JPH07101727A - Lithium manganese double oxide, its production and application - Google Patents
Lithium manganese double oxide, its production and applicationInfo
- Publication number
- JPH07101727A JPH07101727A JP5265539A JP26553993A JPH07101727A JP H07101727 A JPH07101727 A JP H07101727A JP 5265539 A JP5265539 A JP 5265539A JP 26553993 A JP26553993 A JP 26553993A JP H07101727 A JPH07101727 A JP H07101727A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- composite oxide
- manganese composite
- lithium manganese
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はリチウム二次電池用リチ
ウムマンガン複合酸化物およびその製造方法並びにその
用途に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium manganese composite oxide for a lithium secondary battery, a method for producing the same and its use.
【０００２】マンガン酸化物は、電池活物質として、古
くから使用されている材料であり、マンガンとリチウム
の複合物質であるリチウムマンガン複合酸化物は、近
年、リチウム二次電池用活物質として注目されている材
料である。Manganese oxide has been used as a battery active material for a long time, and lithium manganese composite oxide, which is a composite material of manganese and lithium, has recently attracted attention as an active material for lithium secondary batteries. It is a material.
【０００３】また、リチウム二次電池は、高出力、高エ
ネルギー密度な電池として、その実用化が期待されてい
る新型二次電池である。The lithium secondary battery is a new type secondary battery which is expected to be put into practical use as a battery having high output and high energy density.
【０００４】[0004]
【従来の技術】リチウム二次電池用の正極材料は、その
実用化に当たり、電池として使用する場合に高い作動
電圧領域，多い放電容量およびサイクル安定性が求
められている。2. Description of the Related Art In practical use, a positive electrode material for a lithium secondary battery is required to have a high operating voltage range, a large discharge capacity and a cycle stability when used as a battery.
【０００５】リチウムマンガン複合酸化物の中でもスピ
ネル型構造を持つリチウムマンガン複合酸化物は、放電
時に４Ｖ付近および３Ｖ付近に平坦部分のある二段放電
を示すことが知られている。この４Ｖ付近の作動電圧領
域で可逆的にサイクルさせることができれば、高いエネ
ルギーを取り出すことが期待できる。結晶構造から考え
るとスピネル型リチウムマンガン酸化物は安定でかつ結
晶構造中にリチウムイオンが移動可能な通路があること
より、サイクル安定性が期待できるために、近年、リチ
ウム二次電池用の正極材料として注目され、実用化がは
かられている。例えば、特開昭６３−１８７５６９号公
報ではＭｎ2Ｏ3とＬｉ2ＣＯ3をＭｎ：Ｌｉ＝２：１（モ
ル比）で混合し、６５０℃で６時間，８５０℃で１４時
間空気中で焼成する方法でＬｉＭｎ2Ｏ4を得ている。It is known that among the lithium-manganese composite oxides, the lithium-manganese composite oxide having a spinel structure exhibits a two-stage discharge having flat portions near 4V and 3V during discharge. If reversible cycling can be performed in this operating voltage region near 4 V, high energy can be expected to be taken out. Considering the crystal structure, spinel-type lithium manganese oxide is stable, and since there is a path through which lithium ions can move in the crystal structure, cycle stability can be expected, so in recent years, positive electrode materials for lithium secondary batteries have been developed. Has been attracting attention, and is being put to practical use. For example, in JP-A-63-187569, Mn 2 O 3 and Li 2 CO 3 are mixed at Mn: Li = 2: 1 (molar ratio), and the mixture is heated in air at 650 ° C. for 6 hours and 850 ° C. for 14 hours. LiMn 2 O 4 is obtained by the firing method.
【０００６】また、特開平３−１２７４５３号公報では
二酸化マンガンと硝酸リチウムをＭｎ：Ｌｉ＝２．２：
１．０〜１．８：１．０（モル比）で混合し、８８０℃
以上１０００℃以下の温度範囲で焼成する方法でリチウ
ムとマンガンからなる酸化物を得ている。Further, in JP-A-3-127453, manganese dioxide and lithium nitrate are mixed with Mn: Li = 2.2:
Mix at 1.0-1.8: 1.0 (molar ratio), 880 ° C
An oxide composed of lithium and manganese is obtained by a method of firing in a temperature range of 1000 ° C. or lower.
【０００７】前記の両方法で得られたスピネル型リチウ
ムマンガン酸化物は、いずれも正極に用いた場合には、
本発明者らの検討によれば、焼成を高温で行っているた
めに粒子の焼結反応が進み、表面積が低くなり、放電容
量が少なくなるばかりでなく、さらには、結晶性が高く
なるために、充放電時のリチウムイオン挿入・脱離に伴
う結晶格子の膨張・収縮により結晶が崩壊しやすく、サ
イクル特性も悪くなりやすい。The spinel type lithium manganese oxide obtained by both of the above-mentioned methods, when used in the positive electrode,
According to the study by the present inventors, since the sintering reaction of the particles proceeds because the firing is performed at a high temperature, the surface area becomes low, the discharge capacity decreases, and further, the crystallinity increases. In addition, the crystals are likely to collapse due to the expansion and contraction of the crystal lattice accompanying the insertion and desorption of lithium ions during charge and discharge, and the cycle characteristics are likely to deteriorate.
