１７、０．７５、０．０３、０．０５、
０．０４、０．０３であった。この活物質は２７〜３３
°の回折角２θにピークがあった。As a result, the positive electrode 2 produced as described above was
The second discharge capacity is 89mAh / g, average potential is 2.71V.
Met. Comparative Example 4 ・ Synthetic Electrolytic Manganese Dioxide (IC No. 1) of Positive Electrode Active Material and Lithium Hydroxide in the ratio of lithium to manganese, Li: Mn = 1.1:
1 was weighed and pellets were prepared in the same manner as in Example 1. This was baked at 700 ° C. for 5 hours in a nitrogen atmosphere mixed with 15% by volume of oxygen to obtain a positive electrode active material Li 0.9 Mn.
O 2.1 was obtained. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. As a result, 10 to 50 °
The peaks of the main diffraction lines existing at the diffraction angle 2θ between 13.5 °, 18.8 °, 21.0 °, and 21.9.
°, 24.7 °, 28.3 °, 33.0 °, 35.6
°, 36.3 °, 37.0 °, 37.5 °, 38.0
°, 38.7 °, 39.3 ° 40.8 °, 42.4 °,
42.9 °, 43.9 °, 45.1 °, 46.9 °, 4
Present at 7.4 °, 48.2 °, 49.1 °, and 15.3 °
The intensity ratio (I / I 0 ) with respect to ° is 1.0,
0.7, 0.05, 0.08, 0.70, 0.05,
0.20, 0.20, 0.19, 0.21, 0.10,
0.06, 0.03, 0.60, 0.80, 0.16,
0.02, 0.17, 0.75, 0.03, 0.05,
It was 0.04 and 0.03. This active material is 27-33
There was a peak at a diffraction angle 2θ of °.

【００８３】・正極の作製 以上のようにして得られた正極活物質を用いて、実施例
４と同様にして正極を作製した。この正極は、見かけ上
の表面積４ｃｍ2 、電極の厚みが３３μｍ（集電体の厚
みが２０μｍ）であった。 ・正極の評価 実施例４と同様にして評価した。Preparation of Positive Electrode Using the positive electrode active material obtained as described above, a positive electrode was prepared in the same manner as in Example 4. This positive electrode had an apparent surface area of 4 cm 2 and an electrode thickness of 33 μm (current collector thickness of 20 μm). -Evaluation of positive electrode Evaluation was performed in the same manner as in Example 4.

