JP2000281351A - Fine-particulate high-density manganese oxide and its production - Google Patents

Fine-particulate high-density manganese oxide and its production

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Publication number
JP2000281351A
JP2000281351A JP11085106A JP8510699A JP2000281351A JP 2000281351 A JP2000281351 A JP 2000281351A JP 11085106 A JP11085106 A JP 11085106A JP 8510699 A JP8510699 A JP 8510699A JP 2000281351 A JP2000281351 A JP 2000281351A
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JP
Japan
Prior art keywords
manganese oxide
density
fine
manganese
heat treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP11085106A
Other languages
Japanese (ja)
Other versions
JP3495638B2 (en
Inventor
Hiroshi Tazaki
博 田崎
Yoshio Kajitani
芳男 梶谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
Japan Energy Corp
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Filing date
Publication date
Application filed by Japan Energy Corp filed Critical Japan Energy Corp
Priority to JP08510699A priority Critical patent/JP3495638B2/en
Priority to PCT/JP2000/001856 priority patent/WO2000058221A1/en
Publication of JP2000281351A publication Critical patent/JP2000281351A/en
Application granted granted Critical
Publication of JP3495638B2 publication Critical patent/JP3495638B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

PROBLEM TO BE SOLVED: To produce a fine particulate manganese oxide having high density and suitable for producing lithium manganate, or the like, for a lithium secondary battery. SOLUTION: This fine-particulate high-density manganese oxide, which has a median diameter of <=10 μm and exhibits a tapping density of >=1.2 g/cm3, further >=1.8 g/cm3, is obtained by heat treating manganese carbonate in an atmosphere having oxygen content of <15% at 400 to 800 deg.C and further heat treating in an atmosphere having oxygen content of >=15% at 530 to 800 deg.C. In this case, the characteristics necessary for the battery, or the like, are further improved by making the particle form of the obtained manganese oxide spherical by selecting manganese carbonate to be used as the raw material and controlling the heat treating conditions, or the like.

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、例えばリチウム二次
電池の正極材として使用されるマンガン酸リチウム(Li
MnO2 , LiMn24 )等の製造原料として好適なタップ
密度の高い酸化マンガンの製造方法に関するものであ
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lithium manganate (Li
The present invention relates to a method for producing manganese oxide having a high tap density, which is suitable as a raw material for producing MnO 2 and LiMn 2 O 4 ).

【0002】[0002]

【従来技術とその課題】近年、軽量であって電池特性に
優れるリチウム二次電池の需要が拡大の一途をたどって
いる。従来、このリチウム二次電池の正極活物質として
はLiCoO2 やLiNiO2 等の複合酸化物が使用されてきた
が、最近、資源量やコスト的な面からマンガン酸リチウ
ムが(LiMnO2 , LiMn24 )がLiCoO2 やLiNiO2
代わる正極活物質として注目されるようになってきた。
2. Description of the Related Art In recent years, the demand for lithium secondary batteries that are lightweight and have excellent battery characteristics has been steadily expanding. Conventionally, composite oxides such as LiCoO 2 and LiNiO 2 have been used as the positive electrode active material of this lithium secondary battery. Recently, however, lithium manganate has been used (LiMnO 2 , LiMn 2 O 4 ) has attracted attention as a positive electrode active material replacing LiCoO 2 and LiNiO 2 .

【0003】なお、上記マンガン酸リチウムは、マンガ
ン酸化物(酸化マンガン)とリチウム塩(炭酸リチウム
等)とを反応させることにより容易に製造できることが
知られている。現在、このマンガン酸リチウムを製造す
るための“マンガン酸化物原料”としては、一次電池で
あるマンガン乾電池用材料として開発された電解二酸化
マンガンや化学合成二酸化マンガンなどの種々の二酸化
マンガン(MnO2 )や、これら二酸化マンガンを熱処理
して得られた三酸化二マンガン( Mn23 )等が主とし
て使用されている。これらのマンガン酸化物材料は、リ
チウム二次電池用マンガン酸リチウムの製造原料に求め
られる良好な流動性や高い充填密度を示すとされてい
た。
It is known that the above-mentioned lithium manganate can be easily produced by reacting a manganese oxide (manganese oxide) with a lithium salt (such as lithium carbonate). Currently, "manganese oxide raw materials" for producing this lithium manganate include various manganese dioxides (MnO 2 ) such as electrolytic manganese dioxide and chemically synthesized manganese dioxide developed as materials for manganese dry batteries as primary batteries. Further, dimanganese trioxide (Mn 2 O 3 ) obtained by heat-treating these manganese dioxides is mainly used. These manganese oxide materials are said to exhibit good fluidity and high packing density required for raw materials for producing lithium manganate for lithium secondary batteries.