【０００８】また、特開平２−１０９２６０号公報に
は、硝酸マンガンとリチウム塩を２００から５５０℃で
加熱処理して、かさ密度が大きく、かつ結晶性の低いＬ
ｉＭｎ2Ｏ4を得ているが、本発明者らが検討した結果、
結晶性が低いために、４Ｖ級の正極材料として使用でき
ない。Further, in Japanese Patent Application Laid-Open No. 2-109260, manganese nitrate and a lithium salt are heat-treated at 200 to 550 ° C. to obtain L having a large bulk density and low crystallinity.
Although iMn 2 O 4 has been obtained, as a result of examination by the present inventors,
Due to its low crystallinity, it cannot be used as a 4V class positive electrode material.
【０００９】さらに、特開平３−４４４５号公報では、
γ−ＭｎＯＯＨとリチウム塩を５４０〜９５０℃で加熱
処理して、スピネル構造の発達しているリチウムマンガ
ン酸化物を得ているが、この場合、焼成時に粒子の焼結
反応が進み、表面積が低くなるために、粉砕を行う必要
があり、工業的には有利ではなく、また、本発明者の検
討によれば、前記生成物を高電流密度で充放電を行った
場合、大きな放電容量を得にくい、または、サイクル劣
化が大きなりやすいなど、満足のいくものではなかっ
た。Further, in Japanese Patent Laid-Open No. 3-4445,
[gamma] -MnOOH and a lithium salt are heat-treated at 540 to 950 [deg.] C. to obtain a lithium manganese oxide having a developed spinel structure. In this case, the sintering reaction of particles proceeds during firing and the surface area is low. Therefore, it is necessary to pulverize, which is not industrially advantageous, and according to the study of the present inventors, when the product is charged and discharged at a high current density, a large discharge capacity is obtained. It was not satisfactory, such as difficult or easy cycle deterioration.
【００１０】以上のようにスピネル型リチウムマンガン
酸化物を合成する場合には、合成条件により、高温で熱
処理をした場合には、生成物の表面積が低下するために
高い放電容量を得るのが難しい、また、低温で熱処理し
た場合には、従来法によれば生成物の結晶性が低くまた
はＭｎ2Ｏ3が副生するなどして、充放電サイクルの進行
にともなって、性能が低下しやすく、現在のところ、リ
チウム二次電池用の正極材料として、高い作動電圧領
域，多い放電容量およびサイクル安定性を全て満足する
ものはスピネル型リチウムマンガン酸化物系では得られ
ていない。In the case of synthesizing the spinel type lithium manganese oxide as described above, it is difficult to obtain a high discharge capacity because the surface area of the product is reduced when the heat treatment is performed at a high temperature depending on the synthesis conditions. In addition, when heat treatment is performed at a low temperature, according to the conventional method, the crystallinity of the product is low or Mn 2 O 3 is produced as a by-product, so that the performance tends to decrease as the charge / discharge cycle progresses. At present, as a positive electrode material for a lithium secondary battery, a material satisfying all of a high operating voltage region, a large discharge capacity and cycle stability has not been obtained with a spinel type lithium manganese oxide system.
【００１１】[0011]
【発明が解決しようとする課題】本発明の目的は、リチ
ウム二次電池用の正極材料として、高い作動電圧領域，
多い放電容量およびサイクル安定性もつリチウム二次電
池用リチウムマンガン複合酸化物およびその製造方法を
提供することにある。The object of the present invention is to provide a positive electrode material for a lithium secondary battery, which has a high operating voltage range,
An object of the present invention is to provide a lithium manganese composite oxide for a lithium secondary battery, which has a large discharge capacity and cycle stability, and a method for producing the same.
【００１２】さらに、このリチウムマンガン複合酸化物
を正極に用いた、高出力、高エネルギー密度なリチウム
二次電池を提供することにある。Another object of the present invention is to provide a high-output, high-energy-density lithium secondary battery using this lithium-manganese composite oxide as a positive electrode.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、鋭意検討
した結果、ＢＥＴ比表面積が３ｍ2／ｇ以上で粒子形態
が針状であることを特徴とするスピネル型構造からなる
リチウムマンガン複合酸化物およびγ−ＭｎＯＯＨとＬ
ｉＮＯ3との混合物を加熱処理することを特徴とするリ
チウムマンガン複合酸化物の製造方法が前記課題を解決
することを見い出し、さらに該リチウムマンガン複合酸
化物を正極に用いることにより高性能なリチウム二次電
池が得られることを見い出し、本発明を完成した。Means for Solving the Problems As a result of intensive studies, the present inventors have made a lithium manganese composite having a spinel structure characterized by having a BET specific surface area of 3 m 2 / g or more and having a needle-like particle shape. Oxide and γ-MnOOH and L
It has been found that a method for producing a lithium-manganese composite oxide, which is characterized in that a mixture with iNO 3 is heat-treated, solves the above-mentioned problems, and by using the lithium-manganese composite oxide for a positive electrode, high-performance lithium The present invention has been completed by finding that a secondary battery can be obtained.