【００８４】その結果、前記のごとく作製したＬｉ0.9
ＭｎＯ2.1 正極の２回目の放電容量は、７３mAh/g、平
均電位は２．８１Ｖであった。 比較例５ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と水酸化リチウムと
をリチウムとマンガンのと比で、Ｌｉ:Ｍｎ＝１．１：
１になるように秤量し、実施例１と同様にペレットを作
った。これを７５０℃で７時間、２０体積％の酸素を混
合した窒素雰囲気中で焼成し、正極活物質ＬｉＭｎＯ
2.2 を得た。Ｘ線源にＣｕＫα線を用いて、この活物質
の粉末Ｘ線回折を行なった。その結果、１０〜５０°の
間における回折角２θに存在するおもな回折線のピーク
は、１５．４°、１８．７°、２１．０°、２３．０
°、２４．６°、２８．３°、３３．１°、３５．６
°、３６．２°、３７．０°、３７．６°、３８．０
°、３８．９°、３９．３°４０．７°、４２．５°、
４２．９°、４４．０°、４５．０°、４６．９°、４
７．４°、４８．２°、４９．０°に存在し、１５．４
°に対する強度比（Ｉ／Ｉ0）は、それぞれ１．０、
１．０、０．０８、０．１３、０．８０、０．０９、
０．０４、０．２０、０．２１、０．３０、０．１０、
０．１０、０．０４、０．５５、０．２３、０．２０、
０．０４、０．２３、１．３、０．０４、０．０３、
０．０４、０．０８であった。この活物質は２７〜３３
°の回折角２θにピークがあった。As a result, Li 0.9 produced as described above was used.
The second-time discharge capacity of the MnO 2.1 positive electrode was 73 mAh / g, and the average potential was 2.81 V. Comparative Example 5 ・ Synthesis of positive electrode active material Electrolytic manganese dioxide (IC No. 1) and lithium hydroxide were compared with lithium and manganese, and Li: Mn = 1.1:
1 was weighed and pellets were prepared in the same manner as in Example 1. This was baked at 750 ° C. for 7 hours in a nitrogen atmosphere mixed with 20% by volume of oxygen to obtain a positive electrode active material LiMnO 2.
Got 2.2 . This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. As a result, the peaks of the main diffraction lines existing at the diffraction angle 2θ between 10 and 50 ° are 15.4 °, 18.7 °, 21.0 °, 23.0.
°, 24.6 °, 28.3 °, 33.1 °, 35.6
°, 36.2 °, 37.0 °, 37.6 °, 38.0
°, 38.9 °, 39.3 ° 40.7 °, 42.5 °,
42.9 °, 44.0 °, 45.0 °, 46.9 °, 4
Existing at 7.4 °, 48.2 °, 49.0 °, and 15.4 °
The intensity ratio (I / I 0 ) with respect to ° is 1.0,
1.0, 0.08, 0.13, 0.80, 0.09,
0.04, 0.20, 0.21, 0.30, 0.10,
0.10, 0.04, 0.55, 0.23, 0.20,
0.04, 0.23, 1.3, 0.04, 0.03,
It was 0.04 and 0.08. This active material is 27-33
There was a peak at a diffraction angle 2θ of °.

【００８５】・正極の作製 以上のようにして得られた正極活物質を用いて、実施例
４と同様に正極を作製した。この正極は、見かけ上の表
面積４ｃｍ2 、電極の厚みが６３μｍ（集電体の厚みが
２０μｍ）であった。 ・正極の評価 実施例６と同様にして評価した。Production of Positive Electrode A positive electrode was produced in the same manner as in Example 4 using the positive electrode active material obtained as described above. This positive electrode had an apparent surface area of 4 cm 2 and an electrode thickness of 63 μm (current collector thickness of 20 μm). Evaluation of positive electrode Evaluation was performed in the same manner as in Example 6.

【００８６】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2.2 正極の２回目の放電容量は、６３mAh/g、平均電
位は３．１３Ｖであった。 比較例６ ・正極活物質の合成、評価 電解二酸化マンガン（ＩＣ No.1）と水酸化リチウムと
をリチウムとマンガンとの比で、Ｌｉ:Ｍｎ＝１．１：
１になるように秤量し、実施例１と同様にペレットを作
った。これを３５０℃で７時間、窒素雰囲気中で焼成
し、正極活物質ＬｉＭｎＯ2.3 を得た。Ｘ線源にＣｕＫ
α線を用いて、この活物質の粉末Ｘ線回折を行なった。
その結果、ブロードなピークを示した。これより１５．
２〜１５．６°のピーク強度と１８．６〜１８．８°の
ピーク強度の比は求まらなかった。As a result, the LiMn produced as described above was
The second-time discharge capacity of the O 2.2 positive electrode was 63 mAh / g, and the average potential was 3.13 V. Comparative Example 6-Synthesis and Evaluation of Positive Electrode Active Material Electrolytic manganese dioxide (IC No. 1) and lithium hydroxide in the ratio of lithium to manganese, Li: Mn = 1.1:
1 was weighed and pellets were prepared in the same manner as in Example 1. This was baked at 350 ° C. for 7 hours in a nitrogen atmosphere to obtain a positive electrode active material LiMnO 2.3 . CuK for X-ray source
This active material was subjected to powder X-ray diffraction using α ray.
As a result, a broad peak was shown. From this, 15.
The ratio of the peak intensity between 2-15.6 and the peak intensity between 18.6 and 18.8 was not determined.