【0004】しかしながら、流動性が良好で充填密度が
高いとされる上記酸化マンガンは比較的大きな粒径(最
大粒径100μm以上,平均粒径25μm以上)を成し
ており、このような大きな粒径を持つ材料を原料として
リチウム二次電池用の電極を作製した場合には実用に足
る平滑な電極を得るのが困難であるという問題があっ
た。
However, the above-mentioned manganese oxide, which is considered to have good fluidity and high packing density, has a relatively large particle size (maximum particle size of 100 μm or more, average particle size of 25 μm or more). When an electrode for a lithium secondary battery is manufactured using a material having a diameter as a raw material, there is a problem that it is difficult to obtain a practically smooth electrode.

【0005】なお、これらの酸化マンガンを粉砕して粒
径を小さくすることによりリチウム二次電池用としての
特性を改善させることが試みられているが、一次電池用
の材料は元々構造が多孔質であるので粉砕して粒径が小
さくなるとタップ密度が著しく小さくなり(1.5g/cm3
大きく下回ってしまう)、電極への塗布性が悪くなるだ
けではなく、体積当りのエネルギ−密度も低下すること
が明らかとなった。
Although attempts have been made to improve the characteristics of lithium secondary batteries by pulverizing these manganese oxides to reduce the particle size, materials for primary batteries originally have a porous structure. Therefore, if the particle size is reduced by pulverization, the tap density becomes extremely low (far less than 1.5 g / cm 3 ), which not only deteriorates the applicability to the electrode but also lowers the energy density per volume. It became clear to do.

【0006】そこで、マンガン酸化物の密度向上のた
め、酸化マンガンの空孔内にマンガン塩を含む溶液を滲
み込ませた後に溶媒を蒸発させ、続いて塩素ガス等を用
いて空孔内に残ったマンガン塩を酸化する方法等が用い
られてきた。しかし、この方法は、湿式処理であること
から処理コストが嵩み、低価格化要求が一段と高まって
いる電池用材料の処理手段として好ましいものとは言え
なかった。
Therefore, in order to improve the density of manganese oxide, a solution containing a manganese salt is infiltrated into the vacancy of manganese oxide, and then the solvent is evaporated. For example, a method of oxidizing manganese salts has been used. However, this method is not preferable as a means for treating a battery material, for which the processing cost is increased due to the wet treatment and the demand for lowering the price is further increased.

【0007】そのため、簡便かつ低コストで小粒径の高
密度酸化マンガンを提供できる手段の開発が強く望まれ
ていた。このようなことから、本発明が目的としたの
は、例えばリチウム二次電池の正極材に求められる“微
細”かつ“高タップ密度”を持つマンガン酸リチウム等
の製造に好適な、高密度の微細粒酸化マンガンを安定か
つ低コストで実現できる手段を確立することである。
[0007] Therefore, there has been a strong demand for the development of means that can provide high-density manganese oxide having a small particle size with ease and at low cost. In view of the above, an object of the present invention is to provide, for example, a high-density high-density material suitable for producing lithium manganate having “fine” and “high tap density” required for a cathode material of a lithium secondary battery. It is an object of the present invention to establish means capable of stably and at low cost producing fine manganese oxide.

【0008】[0008]

【課題を解決するための手段】本発明者等は、上記目的
を達成すべく鋭意研究を重ねた結果、次に示す一連の事
項を知見することができた。 (1) 最近になって微細粒炭酸マンガンの製造に関する検
討が多く行われるようになり、本発明者等もメジアン径
が5μmをも下回る微細粒炭酸マンガンの工業的製造方
法を確立して特願平10−370020号として提案し
たが、このような炭酸マンガン(MnCO3 )を空気中で
熱処理すると、300℃以上程度の温度では下記の反応
が生じてMnO2 微細粒が生成する。 MnCO3 1/22 =MnO2 +CO2 しかし、この場合、MnO2 の生成時にCO2 ガスの発生
が目立ち、そのため得られるMnO2 は非常に多孔質とな
ってタップ密度が低くなる。 (2) 一方、炭酸マンガン(MnCO3 )の熱処理温度を上
げ、空気中にて530℃以上で熱処理すると下記の反応
が生じて Mn23 微細粒が生成する。 2MnCO3 1/22 = Mn23 +2CO2 この場合、CO2 ガス発生等によるタップ密度の低下は
認められないものの、得られる酸化マンガン(Mn23)の
タップ密度には従前の酸化マンガンのそれに比べても格
別な増加傾向は見られない。
Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found the following series of matters. (1) Recently, many studies on the production of fine-grained manganese carbonate have been conducted, and the present inventors have established an industrial production method for fine-grained manganese carbonate having a median diameter of less than 5 μm and have filed a patent application. When such manganese carbonate (MnCO 3 ) is heat-treated in air, the following reaction occurs at a temperature of about 300 ° C. or more, and MnO 2 fine particles are generated. MnCO 3 + 1/2 O 2 = MnO 2 + CO 2 However, in this case, the generation of CO 2 gas is noticeable when generating MnO 2, MnO 2 obtained for the tap density is low become very porous. (2) On the other hand, when the heat treatment temperature of manganese carbonate (MnCO 3 ) is increased and the heat treatment is performed at 530 ° C. or more in the air, the following reaction occurs and Mn 2 O 3 fine particles are generated. 2MnCO 3 + 1/2 O 2 = Mn 2 O 3 + 2CO 2 In this case, although the CO 2 gas generated no decrease in tap density was observed by such as the tap density of the resulting manganese oxide (Mn 2 O 3) previously No significant increase is seen in comparison with that of manganese oxide.