【００１４】[0014]
【作用】以下、本発明を具体的に説明する。The present invention will be described in detail below.
【００１５】本発明のリチウムマンガン複合酸化物は、
スピネル構造であり、ＪＣＰＤＳ：Ｎｏ．３５−７８２
のＬｉＭｎ2Ｏ4と同様のＸ線回折パターンを示すもので
ある。The lithium manganese composite oxide of the present invention is
It has a spinel structure, and JCPDS: No. 35-782
Shows an X-ray diffraction pattern similar to that of LiMn 2 O 4 .
【００１６】さらに、本発明のリチウムマンガン複合酸
化物は粒子構造が針状である。この針状粒子であること
は、原料のγ−ＭｎＯＯＨの粒子形態に起因するもので
あると考えられるが、この針状粒子であるということ
が、リチウム電池の正極材料として用いた場合に電解液
および導電材との適度な接触をもたらすために高性能で
あるのではないかと推定している。Furthermore, the lithium manganese composite oxide of the present invention has a needle-like particle structure. The acicular particles are considered to be due to the particle morphology of the raw material γ-MnOOH. The acicular particles, when used as a positive electrode material of a lithium battery, are not suitable for the electrolyte solution. It is presumed that it has high performance to bring about proper contact with the conductive material.
【００１７】また、本発明のリチウムマンガン複合酸化
物はそのＢＥＴ比表面積が３ｍ2／ｇで以上であること
を必須とする。該比表面積が３ｍ2／ｇ未満であると表
面での主にＬｉと電子の移動が悪くなり、放電容量が少
なくなる、高エネルギー密度放電をおこなった場合に構
造破壊の原因となるなど電池性能を低下させる恐れがあ
る。It is essential that the lithium manganese composite oxide of the present invention has a BET specific surface area of 3 m 2 / g or more. If the specific surface area is less than 3 m 2 / g, the movement of Li and electrons mainly on the surface will be poor, the discharge capacity will be reduced, and the structure will be destroyed when high energy density discharge is performed. May decrease.
【００１８】前述のような本発明のリチウムマンガン複
合酸化物は以下のようにして、製造できる。The lithium manganese composite oxide of the present invention as described above can be manufactured as follows.
【００１９】まず、本発明のリチウムマンガン複合酸化
物製造で用いるγ−ＭｎＯＯＨは、例えば、以下の方法
で得ることができる。First, γ-MnOOH used in the production of the lithium manganese composite oxide of the present invention can be obtained, for example, by the following method.
【００２０】水酸化マンガン（Ｍｎ（ＯＨ）2）を過
酸化水素（Ｈ2Ｏ2）で酸化する方法。A method of oxidizing manganese hydroxide (Mn (OH) 2 ) with hydrogen peroxide (H 2 O 2 ).
【００２１】（Ｏｗｅｎ Ｂｒｉｃｋｅｒ， Ｔｈｅ
Ａｍｅｒｉｃａｎ Ｍｉｎｅｒａｌ−ｏｇｉｓｔ， ｖ
ｏｌ．５０， ｐ．１２９６（１９６５）） ２０℃以下の温度で、硫酸マンガン（ＭｎＳＯ4）と
過酸化水素の混合液にアンモニア（ＮＨ4ＯＨ）を加え
る方法。(Owen Bricker, The
American Mineral-ogist, v
ol. 50, p. 1296 (1965)) A method of adding ammonia (NH 4 OH) to a mixed liquid of manganese sulfate (MnSO 4 ) and hydrogen peroxide at a temperature of 20 ° C. or lower.
【００２２】（Ｋ．Ｍａｔｓｕｋｉ， Ｅｌｅｃｔｒｏ
ｃｈｉｍｉｃａ Ａｃｔａ， ｖｏｌ．３１， ｐ．１
３（１９８６））前記のγ−ＭｎＯＯＨは針状の粒子で
ある。(K. Matsuki, Electro
chimica Acta, vol. 31, p. 1
3 (1986)) The γ-MnOOH is acicular particles.
【００２３】本発明のリチウムマンガン複合酸化物製造
で用いるＬｉ源は、硝酸リチウム（ＬｉＮＯ3）である
ことを必須とする。これは、硝酸リチウムが溶融温度が
２６４℃および分解温度が６００℃と低温であるため後
述する熱処理に対して有効であるためである。It is essential that the Li source used in the production of the lithium-manganese composite oxide of the present invention is lithium nitrate (LiNO 3 ). This is because lithium nitrate has a low melting temperature of 264 ° C. and a decomposition temperature of 600 ° C. and is effective for the heat treatment described later.