【００８７】以上のようにして得られた正極活物質を用
いて、比較例４と同様にして正極を作製し、評価したと
ころ、初めの充電量が３６mAh/gと小さく、充電状態か
ら始められないことが分かった。 比較例７ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と酸化リチウムと
を、リチウムとマンガンのと比で、Ｌｉ:Ｍｎ＝１．
１：１になるように秤量し、実施例１と同様にペレット
を作った。これを９００℃で５時間、６０体積％のプロ
パンを混合した窒素雰囲気中（ボンベからガスフローで
供給した）で焼成したところ、気相ですすが発生し、正
極活物質との混合物として得られたため、正極として使
用することができなかった。 比較例８ ・正極活物質の合成 電解二酸化マンガン（ＩＣ No.1）と酸化リチウムと
を、リチウムとマンガンのと比で、Ｌｉ：Ｍｎ＝１．
１：１になるように秤量し、実施例１と同様にペレット
を作った。これを２５０℃で２０時間、５５体積％のプ
ロパンを混合した窒素雰囲気中（ボンベからガスフロー
で供給した）で焼成し、正極活物質ＬｉＭｎＯ2.2 を得
た。Ｘ線源にＣｕＫα線を用いて、この活物質の粉末Ｘ
線回折を行なった。その結果、１５．５°近傍にピーク
は観測されなかった。Using the positive electrode active material obtained as described above, a positive electrode was prepared and evaluated in the same manner as in Comparative Example 4. The initial charge amount was as small as 36 mAh / g, and it was possible to start from the charged state. I found it wasn't. Comparative Example 7-Synthesis of positive electrode active material Electrolytic manganese dioxide (IC No. 1) and lithium oxide were compared in the ratio of lithium and manganese to Li: Mn = 1.
Weighed to be 1: 1 and pelletized in the same manner as in Example 1. When this was baked at 900 ° C. for 5 hours in a nitrogen atmosphere mixed with 60% by volume of propane (supplied by a gas flow from a cylinder), soot was generated in the gas phase and obtained as a mixture with the positive electrode active material. Therefore, it could not be used as a positive electrode. Comparative Example 8-Synthesis of positive electrode active material Electrolytic manganese dioxide (IC No. 1) and lithium oxide were compared in the ratio of lithium and manganese, and Li: Mn = 1.
Weighed to be 1: 1 and pelletized in the same manner as in Example 1. This was baked at 250 ° C. for 20 hours in a nitrogen atmosphere mixed with 55 vol% propane (supplied by a gas flow from a cylinder) to obtain a positive electrode active material LiMnO 2.2 . Using CuKα rays as an X-ray source, powder X of this active material
Line diffraction was performed. As a result, no peak was observed near 15.5 °.

【００８８】・正極の作製 以上のようにして得られた正極活物質を用いて、実施例
４と同様に正極を作製した。この正極は、見かけ上の表
面積４ｃｍ2 、電極の厚みが８９μｍ（集電体の厚みが
２０μｍ）であった。 ・正極の評価 実施例７と同様にして評価した。Production of Positive Electrode A positive electrode was produced in the same manner as in Example 4 using the positive electrode active material obtained as described above. This positive electrode had an apparent surface area of 4 cm 2 and an electrode thickness of 89 μm (current collector thickness of 20 μm). -Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００８９】その結果、前記のごとく作製したＬｉＭｎ
Ｏ2.2 正極の２回目の放電容量は、７５mAh/g、平均電
位は３．１１Ｖであった。 比較例９ ・正極活物質の合成 ４００℃で５時間、４０体積％の水素を混合した窒素雰
囲気中で焼成した以外は、実施例１０と同様に正極活物
質ＬｉＭｎＯ1.7 を得た。Ｘ線源にＣｕＫα線を用い
て、この活物質の粉末Ｘ線回折を行なった。その結果、
１５．５°近傍にピークは観測されなかった。As a result, the LiMn prepared as described above was
The second discharge capacity of the O 2.2 positive electrode was 75 mAh / g, and the average potential was 3.11V. Comparative Example 9-Synthesis of Positive Electrode Active Material A positive electrode active material LiMnO 1.7 was obtained in the same manner as in Example 10 except that the positive electrode active material was baked at 400 ° C. for 5 hours in a nitrogen atmosphere mixed with 40% by volume of hydrogen. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. as a result,
No peak was observed near 15.5 °.