【0009】(3) ところが、炭酸マンガン(MnCO3
を出発原料とし、まず低酸化雰囲気(酸素濃度15%未
満の雰囲気)で熱処理すると、 MnCO3 +xO2=( Mn34 、又は Mn34 と Mn2
3 の混合物)+CO2 なる反応が生じて、多孔質のMnO2 を生成させずに低酸
化状態のマンガン酸化物を生成する。そして、これに引
き続き、雰囲気を酸化性(酸素濃度15%以上の雰囲
気)にして530℃以上の温度で熱処理すると、( Mn3
4 、又は Mn34 と Mn23 の混合物)+yO2 = M
n23なる反応が促進されて、最終的にタップ密度が非
常に高い値である1.2g/cm3以上の、更には1.8g/cm3以上
もの微細粒高密度酸化マンガン(Mn23)を得ることがで
き、これをリチウム二次電池用マンガン酸リチウムの製
造原料等とした場合には得られる製品の性能向上に大き
く資することになる。
(3) However, manganese carbonate (MnCO 3 )
Is used as a starting material and first heat-treated in a low-oxidizing atmosphere (an atmosphere with an oxygen concentration of less than 15%) to obtain MnCO 3 + xO 2 = (Mn 3 O 4 or Mn 3 O 4 and Mn 2 O
3 ) + CO 2 to produce manganese oxide in a low oxidation state without producing porous MnO 2 . Then, subsequent to this, the heat treatment atmosphere at a temperature of 530 ° C. or higher in the oxidizing (oxygen concentration of 15% or more of the atmosphere), (Mn 3
O 4 or a mixture of Mn 3 O 4 and Mn 2 O 3 ) + yO 2 = M
n 2 O 3 becomes the reaction is promoted, and finally tap density of 1.2 g / cm 3 or more is a very high value, even 1.8 g / cm 3 or more even in the fine grained high density manganese oxide (Mn 2 O 3 ) can be obtained, and when this is used as a raw material for producing lithium manganate for lithium secondary batteries, it greatly contributes to improving the performance of the obtained product.

【0010】本発明は、上記知見事項等を基にして完成
されたものであり、次に示す微細粒高密度酸化マンガン
(Mn23)と微細粒高密度酸化マンガンの製造方法とを提
供するものである。 1) メジアン径が10μm以下で、タップ密度1.8g/cm3
以上を示すことを特徴とする微細粒高密度酸化マンガ
ン。 2) 粒子形状が球状である、上記1)項記載の微細粒高密
度酸化マンガン。 3) 炭酸マンガンを酸素濃度15%未満の雰囲気中にて
400〜800℃で熱処理した後、更に酸素濃度15%
以上の雰囲気中にて530〜800℃で熱処理すること
を特徴とする、メジアン径が10μm以下であってタッ
プ密度1.2g/cm3以上を示す微細粒高密度酸化マンガンの
製造方法。 4) 炭酸マンガンを酸素濃度15%未満の雰囲気中にて
400〜800℃で熱処理した後、更に酸素濃度15%
以上の雰囲気中にて530〜800℃で熱処理すること
を特徴とする、メジアン径が10μm以下であってタッ
プ密度1.8g/cm3以上を示す微細粒高密度酸化マンガンの
製造方法。 5) 粒子形状が球状の酸化マンガンを得る、前記3)又は
4)項記載の微細粒高密度酸化マンガンの製造方法。
The present invention has been completed based on the above findings and the like.
(Mn 2 O 3 ) and a method for producing fine-grained high-density manganese oxide. 1) The median diameter is 10μm or less and the tap density is 1.8g / cm 3
A fine-grained high-density manganese oxide characterized by the above. 2) The fine-grained high-density manganese oxide according to 1) above, wherein the particle shape is spherical. 3) After heat-treating manganese carbonate at 400 to 800 ° C. in an atmosphere having an oxygen concentration of less than 15%, the oxygen concentration is further reduced to 15%.
A method for producing fine-grained high-density manganese oxide having a median diameter of 10 μm or less and a tap density of 1.2 g / cm 3 or more, characterized by performing a heat treatment at 530 to 800 ° C. in the above atmosphere. 4) After heat-treating manganese carbonate at 400 to 800 ° C. in an atmosphere having an oxygen concentration of less than 15%, the oxygen concentration is further reduced to 15%.
A method for producing fine-grained high-density manganese oxide having a median diameter of 10 μm or less and a tap density of 1.8 g / cm 3 or more, characterized by performing a heat treatment at 530 to 800 ° C. in the above atmosphere. 5) obtain manganese oxide having a spherical particle shape, 3) or
4) The method for producing fine-grained high-density manganese oxide according to the above item.