【００２４】本発明のリチウムマンガン複合酸化物の製
造では、前述のγ−ＭｎＯＯＨとＬｉＮＯ3を混合す
る。In the production of the lithium manganese composite oxide of the present invention, the aforementioned γ-MnOOH and LiNO 3 are mixed.
【００２５】混合の比率はモル比でＭｎ：Ｌｉ＝２．
０：０．８〜２．０：１．２とするのが好ましく、Ｍ
ｎ：Ｌｉ＝２．０：０．９〜２．０：１．１がさらに好
ましい。混合は通常の方法でよく、両原料を乾式混合す
る、または硝酸リチウム水溶液中にγ−ＭｎＯＯＨを懸
濁させた後、該懸濁液を乾燥するなど均一に混合できる
方法であればよい。The mixing ratio is Mn: Li = 2.
The ratio is preferably 0: 0.8 to 2.0: 1.2, and M
It is more preferable that n: Li = 2.0: 0.9 to 2.0: 1.1. The mixing may be carried out by an ordinary method, such as dry mixing of the two raw materials, or by suspending γ-MnOOH in an aqueous lithium nitrate solution, and then drying the suspension, so long as it can be uniformly mixed.
【００２６】前記混合物を加熱処理する。本発明のリチ
ウムマンガン複合酸化物の製造ではこの加熱処理によ
り、従来法では得ることの難しかった新規なリチウムマ
ンガン複合酸化物を得ることができる。The mixture is heat treated. In the production of the lithium-manganese composite oxide of the present invention, this heat treatment makes it possible to obtain a novel lithium-manganese composite oxide which is difficult to obtain by the conventional method.
【００２７】本発明の製造方法によれば、原料のγ−Ｍ
ｎＯＯＨの粒子形態を維持しつつ、ＬｉＭｎ2Ｏ4を合成
可能であり、焼成に伴う表面積の低下が少ない。According to the manufacturing method of the present invention, the raw material γ-M
LiMn 2 O 4 can be synthesized while maintaining the particle morphology of nOOH, and the decrease in surface area due to firing is small.
【００２８】本発明の熱処理は、５５０〜８５０℃で行
う。The heat treatment of the present invention is performed at 550 to 850 ° C.
【００２９】該温度が８５０℃より高いとＢＥＴ比表面
積が低くなり、さらに生成物の粒子の焼結反応が進み、
表面積が低く、放電容量が少なくなるなど生成物の電池
性能が低下する、さらに、該温度が５５０℃より低いと
生成物がスピネル型の結晶構造とならない、または、結
晶性が低くなり、生成物の電池性能が低下するなど好ま
しくない。When the temperature is higher than 850 ° C., the BET specific surface area becomes low, and the sintering reaction of the product particles further proceeds,
When the temperature is lower than 550 ° C., the product does not have a spinel type crystal structure, or the crystallinity is low, resulting in a low surface area and a low discharge capacity. It is not preferable because the battery performance is deteriorated.
【００３０】前記熱処理温度は６５０〜７５０℃である
のが好ましい。The heat treatment temperature is preferably 650 to 750 ° C.
【００３１】本発明では、前記熱処理温度で処理する途
中、最終処理温度より低い、次の温度で処理する多段熱
処理とするのが好ましい。In the present invention, it is preferable to use a multi-step heat treatment in which the treatment is performed at the following temperature lower than the final treatment temperature during the treatment at the heat treatment temperature.
【００３２】 １段目： ２６０±１０℃ ，１〜５０時間 ２段目： ３００〜５００℃ ，１〜５０時間 最 終： ５５０〜８５０℃ ，１〜５０時間 前記各段階での温度については、以下のように推定して
いる。First stage: 260 ± 10 ° C., 1 to 50 hours Second stage: 300 to 500 ° C., 1 to 50 hours Final stage: 550 to 850 ° C., 1 to 50 hours Regarding the temperature at each stage, It is estimated as follows.
【００３３】すなわち、１段目の２６０±１０℃，１〜
５０時間の熱処理においてＬｉ源であるＬｉＮＯ3が融
解する。ついで、２段目の３００〜５００℃，１〜５０
時間の熱処理でＬｉ，ＭｎおよびＯからなる複合酸化物
を形成し、最終的に６５０〜８５０℃，１〜５０時間の
熱処理でスピネル型リチウムマンガン複合酸化物が生成
するものと推定している。That is, the first stage 260 ± 10 ° C., 1 to
LiNO 3, which is the Li source, melts during the heat treatment for 50 hours. Then, the second stage 300-500 ℃, 1-50
It is presumed that a complex oxide composed of Li, Mn, and O is formed by heat treatment for an hour, and finally a spinel-type lithium manganese complex oxide is formed by heat treatment at 650 to 850 ° C. for 1 to 50 hours.