【００９０】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み７７μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 77 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００９１】その結果、前記のごとく作製したＬｉＭｎ
Ｏ1.7 正極の２回目の放電容量は、３０mAh/g、平均電
位は３．２４Ｖであった。 比較例１０ ・正極活物質の合成 ２００℃で５時間、４０体積％の水素を混合した窒素雰
囲気中で焼成した以外は、実施例１１と同様に正極活物
質ＬｉＭｎＯ1.9 を得た。Ｘ線源にＣｕＫα線を用い
て、この活物質の粉末Ｘ線回折を行なった。その結果、
１５．５°近傍にピークは観測されなかった。As a result, the LiMn prepared as described above was
The second-time discharge capacity of the O 1.7 positive electrode was 30 mAh / g, and the average potential was 3.24V. Comparative Example 10-Synthesis of positive electrode active material A positive electrode active material LiMnO 1.9 was obtained in the same manner as in Example 11 except that the positive electrode active material was baked at 200 ° C for 5 hours in a nitrogen atmosphere mixed with 40% by volume of hydrogen. This active material was subjected to powder X-ray diffraction using CuKα ray as an X-ray source. as a result,
No peak was observed near 15.5 °.

【００９２】・正極の作製 以上のようにして得られた正極活物質を、実施例４と同
様に正極に作製した。この正極は、見かけ上の表面積４
ｃｍ2 、電極厚み８３μｍ（集電体の厚みが２０μｍ）
であった。 ・正極の評価 実施例７と同様にして評価を行った。Preparation of Positive Electrode The positive electrode active material obtained as described above was formed into a positive electrode in the same manner as in Example 4. This positive electrode has an apparent surface area of 4
cm 2 , electrode thickness 83 μm (current collector thickness 20 μm)
Met. Evaluation of positive electrode Evaluation was performed in the same manner as in Example 7.

【００９３】その結果、前記のごとく作製したＬｉＭｎ
Ｏ1.9 正極の２回目の放電容量は、６３mAh/g、平均電
位は３．０２Ｖであった。As a result, the LiMn produced as described above was
The second-time discharge capacity of the O 1.9 positive electrode was 63 mAh / g, and the average potential was 3.02 V.

【００９４】[0094]

【発明の効果】本発明による非水系二次電池によれば、
負極としてリチウムを含むか又はリチウムが挿入・脱離
可能な活物質と、正極としてリチウム・マンガン複合酸
化物を含む活物質との組み合わせのように、安価な原料
を使用することができるとともに、そのような組み合わ
せにおいても、繰返し充放電によってデンドライトの発
生しない良好な非水型二次電池を得ることができる。ま
た、従来必要であった正極の放電又は負極の充電工程を
行う必要なくなるので、電池製造工程を比較的簡素化す
ることができる。According to the non-aqueous secondary battery of the present invention,
An inexpensive raw material can be used, such as a combination of an active material containing lithium as a negative electrode or capable of lithium insertion / desorption and an active material containing a lithium-manganese composite oxide as a positive electrode. Even with such a combination, it is possible to obtain a good non-aqueous secondary battery in which dendrite does not occur due to repeated charge and discharge. Further, since it is not necessary to perform the step of discharging the positive electrode or the step of charging the negative electrode, which is conventionally required, the battery manufacturing process can be relatively simplified.