【0011】上述のように、本発明は、炭酸マンガンを
原料とし、乾式熱処理のみの簡便な方法でタップ密度が
従来例を見ない高タップ密度の微細粒酸化マンガン(Mn2
3)を実現できるようにした点に大きな特徴を有するも
のであるが、以下、本発明の実施の形態をその作用と共
に詳述する。
[0011] As described above, the present invention, manganese carbonate as a raw material, fine particle manganese oxide high tap density tap density does not see a conventional example in a simple manner only dry heat treatment (Mn 2
O 3 ) has a great feature in that it can be realized. Hereinafter, an embodiment of the present invention will be described in detail together with its operation.

【0012】まず、本発明に係る微細粒高密度酸化マン
ガンに関し、そのメジアン径を10μm以下、そしてタ
ップ密度を1.8g/cm3以上とそれぞれ限定したのは、酸化
マンガン粒子のメジアン径が10μm以下でタップ密度
が1.8g/cm3以上になると、これを例えばリチウム二次電
池用のマンガン酸リチウム(LiMnO2, LiMn24 )の製
造原料として使用した場合に電池特性(電流負荷特性,
サイクル特性等)の顕著な向上がもたらされるからであ
る。また、酸化マンガン粒子の形状が球状であるほどこ
れらの特性を得るのに有利であるが、酸化マンガン粒子
の形状を球状とするためには、その製造原料である炭酸
マンガン(MnCO3 )として球状で極力均一なものを選
んだり、これを熱処理して酸化マンガンを得る際の熱処
理温度が過度に高くならないように留意する必要があ
る。
First, regarding the fine-grained high-density manganese oxide according to the present invention, the median diameter of the manganese oxide particles is limited to 10 μm or less, and the tap density is limited to 1.8 g / cm 3 or more. When the tap density becomes 1.8 g / cm 3 or more, when this is used as a raw material for producing lithium manganate (LiMnO 2 , LiMn 2 O 4 ) for a lithium secondary battery, for example, the battery characteristics (current load characteristics,
This is because remarkable improvement in cycle characteristics and the like is provided. The more the shape of the manganese oxide particles is spherical, the more advantageous it is to obtain these characteristics. However, in order to make the shape of the manganese oxide particles spherical, the manganese oxide (MnCO 3 ), which is a raw material for producing the manganese oxide particles, is spherical. It is necessary to select a material as uniform as possible, and to keep the heat treatment temperature for obtaining manganese oxide from excessively high.

【0013】このような微細粒高密度酸化マンガンは、
炭酸マンガンを出発原料とし、これを低酸化性雰囲気中
で熱処理した後、更に酸化性雰囲気中で530℃以上程
度で熱処理することにより製造することができるが、原
料とする炭酸マンガンには特に制限はないものの、球状
で微細粒であることが特徴である前記特願平10−37
0020号として提案したものを適用するのが望まし
い。なお、この特願平10−370020号として提案
した炭酸マンガンは、二価のマンガンイオンと炭酸イオ
ンあるいは炭酸水素イオンとをアンモニア水の共存下で
反応させることによって得られるものである。
[0013] Such fine-grained high-density manganese oxide is
Manganese carbonate can be used as a starting material, heat-treated in a low oxidizing atmosphere, and then heat-treated at about 530 ° C. or more in an oxidizing atmosphere. No. 10-37, which is characterized by being spherical and fine particles.
It is desirable to apply what is proposed as 0020. The manganese carbonate proposed in Japanese Patent Application No. 10-370020 is obtained by reacting divalent manganese ions with carbonate ions or hydrogen carbonate ions in the presence of aqueous ammonia.

【0014】第1段目の熱処理で適用される低酸化雰囲
気は、雰囲気中の酸素濃度をコントロ−ルすることによ
って得られる。低酸化雰囲気中で炭酸マンガンを熱処理
すると MnCO3 +xO2 =( Mn34 、又は Mn34 と Mn2
3 の混合物) なる反応が生じて、多孔質のMnO2 が生じることなく低
酸化状態のマンガン酸化物を生成する。この低酸化状態
のマンガン酸化物は Mn23 と Mn34 の混合物(熱処
理温度が低い場合や熱処理の初期では Mn34 が主体)
であり、色調は赤紫で、SEM(Scanning Electron Mi
croscope)による表面観察では表面が溶融した状態であ
った。そして、熱処理が進むにつれて、混入している M
n34 は Mn23 へと変化する。
The low-oxidation atmosphere applied in the first heat treatment can be obtained by controlling the oxygen concentration in the atmosphere. When manganese carbonate is heat treated in a low oxidizing atmosphere, MnCO 3 + xO 2 = (Mn 3 O 4 , or Mn 3 O 4 and Mn 2 O
3 ) to produce a low-oxidation state manganese oxide without producing porous MnO 2 . This low-oxidation state manganese oxide is a mixture of Mn 2 O 3 and Mn 3 O 4 (mainly Mn 3 O 4 when the heat treatment temperature is low or at the beginning of the heat treatment).
And the color tone is magenta, and the SEM (Scanning Electron Mi
When the surface was observed with a croscope, the surface was in a molten state. Then, as the heat treatment progresses,
n 3 O 4 changes to Mn 2 O 3 .