【００３４】前記多段熱処理は、連続して熱処理しても
よく、単独に各温度で行ってもよい。又、前記多段熱処
理を行う場合、各温度で熱処理後、混合するのが均一性
を向上させるために好ましく、連続して熱処理する場合
には、ロータリーキルンなどを用いればよい。The multi-step heat treatment may be a continuous heat treatment or may be performed individually at each temperature. In the case of performing the multi-step heat treatment, it is preferable to mix after the heat treatment at each temperature in order to improve the uniformity, and in the case of continuously performing the heat treatment, a rotary kiln or the like may be used.
【００３５】前記保持時間が１時間未満では、熱処理に
より均一のものを得ることが難しくなり、５０時間より
長くするのは、効果がなく経済的ではない。If the holding time is less than 1 hour, it becomes difficult to obtain a uniform product by heat treatment, and making it longer than 50 hours is not effective and economical.
【００３６】本発明で熱処理を行う場合の昇降温速度は
１時間当たり１０〜５００℃程度から適時選択すれば良
い。When the heat treatment is performed in the present invention, the temperature raising / lowering rate may be appropriately selected from about 10 to 500 ° C. per hour.
【００３７】本発明では、上記熱処理をおこなった後も
粒子形状は変わらず、さらに粉砕などをおこなわなくて
も、ＢＥＴ比表面積は３ｍ2／ｇ以上である。このこと
は製造工程で生成物の結晶構造に歪または欠陥が生じ難
く、性能のよいリチウム二次電池用材料となると推定し
ている。In the present invention, the particle shape does not change even after the above heat treatment, and the BET specific surface area is 3 m 2 / g or more without further pulverization. It is presumed that this is a material for lithium secondary batteries with which the crystal structure of the product is less likely to be distorted or defective in the manufacturing process and has good performance.
【００３８】前記のようにして製造した該リチウムマン
ガン複合酸化物を用いてリチウム二次電池を作製する。A lithium secondary battery is produced using the lithium manganese composite oxide produced as described above.
【００３９】本発明のリチウム二次電池で用いる負極に
は、金属リチウム又はリチウムを吸蔵放出可能な物資を
用いる。例えば、金属リチウム、リチウム／アルミニウ
ム合金、リチウム／スズ合金、リチウム／鉛合金、電気
化学的にリチウムイオンをドープ脱ドープする炭素系材
料が例示される。For the negative electrode used in the lithium secondary battery of the present invention, metallic lithium or a material capable of inserting and extracting lithium is used. Examples thereof include metallic lithium, lithium / aluminum alloys, lithium / tin alloys, lithium / lead alloys, and carbon-based materials that are electrochemically doped and dedoped with lithium ions.
【００４０】また、本発明のリチウム二次電池で用いる
電解質としては、特に制限されないが、例えば、カーボ
ネート類、スルホラン類、ラクトン類、エーテル類等の
有機溶媒中にリチウム塩を溶解したものや、リチウムイ
オン導電性の固体電解質を用いることができる。The electrolyte used in the lithium secondary battery of the present invention is not particularly limited, but for example, one obtained by dissolving a lithium salt in an organic solvent such as carbonates, sulfolanes, lactones and ethers, A lithium ion conductive solid electrolyte can be used.
【００４１】本発明の、リチウムマンガン複合酸化物を
用いて、図１に示す３極式セルを構成した。The lithium manganese composite oxide of the present invention was used to construct the three-electrode cell shown in FIG.
【００４２】図中において、１：試験極ホルダー、２：
試験極、３：参照極、４：対極、５：容器を示す。In the figure, 1: test pole holder, 2:
Test electrode, 3: reference electrode, 4: counter electrode, and 5: container.
【００４３】[0043]
【実施例】以下実施例を述べるが、本発明はこれに限定
されるものではない。EXAMPLES Examples will be described below, but the present invention is not limited thereto.
【００４４】なお、本発明の実施例及び比較例における
Ｘ線回折パターンは、以下の条件で測定した。The X-ray diffraction patterns in Examples and Comparative Examples of the present invention were measured under the following conditions.
【００４５】 測定機種 ：マックサイエンス社 ＭＸＰ−３ 照射Ｘ線 ：Ｃｕ Ｋα線 測定モード ：ステップスキャン スキャン条件：毎秒０．０４度 計測時間 ：３秒 測定範囲 ：２θとして５度から８０度 実施例１ 『スピネル型リチウムマンガン複合酸化物の合成』実施
例１として、スピネル型リチウムマンガン複合酸化物を
以下の方法で合成した。Measurement model: Mac Science MXP-3 irradiation X-ray: Cu Kα ray Measurement mode: Step scan Scan condition: 0.04 degrees per second Measurement time: 3 seconds Measurement range: 5 degrees to 80 degrees as 2θ Example 1 [Synthesis of Spinel Type Lithium Manganese Composite Oxide] As Example 1, a spinel type lithium manganese composite oxide was synthesized by the following method.