【００９５】さらに、本発明による非水系二次電池の正
極活物質の製造方法によれば、原料化合物を、１０％以
下の酸素が含まれた雰囲気、減圧雰囲気又は真空雰囲気
で焼成することにより、所望のリチウム・マンガン複合
酸化物を好適に作成することができる。また、原料化合
物の焼成雰囲気を、還元性雰囲気にすると、焼成温度を
さらに低くくすることができる。Further, according to the method for producing a positive electrode active material for a non-aqueous secondary battery according to the present invention, by firing the raw material compound in an atmosphere containing 10% or less oxygen, a reduced pressure atmosphere or a vacuum atmosphere, A desired lithium-manganese composite oxide can be preferably prepared. Further, if the firing atmosphere of the raw material compound is a reducing atmosphere, the firing temperature can be further lowered.

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

【図１】本発明の実施例１における正極活物質を合成す
るための原料であるＬｉ2.1ＭｎＯ3.0のＸ線回折パター
ンである。FIG. 1 is an X-ray diffraction pattern of Li 2.1 MnO 3.0 that is a raw material for synthesizing a positive electrode active material in Example 1 of the present invention.

【図２】実施例１で合成した正極活物質Ｌｉ1.1ＭｎＯ
2.1のＸ線回折パターンである。FIG. 2 is a positive electrode active material synthesized in Example 1, Li 1.1 MnO 2.
2 is an X-ray diffraction pattern of 2.1 .

【図３】実施例２で合成した正極活物質ＬｉＭｎＯ2の
Ｘ線回折パターンである。FIG. 3 is an X-ray diffraction pattern of the positive electrode active material LiMnO 2 synthesized in Example 2.

【図４】実施例３で合成した正極活物質ＬｉＭｎＯ1.9
のＸ線回折パターンである。FIG. 4 is a positive electrode active material LiMnO 1.9 synthesized in Example 3.
2 is an X-ray diffraction pattern of FIG.

【図５】本発明の非水系二次電池を示す概略断面図であ
る。FIG. 5 is a schematic cross-sectional view showing a non-aqueous secondary battery of the present invention.

【図６】比較例１で合成した正極活物質ＬｉＭｎ2Ｏ3.9
のＸ線回折パターンである。FIG. 6 is a positive electrode active material LiMn 2 O 3.9 synthesized in Comparative Example 1.
2 is an X-ray diffraction pattern of FIG.

【図７】比較例２で合成した正極活物質Ｌｉ1.9Ｍｎ2Ｏ
4.6のＸ線回折パターンであ。FIG. 7: Positive electrode active material Li 1.9 Mn 2 O synthesized in Comparative Example 2
It is an X-ray diffraction pattern of 4.6 .

【図８】比較例３で合成した正極活物質Ｌｉ1.2ＭｎＯ
2.3のＸ線回折パターンである。FIG. 8: Positive electrode active material Li 1.2 MnO 2 synthesized in Comparative Example 3
2 is an X-ray diffraction pattern of 2.3 .