【0015】なお、第1段目熱処理で高タップ密度の酸
化マンガンを生成させるためには、熱処理雰囲気中の酸
素濃度は15%未満(好ましくは10%以下、より望ま
しくは5%以下)とすべきである。なぜなら、熱処理雰
囲気中の酸素濃度が15%以上であると多孔性のMnO2
が生成しタップ密度が減少するからである。また、熱処
理温度は、処理時間,被処理炭酸マンガンの量,焼成炉
の性能等に依存するものの、400〜800℃が適当で
ある。なぜなら、第1段目熱処理での処理温度が400
℃未満であると効果的に低酸化状態のマンガン酸化物が
得られず、一方、800℃を超えると生成する酸化マン
ガンの凝集が著しくなって不定形粒が増加し、微細で高
タップ密度(非常に高い値である1.2g/cm3以上、 特には
1.8g/cm3以上)の酸化マンガンが得られなくなるためで
ある。
In order to generate manganese oxide having a high tap density in the first heat treatment, the oxygen concentration in the heat treatment atmosphere is set to less than 15% (preferably 10% or less, more preferably 5% or less). Should. This is because when the oxygen concentration in the heat treatment atmosphere is 15% or more, porous MnO 2
Is generated, and the tap density decreases. The temperature of the heat treatment depends on the treatment time, the amount of manganese carbonate to be treated, the performance of the sintering furnace and the like. This is because the processing temperature in the first stage heat treatment is 400
If the temperature is lower than 800 ° C., a low-oxidation manganese oxide cannot be effectively obtained. a very high value 1.2 g / cm 3 or more, particularly
This is because manganese oxide (1.8 g / cm 3 or more) cannot be obtained.

【0016】ところで、この第1段目熱処理を施すこと
によって高タップ密度の酸化マンガンが得られるが、こ
の処理を通じてタップ密度の高い酸化マンガンが得られ
る機構については、前述したように多孔性MnO2 の生成
が抑えられることもあるものの、この処理中にタップ密
度が次第に増加する事実も認められることからしてそれ
だけでは説明できない面もある。このように、第1段目
熱処理を施すことにより高タップ密度の酸化マンガンが
得られる機構は十分に解明されていないが、熱処理より
CO2 ガスを放出した後のマンガン酸化物の空孔に“溶
融した Mn23や Mn34 ”が滲み込むためにタップ密
度が向上するという現象も関わっているのではないかと
推測される。
By the way, manganese oxide having a high tap density can be obtained by performing the first-stage heat treatment. The mechanism by which manganese oxide having a high tap density can be obtained through this treatment is, as described above, porous MnO 2. May be suppressed, but the fact that the tap density gradually increases during this processing is also recognized, and there are aspects that cannot be explained by itself. As described above, although the mechanism of obtaining manganese oxide having a high tap density by performing the first-stage heat treatment has not been sufficiently elucidated, the manganese oxide vacancies after releasing the CO 2 gas from the heat treatment have “ It is speculated that the phenomenon that the tap density is improved due to the penetration of the molten Mn 2 O 3 or Mn 3 O 4 ″ may be involved.

【0017】さて、上記の第1段目熱処理を施すことに
よって高タップ密度の酸化マンガンが生成されるが、低
酸素濃度のままでは Mn23 単相になるまでに長い時間
がかかる。そのため、本発明では、タップ密度が増加し
たところで酸素濃度を15%以上(好ましくは20%以
上)にまで高め、 Mn34 が Mn23 に変換する時間の
短縮を図る。これによって、酸化マンガンの製造時間は
実用操業として十分に満足できる程度にまで短縮され
る。この第2段目熱処理での処理温度は、530〜80
0℃(好ましくは550〜750℃)とする。第2段目
熱処理において、熱処理温度が530℃未満であった
り、熱処理雰囲気中酸素濃度が15%未満であったりす
ると、混入している Mn34 が Mn23に速やかに変換
されず、処理に長時間を要したり製品性能の悪化を招く
おそれが出てくる。なお、第2段目熱処理での処理温度
が800℃を超えると、やはり得られる酸化マンガンの
凝集が著しくなって微細で高タップ密度(1.2g/cm3
上、特には1.8g/cm3以上)の製品が得られなくなる。
By performing the first-stage heat treatment, manganese oxide having a high tap density is generated, but it takes a long time to form a single phase of Mn 2 O 3 if the oxygen concentration is low. Therefore, in the present invention, when the tap density increases, the oxygen concentration is increased to 15% or more (preferably 20% or more), and the time for converting Mn 3 O 4 to Mn 2 O 3 is reduced. As a result, the production time of manganese oxide is reduced to a level that can be sufficiently satisfied as a practical operation. The processing temperature in this second stage heat treatment is 530 to 80
0 ° C (preferably 550 to 750 ° C). In the second stage heat treatment, if the heat treatment temperature is lower than 530 ° C. or the oxygen concentration in the heat treatment atmosphere is lower than 15%, the mixed Mn 3 O 4 is not quickly converted to Mn 2 O 3. In addition, there is a possibility that the processing takes a long time or the product performance is deteriorated. If the processing temperature in the second stage heat treatment exceeds 800 ° C., the obtained manganese oxide also becomes remarkably agglomerated, resulting in a fine and high tap density (1.2 g / cm 3 or more, particularly 1.8 g / cm 3 or more). ) Products cannot be obtained.