【００４６】γ−ＭｎＯＯＨ（東ソー株式会社製、以下
東ソー社製γ−ＭｎＯＯＨと略記す。）５．５ｇと硝酸
リチウム２．１６ｇを乳鉢で混合した後、空気雰囲気で
以下の〜の条件で熱処理した。After mixing 5.5 g of γ-MnOOH (manufactured by Tosoh Corporation, hereinafter abbreviated as γ-MnOOH manufactured by Tosoh Corporation) with 2.16 g of lithium nitrate in a mortar, heat treatment was performed in an air atmosphere under the following conditions. did.
【００４７】 昇温：室温から２６０℃まで２．５時間 保持：２６０℃，２４時間 昇温：２６０℃から４５０℃まで２．０時間 保持：４５０℃，２４時間 昇温：４５０℃から６５０℃まで２．０時間 保持：６５０℃，２４時間 降温：６５０℃から室温まで６．５時間 図２および表１に得られた化合物のＸ線回折パターンお
よび組成分析およびＢＥＴ比表面積測定の結果を示し
た。Temperature increase: 2.5 hours from room temperature to 260 ° C. Hold: 260 ° C., 24 hours Temperature increase: 2.0 hours from 260 ° C. to 450 ° C. Hold: 450 ° C., 24 hours Temperature increase: 450 ° C. to 650 ° C. Until 2.0 hours Hold: 650 ° C., 24 hours Cooling temperature: 650 ° C. to room temperature for 6.5 hours FIG. 2 and Table 1 show the results of X-ray diffraction pattern, composition analysis and BET specific surface area measurement of the obtained compounds. It was
【００４８】[0048]
【表１】 [Table 1]
【００４９】この結果より生成物は、スピネル構造であ
り、ＪＣＰＤＳ：Ｎｏ．３５−７８２のＬｉＭｎ2Ｏ4と
同様のＸ線回折パターンを示し、組成分析の結果より、
Ｌｉ／Ｍｎ＝０．５，Ｍｎの酸化度は＋３．５価であ
り、以上より生成物はスピネル構造のＬｉＭｎ2Ｏ4であ
ると同定した。From this result, the product has a spinel structure, and JCPDS: No. 35-782 shows an X-ray diffraction pattern similar to that of LiMn 2 O 4, and from the results of composition analysis,
Li / Mn = 0.5, the degree of oxidation of Mn was +3.5, and it was identified from the above that the product was LiMn 2 O 4 having a spinel structure.
【００５０】また、ＢＥＴ比表面積は４．６ｍ2／ｇで
あり、３ｍ2／ｇ以上であった。The BET specific surface area was 4.6 m 2 / g, which was 3 m 2 / g or more.
【００５１】図３に原料である東ソー社製γ−ＭｎＯＯ
Ｈおよび生成物のＳＥＭ写真を示した。この写真から明
らかな様に、原料東ソー社製γ−ＭｎＯＯＨおよび生成
物の粒子形状が針状であることが明かとなった。FIG. 3 shows the raw material γ-MnOO manufactured by Tosoh Corporation.
S and SEM photographs of the product are shown. As is clear from this photograph, it was revealed that the raw material Tosoh γ-MnOOH and the product had a needle-like particle shape.
【００５２】実施例２ 熱処理条件を以下の〜のようにした以外は、実施例
１と同一の条件で合成した。Example 2 Synthesis was carried out under the same conditions as in Example 1 except that the heat treatment conditions were as follows.
【００５３】 昇温：室温から２６０℃まで２．５時間 保持：２６０℃，２４時間 昇温：２６０℃から３５０℃まで１．０時間 保持：３５０℃，２４時間 昇温：３５０℃から５５０℃まで２．０時間 保持：５５０℃，２４時間 降温：５５０℃から室温まで５．５時間 得られた化合物は実施例１と同様にスピネル構造であっ
た。Temperature increase: 2.5 hours from room temperature to 260 ° C Hold: 260 ° C, 24 hours Temperature increase: 1.0 hour from 260 ° C to 350 ° C Hold: 350 ° C, 24 hours Temperature increase: 350 ° C to 550 ° C Until 2.0 hours Hold: 550 ° C., 24 hours Temperature drop: 550 ° C. to room temperature for 5.5 hours The obtained compound had a spinel structure as in Example 1.
【００５４】また、ＢＥＴ比表面積は５．５ｍ2／ｇで
あり、３ｍ2／ｇ以上であった。The BET specific surface area was 5.5 m 2 / g, which was 3 m 2 / g or more.
【００５５】実施例３ 熱処理条件の最終処理温度を７００℃にする以外は、実
施例１と同一の条件で合成した。Example 3 Synthesis was carried out under the same conditions as in Example 1 except that the final heat treatment condition was 700 ° C.
【００５６】得られた化合物は実施例１と同様にスピネ
ル構造であった。The obtained compound had a spinel structure as in Example 1.