Claims (8)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 正極、負極及び非水系のイオン伝導体か
らなる非水系二次電池であって、負極がリチウムを含む
か又はリチウムが挿入・脱離可能な活物質からなり、正
極がリチウム・マンガンの複合酸化物を含む活物質から
なり、かつその酸化物のＣｕＫα線によるＸ線回折線
が、少なくとも１５．２〜１５．６゜、１８．６〜１
８．８゜及び２４．５〜２５．１゜の範囲にそれぞれピ
ークを有しており、前記１５．２〜１５．６゜の範囲の
ピーク強度に対する２７〜３３゜の範囲のピーク強度の
比が０．０２より小さいことを特徴とする非水系二次電
池。1. A non-aqueous secondary battery comprising a positive electrode, a negative electrode and a non-aqueous ionic conductor, wherein the negative electrode contains lithium or an active material into which lithium can be inserted / removed, and the positive electrode contains lithium. It is composed of an active material containing a complex oxide of manganese, and the oxide has an X-ray diffraction line by CuKα ray of at least 15.2 to 15.6 ° and 18.6 to 1.
It has peaks in the range of 8.8 ° and 24.5 to 25.1 °, respectively, and the ratio of the peak intensity in the range of 27 to 33 ° to the peak intensity in the range of 15.2 to 15.6 °. Is less than 0.02, a non-aqueous secondary battery. 【請求項２】 Ｘ線回折線の１５．２〜１５．６゜の範
囲のピーク強度に対する１８．６〜１８．８゜の範囲の
ピーク強度の比が０．０２〜１．５の範囲内である請求
項１記載の非水系二次電池。2. The ratio of the peak intensity in the range of 18.6 to 18.8 ° to the peak intensity in the range of 15.2 to 15.6 ° of the X-ray diffraction line is in the range of 0.02 to 1.5. The non-aqueous secondary battery according to claim 1. 【請求項３】 リチウム・マンガンの複合酸化物が、 Ｌｉx ＭｎＯy （０．８≦ｘ≦１．２、１．９≦ｙ≦２．２） なる組成式を満たすものを含む請求項１記載の非水系二
次電池。3. The lithium-manganese composite oxide contains one that satisfies a composition formula of Li x MnO y (0.8 ≦ x ≦ 1.2, 1.9 ≦ y ≦ 2.2). The non-aqueous secondary battery described. 【請求項４】 負極の活物質が、リチウムが挿入・脱離
の可能な炭素である請求項１記載の非水系二次電池。4. The non-aqueous secondary battery according to claim 1, wherein the active material of the negative electrode is carbon into which lithium can be inserted and released. 【請求項５】 負極の活物質が、リチウムが挿入・脱離
の可能な黒鉛である請求項１記載の非水系二次電池。5. The non-aqueous secondary battery according to claim 1, wherein the negative electrode active material is graphite into which lithium can be inserted and released. 【請求項６】 α型、β型、γ型、δ型、ε型、η型、
λ型、電解型又はラムスデライト型のＭｎＯ2、Ｍｎ5Ｏ
8、Ｍｎ2Ｏ3、ＭｎＯＯＨ及びＬｉＭｎ2 Ｏ4からなる群
より選ばれた少なくとも１種のマンガン化合物と、塩化
リチウム、臭化リチウム、ヨウ化リチウム、水酸化リチ
ウム、酸化リチウム、硝酸リチウム、炭酸リチウム、蟻
酸リチウム、酢酸リチウム、安息香酸リチウム、クエン
酸リチウム、乳酸リチウム、シュウ酸リチウム、ピルビ
ン酸リチウム、ステアリン酸リチウム、酒石酸リチウム
及びＬｉ2ＭｎＯ3なる群より選ばれた少なくとも１種の
リチウム化合物とを混合し、該混合物を、４００〜２０
００℃の温度で、かつ酸素含有量が実質的に０体積％よ
り大きく１０体積％以下の範囲内の雰囲気中で焼成して
リチウム・マンガン複合酸化物を得ることからなる請求
項１記載の非水系二次電池の製造方法。6. An α type, β type, γ type, δ type, ε type, η type,
λ type, electrolytic type or ramsdellite type MnO 2 , Mn 5 O
8 , at least one manganese compound selected from the group consisting of Mn 2 O 3 , MnOOH and LiMn 2 O 4 , and lithium chloride, lithium bromide, lithium iodide, lithium hydroxide, lithium oxide, lithium nitrate, carbonic acid At least one lithium compound selected from the group consisting of lithium, lithium formate, lithium acetate, lithium benzoate, lithium citrate, lithium lactate, lithium oxalate, lithium pyruvate, lithium stearate, lithium tartrate and Li 2 MnO 3 . And are mixed, and the mixture is mixed with 400 to 20