【0018】ただ、 Mn34 を Mn23 へ変換するため
の熱処理温度の切り替えは、低酸化状態の酸化マンガン
の生成時と同時であっても良く、必ずしも熱処理雰囲気
中酸素濃度を15%以上に高めた時点である必要はな
い。
However, the switching of the heat treatment temperature for converting Mn 3 O 4 to Mn 2 O 3 may be performed simultaneously with the generation of manganese oxide in a low oxidation state. It is not necessary to be at the point where the percentage was increased to more than%.

【0019】また、熱処理時間としては、やはり熱処理
温度,被処理炭酸マンガンの量,焼成炉の性能等に依存
するものの、作業性と得られる酸化マンガンの特性を考
慮すれば、第1段目熱処理では 0.5〜10時間程度、第
2段目熱処理では 0.5〜10時間程度が適当である。
The heat treatment time also depends on the heat treatment temperature, the amount of manganese carbonate to be treated, the performance of the sintering furnace, and the like. About 0.5 to 10 hours is appropriate for the second stage heat treatment.

【0020】次に、実施例及び比較例によって本発明を
更に具体的に説明する。
Next, the present invention will be described more specifically with reference to examples and comparative examples.

【実施例】〔実施例1〕まず、ステンレス鋼製反応容器
中に最大粒径10.1μm,メジアン径 4.5μm,タップ密
度1.33g/cm3 の炭酸マンガン粉末を100g装入し、続
いて該反応容器に酸素濃度が5%となるように空気と窒
素の混合ガスを500mL/minの流量で通気した。
Example 1 First, 100 g of manganese carbonate powder having a maximum particle size of 10.1 μm, a median diameter of 4.5 μm, and a tap density of 1.33 g / cm 3 was charged into a stainless steel reaction vessel. A mixed gas of air and nitrogen was passed through the container at a flow rate of 500 mL / min so that the oxygen concentration became 5%.

【0021】この状態で、装入原料(炭酸マンガン粉
末)を650℃にて1時間加熱処理した後、酸素濃度を
21%に上げ、引き続いて同温度にて更に1時間の加熱
処理を行った。
In this state, the charged material (manganese carbonate powder) was heated at 650 ° C. for 1 hour, then the oxygen concentration was increased to 21%, and subsequently, the heat treatment was further performed at the same temperature for 1 hour. .

【0022】上記処理によって黒色の化合物が得られた
が、この黒色化合物を粉末X線回折測定を行ったところ
Mn23 単相であることが確認された。また、その粒径
を微粒子分析器(Particle size analyzer)を用いて測
定したところ、原料(炭酸マンガン粉末)と同じく最大
粒径が10.1μmでメジアン径が4.5 μmであり、タップ
密度は2.12g/cm3 を示した。更に、得られた Mn23
の形状をSEMを用いて観察したところ、図1として示
したSEM写真図から確認できるように、真球に近い球
状をなしていた。
A black compound was obtained by the above treatment. The black compound was subjected to powder X-ray diffraction measurement.
It was confirmed that it was a single phase of Mn 2 O 3 . When the particle diameter was measured using a particle size analyzer, the maximum particle diameter was 10.1 μm, the median diameter was 4.5 μm, and the tap density was 2.12 g / m, similar to the raw material (manganese carbonate powder). showed cm 3. Further, when the shape of the obtained Mn 2 O 3 particles was observed using an SEM, it was found to be a spherical shape close to a true sphere as can be confirmed from the SEM photograph shown in FIG.

【0023】〔実施例2〕ステンレス鋼製反応容器に実
施例1の場合と同様の炭酸マンガン粉末(最大粒径10.1
μm,メジアン径 4.5μm,タップ密度1.33g/cm3 )を
100g装入し、続いて該反応容器に酸素濃度が10%
となるように空気と窒素の混合ガスを500mL/minの流
量で通気した。
Example 2 The same manganese carbonate powder as in Example 1 (maximum particle size 10.1) was placed in a stainless steel reaction vessel.
μm, a median diameter of 4.5 μm, and a tap density of 1.33 g / cm 3 ).
Then, a mixed gas of air and nitrogen was passed at a flow rate of 500 mL / min.