【００５７】ＢＥＴ比表面積は３．８ｍ2／ｇであり、
３ｍ2／ｇ以上であった。The BET specific surface area is 3.8 m 2 / g,
It was 3 m 2 / g or more.
【００５８】比較例１ 熱処理条件を以下の〜のようにした以外は、実施例
１と同一の条件で合成した。Comparative Example 1 Synthesis was carried out under the same conditions as in Example 1 except that the heat treatment conditions were as follows.
【００５９】熱処理条件 昇温：室温から９００℃まで９．０時間 保持：９００℃，２４時間 降温：９００℃から室温まで９．０時間 図２および表１に得られた化合物のＸ線回折パターンお
よび組成分析およびＢＥＴ比表面積測定の結果を示し
た。この結果より生成物は、スピネル型リチウムマンガ
ン複合酸化物であった。Heat treatment conditions Temperature rising: from room temperature to 900 ° C. for 9.0 hours Holding: 900 ° C., 24 hours Temperature falling: from 900 ° C. to room temperature 9.0 hours X-ray diffraction pattern of the compound obtained in FIG. 2 and Table 1. The results of composition analysis and BET specific surface area measurement are shown. From this result, the product was a spinel type lithium manganese composite oxide.
【００６０】組成分析の結果より、Ｌｉ／Ｍｎ＝０．
５，Ｍｎの酸化度は＋３．５価であった。From the results of the composition analysis, Li / Mn = 0.
The degree of oxidation of 5, Mn was +3.5.
【００６１】また、ＢＥＴ比表面積は０．２ｍ2／ｇで
あり、３ｍ2／ｇ未満であった。The BET specific surface area was 0.2 m 2 / g, which was less than 3 m 2 / g.
【００６２】実施例４ 『電池性能評価』実施例１および比較例１で得られたリ
チウムマンガン複合酸化物を正極として使用し、以下の
ように３極セルを構成し、充放電特性を測定した。Example 4 "Battery Performance Evaluation" Using the lithium manganese composite oxide obtained in Example 1 and Comparative Example 1 as a positive electrode, a three-electrode cell was constructed as follows, and the charge / discharge characteristics were measured. .
【００６３】まず実施例１および比較例１の生成物と導
電剤のカーボン粉末及び結着剤のポリテトラフルオロエ
チレン粉末を、それぞれ重量比で８８：７：５の割合で
混合した。この混合物７５ｍｇを２ｔｏｎ／ｃｍ2の圧
力で８ｍｍφのペレットに成形した。このペレットを２
００℃で２時間減圧乾燥した後、図１の２の試験極とし
て用いて、図１の４の対極にはリチウム箔を、図１の３
の参照極には、リチウム箔から切り抜いたリチウム片を
用い、電解液には過塩素酸リチウムを１ｍｏｌ／ｄｍ3
濃度で溶解したプロピレンカーボネートを用いて、図１
の３極セルを構成した。First, the products of Example 1 and Comparative Example 1, carbon powder as a conductive agent and polytetrafluoroethylene powder as a binder were mixed in a weight ratio of 88: 7: 5. 75 mg of this mixture was molded into 8 mmφ pellets at a pressure of 2 ton / cm 2 . 2 this pellet
After drying under reduced pressure at 00 ° C. for 2 hours, it was used as the test electrode of 2 in FIG. 1, and lithium foil was used as the counter electrode of 4 of FIG.
As a reference electrode, a lithium piece cut out from a lithium foil was used, and lithium perchlorate was used as an electrolyte at 1 mol / dm 3
Figure 1 using propylene carbonate dissolved at a concentration
A three-electrode cell was constructed.
【００６４】上記方法で構成した３極セルについて、
０．５ｍＡの一定電流で、参照極に対する試験極の電極
電位が、３．５Ｖから４．５Ｖの範囲で充放電を行っ
た。Regarding the three-pole cell constructed by the above method,
Charging / discharging was performed at a constant current of 0.5 mA, with the electrode potential of the test electrode relative to the reference electrode being in the range of 3.5V to 4.5V.
【００６５】図４に実施例１の１サイクル目の放電容量
を１００とした場合の実施例１および比較例１の放電容
量維持率を示した。FIG. 4 shows the discharge capacity retention ratios of Example 1 and Comparative Example 1 when the discharge capacity in the first cycle of Example 1 was 100.
【００６６】実施例１では５０サイクル目で１サイクル
目の８０％以上の容量を保持したのに対して、比較例１
では、１サイクル目で実施例１より放電容量が少なく、
かつ放電容量維持率も実施例１より小さく、サイクル特
性が悪かった。In Example 1, the capacity of 80% or more in the first cycle was maintained at the 50th cycle, whereas in Comparative Example 1
In the first cycle, the discharge capacity was smaller than that in Example 1,
Moreover, the discharge capacity retention ratio was smaller than that of Example 1, and the cycle characteristics were poor.