The lithium-manganese composite oxide according to claim 1, which is obtained by firing at a temperature of 00 ° C. and in an atmosphere in which the oxygen content is substantially more than 0% by volume and 10% by volume or less. Manufacturing method of water-based secondary battery. 【請求項７】 α型、β型、γ型、δ型、ε型、η型、
λ型、電解型又はラムスデライト型のＭｎＯ2、Ｍｎ5Ｏ
8、Ｍｎ2Ｏ3、ＭｎＯＯＨ及びＬｉＭｎ2 Ｏ4からなる群
より選ばれた少なくとも１種のマンガン化合物と、塩化
リチウム、臭化リチウム、ヨウ化リチウム、水酸化リチ
ウム、酸化リチウム、硝酸リチウム、炭酸リチウム、蟻
酸リチウム、酢酸リチウム、安息香酸リチウム、クエン
酸リチウム、乳酸リチウム、シュウ酸リチウム、ピルビ
ン酸リチウム、ステアリン酸リチウム、酒石酸リチウム
及びＬｉ2ＭｎＯ3なる群より選ばれた少なくとも１種の
リチウム化合物とを混合し、該混合物を、２５０℃以上
の温度で、かつ還元性雰囲気中で焼成してリチウム・マ
ンガン複合酸化物を得ることからなり、還元性雰囲気
が、水素を０体積％より大きく３０体積％以下の範囲内
で含有する雰囲気又はプロパンを０体積％より大きく５
０体積％以下の範囲内で含有する雰囲気である請求項１
記載の非水系二次電池の製造方法。7. An α type, β type, γ type, δ type, ε type, η type,
λ type, electrolytic type or ramsdellite type MnO 2 , Mn 5 O
8 , at least one manganese compound selected from the group consisting of Mn 2 O 3 , MnOOH and LiMn 2 O 4 , and lithium chloride, lithium bromide, lithium iodide, lithium hydroxide, lithium oxide, lithium nitrate, carbonic acid At least one lithium compound selected from the group consisting of lithium, lithium formate, lithium acetate, lithium benzoate, lithium citrate, lithium lactate, lithium oxalate, lithium pyruvate, lithium stearate, lithium tartrate and Li 2 MnO 3 . And the mixture is mixed in a reducing atmosphere at a temperature of 250 ° C. or higher to obtain a lithium-manganese composite oxide, and the reducing atmosphere contains 30% by volume or more of hydrogen. The atmosphere or propane contained in the range of less than or equal to volume% is greater than 0% by volume and 5
The atmosphere is contained within a range of 0% by volume or less.
A method for producing the non-aqueous secondary battery described. 【請求項８】 プロパンを０体積％より大きく５０体積
％以下の範囲内で含有する還元性雰囲気中、３００〜２
０００℃の温度範囲内で焼成する請求項７記載の非水系
二次電池の製造方法。8. A reducing atmosphere containing propane in an amount of more than 0% by volume and not more than 50% by volume in a range of 300 to 2
The method for producing a non-aqueous secondary battery according to claim 7 , wherein the firing is performed within a temperature range of 000 ° C.
JP30787594A 1993-12-24 1994-12-12 Non-aqueous secondary battery and method for producing positive electrode active material thereof Expired - Fee Related JP3373069B2 (en)

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JP4769998B2 (en) * 2000-04-20 2011-09-07 株式会社豊田中央研究所 Method for producing lithium manganese composite oxide
EP1295851A4 (en) 2000-11-16 2008-08-20 Hitachi Maxell Lithium-containing composite oxide and nonaqueous secondary cell using the same, and method for manufacturing the same
KR20060102522A (en) * 2005-03-22 2006-09-27 니폰 가가쿠 고교 가부시키가이샤 Lithium manganate, process for preparing the same, positive electrode sub-active material of lithium secondary battery, positive electrode active material of lithium secondary battery and lithium secondary battery
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JP2014211948A (en) * 2011-08-31 2014-11-13 三洋電機株式会社 Nonaqueous electrolyte secondary battery
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