【0024】この状態で、装入原料(炭酸マンガン粉
末)を650℃にて1時間加熱処理した後、酸素濃度を
21%に上げ、引き続いて同温度にて更に1時間の加熱
処理を行った。
In this state, the charged material (manganese carbonate powder) was heated at 650 ° C. for 1 hour, then the oxygen concentration was increased to 21%, and subsequently, the heat treatment was further performed at the same temperature for 1 hour. .

【0025】上記処理によって黒色の化合物が得られた
が、この黒色化合物を粉末X線回折測定を行ったところ
Mn23 単相であることが確認された。また、その粒径
を微粒子分析器を用いて測定したところ、原料と同じく
最大粒径が10.1μmメジアン径が 4.5μmであり、タッ
プ密度は2.06g/cm3 を示した。更に、得られた Mn23
粒の形状をSEMを用いて観察したところ、真球に近い
球状をなしていた。
A black compound was obtained by the above treatment. The black compound was subjected to powder X-ray diffraction measurement.
It was confirmed that it was a single phase of Mn 2 O 3 . When the particle size was measured using a fine particle analyzer, the maximum particle size was 10.1 μm, the median diameter was 4.5 μm, and the tap density was 2.06 g / cm 3 , as in the case of the raw materials. Further, the obtained Mn 2 O 3
Observation of the shape of the grains using a SEM revealed that the grains had a spherical shape close to a true sphere.

【0026】〔比較例1〕ステンレス鋼製反応容器中
に、最大粒径10.1μm,メジアン径 4.5μm,タップ密
度1.15g/cm3 の炭酸マンガン粉末を100g装入し、続
いて該反応容器に酸素濃度が21%となるように空気と
窒素の混合ガスを500mL/minの流量で通気した。そし
て、この状態で、装入原料(炭酸マンガン粉末)を65
0℃にて2時間加熱処理した。
Comparative Example 1 100 g of manganese carbonate powder having a maximum particle size of 10.1 μm, a median diameter of 4.5 μm, and a tap density of 1.15 g / cm 3 was charged into a stainless steel reaction vessel. A mixed gas of air and nitrogen was passed at a flow rate of 500 mL / min so that the oxygen concentration became 21%. Then, in this state, the charged material (manganese carbonate powder)
Heat treatment was performed at 0 ° C. for 2 hours.

【0027】このようにして得られた黒色の化合物を粉
末X線回折測定したところ Mn23単相であった。そし
て、得られた黒色化合物( Mn23 )の粒径を微粒子分
析器を用いて測定したところ、原料と同じ最大粒径10.1
μm、メジアン径 4.5μmであったが、タップ密度は1.
19g/cm3 であった。
When the black compound thus obtained was subjected to powder X-ray diffraction measurement, it was found to be a single phase of Mn 2 O 3 . Then, the particle size of the obtained black compound (Mn 2 O 3 ) was measured using a fine particle analyzer.
μm and median diameter 4.5 μm, but the tap density was 1.
It was 19 g / cm 3 .

【0028】〔比較例2〕ステンレス鋼製反応容器中
に、最大粒径10.1μm,メジアン径 4.5μm,タップ密
度1.15g/cm3 の炭酸マンガン粉末を100g装入し、続
いて該反応容器に純酸素を500mL/minの流量で通気し
た。そして、この状態で、装入原料(炭酸マンガン粉
末)を650℃にて2時間加熱処理した。
Comparative Example 2 100 g of manganese carbonate powder having a maximum particle size of 10.1 μm, a median diameter of 4.5 μm, and a tap density of 1.15 g / cm 3 was charged into a stainless steel reaction vessel. Pure oxygen was bubbled in at a flow rate of 500 mL / min. Then, in this state, the charged raw material (manganese carbonate powder) was heated at 650 ° C. for 2 hours.

【0029】このようにして得られた黒色の化合物を粉
末X線回折測定したところ Mn23単相であった。そし
て、得られた黒色化合物( Mn23 )の粒径を微粒子分
析器を用いて測定したところ、原料と同じ最大粒径10.1
μm、メジアン径 4.5μmであったが、タップ密度は1.
10g/cm3 であった。
The black compound thus obtained was subjected to powder X-ray diffraction measurement and found to be a single phase of Mn 2 O 3 . Then, the particle size of the obtained black compound (Mn 2 O 3 ) was measured using a fine particle analyzer.
μm and median diameter 4.5 μm, but the tap density was 1.
It was 10 g / cm 3 .

【0030】[0030]

【効果の総括】以上に説明した如く、この発明によれ
ば、小粒径であってもタップ密度の高い酸化マンガンを
安定して提供することが可能となり、これを原料とする
ことで例えば十分に満足できる電池特性を有したリチウ
ム二次電池用マンガン酸リチウムを製造できるなど、産
業上極めて有用な効果がもたらされる。
As described above, according to the present invention, it is possible to stably provide manganese oxide having a high tap density even with a small particle size. Industrially extremely useful effects can be obtained, such as production of lithium manganate for lithium secondary batteries having satisfactory battery characteristics.