【００６７】[0067]
【発明の効果】以上述べてきたとおり、本発明により、
リチウム二次電池用の正極材料として、高い作動領域，
多い放電容量およびサイクル安定性もつリチウム二次電
池用リチウムマンガン複合酸化物およびその製造方法を
提供することでき、さらに、このリチウムマンガン複合
酸化物を正極に用いた、高出力、高エネルギー密度なリ
チウム二次電池を構成可能になる。As described above, according to the present invention,
As a positive electrode material for lithium secondary batteries, high operating range,
It is possible to provide a lithium-manganese composite oxide for a lithium secondary battery, which has a large discharge capacity and cycle stability, and a method for producing the same. A secondary battery can be configured.
【図１】実施例及び比較例で構成した電池の実施態様を
示す断面図である。図中、 １：正極用リード線 ２：正極集電用メッシュ ３：正極 ４：セパレーター ５：負極 ６：負極集電用メッシュ ７：負極用リード線 ８：容器 を示す。FIG. 1 is a cross-sectional view showing an embodiment of a battery constituted by an example and a comparative example. In the figure, 1: lead wire for positive electrode 2: mesh for collecting positive electrode 3: positive electrode 4: separator 5: negative electrode 6: mesh for collecting negative electrode 7: lead wire for negative electrode 8: container
【図２】実施例１及び比較例１の生成物のＸ線回折図を
示す。FIG. 2 shows X-ray diffraction patterns of the products of Example 1 and Comparative Example 1.
【図３】原料東ソー社製γ−ＭｎＯＯＨ及び実施例１の
生成物の粒子構造を示す写真である。FIG. 3 is a photograph showing the particle structure of the raw material Tosoh γ-MnOOH and the product of Example 1.
【図４】実施例１の１サイクル目の放電容量を１００と
したときの実施例１及び比較例１の放電容量維持率を示
す。FIG. 4 shows the discharge capacity retention ratios of Example 1 and Comparative Example 1 when the discharge capacity in the first cycle of Example 1 is 100.
Claims (4)
態が針状であることを特徴とするスピネル型構造からな
るリチウムマンガン複合酸化物。1. A lithium-manganese composite oxide having a spinel structure, which has a BET specific surface area of 3 m 2 / g or more and an acicular particle shape.
加熱処理することを特徴とする請求項１に記載のリチウ
ムマンガン複合酸化物の製造方法。2. The method for producing a lithium-manganese composite oxide according to claim 1, wherein a mixture of γ-MnOOH and LiNO 3 is heat-treated.
化物の製造方法において、加熱処理温度が５５０℃〜８
５０℃の範囲であることを特徴とするリチウムマンガン
複合酸化物の製造方法。3. The method for producing a lithium-manganese composite oxide according to claim 2, wherein the heat treatment temperature is 550 ° C. to 8 ° C.
A method for producing a lithium-manganese composite oxide, which is in the range of 50 ° C.
化物を正極に用いることを特徴とするリチウム二次電
池。4. A lithium secondary battery, wherein the lithium manganese composite oxide according to claim 1 is used for a positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5265539A JPH07101727A (en) | 1993-09-30 | 1993-09-30 | Lithium manganese double oxide, its production and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5265539A JPH07101727A (en) | 1993-09-30 | 1993-09-30 | Lithium manganese double oxide, its production and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07101727A true JPH07101727A (en) | 1995-04-18 |
Family
ID=17418535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5265539A Pending JPH07101727A (en) | 1993-09-30 | 1993-09-30 | Lithium manganese double oxide, its production and application |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07101727A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0744381A1 (en) * | 1995-05-24 | 1996-11-27 | BASF Magnetics GmbH | Lithium and manganese (III/IV) containing spinels |
| JPH11102703A (en) * | 1997-09-26 | 1999-04-13 | Asahi Chem Ind Co Ltd | Nonaqueous secondary battery |
| JP2014205617A (en) * | 2014-06-12 | 2014-10-30 | 東ソー株式会社 | Manganese oxide and method for producing lithium manganate using the same |
| CN106276852A (en) * | 2016-08-10 | 2017-01-04 | 玉灵华科技有限公司 | A kind of electrochemical oxidation generator for preparing quantum carbon element |
-
1993
- 1993-09-30 JP JP5265539A patent/JPH07101727A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0744381A1 (en) * | 1995-05-24 | 1996-11-27 | BASF Magnetics GmbH | Lithium and manganese (III/IV) containing spinels |
| JPH11102703A (en) * | 1997-09-26 | 1999-04-13 | Asahi Chem Ind Co Ltd | Nonaqueous secondary battery |
| JP2014205617A (en) * | 2014-06-12 | 2014-10-30 | 東ソー株式会社 | Manganese oxide and method for producing lithium manganate using the same |
| CN106276852A (en) * | 2016-08-10 | 2017-01-04 | 玉灵华科技有限公司 | A kind of electrochemical oxidation generator for preparing quantum carbon element |
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