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

【図1】実施例で得られた微細粒酸化マンガンのSEM
写真図である。
FIG. 1 SEM of fine-grained manganese oxide obtained in Example
FIG.

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4G048 AA02 AB01 AB05 AC06 AD03 AD04 AE05 5H003 AA02 AA08 BA01 BB04 BB05 BC01 BD01 BD02 BD05 BD06 5H014 AA01 BB01 EE10 HH06 HH08 5H029 AJ03 AJ14 AK02 AK03 CJ02 CJ28 DJ16 HJ05 HJ08 HJ14 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G048 AA02 AB01 AB05 AC06 AD03 AD04 AE05 5H003 AA02 AA08 BA01 BB04 BB05 BC01 BD01 BD02 BD05 BD06 5H014 AA01 BB01 EE10 HH06 HH08 5H029 AJ03 AJ14 AK02 H05H08

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】 メジアン径が10μm以下で、タップ密
度1.8g/cm3以上を示すことを特徴とする微細粒高密度酸
化マンガン。
1. A fine-grained high-density manganese oxide having a median diameter of 10 μm or less and a tap density of 1.8 g / cm 3 or more.
【請求項2】 粒子形状が球状である、請求項1記載の
微細粒高密度酸化マンガン。
2. The fine-grained high-density manganese oxide according to claim 1, wherein the particle shape is spherical.
【請求項3】 炭酸マンガンを酸素濃度15%未満の雰
囲気中にて400〜800℃で熱処理した後、更に酸素
濃度15%以上の雰囲気中にて530〜800℃で熱処
理することを特徴とする、メジアン径が10μm以下で
あってタップ密度1.2g/cm3以上を示す微細粒高密度酸化
マンガンの製造方法。
3. A heat treatment of manganese carbonate at 400 to 800 ° C. in an atmosphere having an oxygen concentration of less than 15%, and a heat treatment at 530 to 800 ° C. in an atmosphere having an oxygen concentration of 15% or more. And a method for producing fine-particle high-density manganese oxide having a median diameter of 10 μm or less and a tap density of 1.2 g / cm 3 or more.
【請求項4】 炭酸マンガンを酸素濃度15%未満の雰
囲気中にて400〜800℃で熱処理した後、更に酸素
濃度15%以上の雰囲気中にて530〜800℃で熱処
理することを特徴とする、メジアン径が10μm以下で
あってタップ密度1.8g/cm3以上を示す微細粒高密度酸化
マンガンの製造方法。
4. A heat treatment of manganese carbonate at 400 to 800 ° C. in an atmosphere having an oxygen concentration of less than 15%, and a heat treatment at 530 to 800 ° C. in an atmosphere having an oxygen concentration of 15% or more. And a method for producing fine-grained high-density manganese oxide having a median diameter of 10 μm or less and a tap density of 1.8 g / cm 3 or more.
【請求項5】 粒子形状が球状の酸化マンガンを得る、
請求項3又は4記載の微細粒高密度酸化マンガンの製造
方法。
5. A manganese oxide having a spherical particle shape is obtained.
The method for producing a fine-grained high-density manganese oxide according to claim 3.
JP08510699A 1999-03-29 1999-03-29 Fine-grained dimanganese trioxide for lithium secondary batteries and method for producing the same Expired - Lifetime JP3495638B2 (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003084874A1 (en) * 2002-04-08 2003-10-16 Nikko Materials Co., Ltd. Manganese oxide producing method
JP2008066028A (en) * 2006-09-05 2008-03-21 Nippon Chem Ind Co Ltd Lithium manganate for lithium secondary battery positive electrode secondary active material, and manufacturing method of lithium manganate, lithium secondary battery positive electrode active material, and lithium secondary battery
WO2012046735A1 (en) 2010-10-06 2012-04-12 東ソー株式会社 Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same
KR101543928B1 (en) 2013-12-26 2015-08-12 주식회사 포스코 Method for preparing manganese oxide from manganese dust
KR101545719B1 (en) * 2013-12-26 2015-08-20 주식회사 포스코 Method of preparing manganese oxide with high purity

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003084874A1 (en) * 2002-04-08 2003-10-16 Nikko Materials Co., Ltd. Manganese oxide producing method
CN100453468C (en) * 2002-04-08 2009-01-21 日矿马铁利亚股份有限公司 Manganese oxide producing method
JP2008066028A (en) * 2006-09-05 2008-03-21 Nippon Chem Ind Co Ltd Lithium manganate for lithium secondary battery positive electrode secondary active material, and manufacturing method of lithium manganate, lithium secondary battery positive electrode active material, and lithium secondary battery
WO2012046735A1 (en) 2010-10-06 2012-04-12 東ソー株式会社 Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same
US9150427B2 (en) 2010-10-06 2015-10-06 Tosoh Corporation Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same
KR101543928B1 (en) 2013-12-26 2015-08-12 주식회사 포스코 Method for preparing manganese oxide from manganese dust
KR101545719B1 (en) * 2013-12-26 2015-08-20 주식회사 포스코 Method of preparing manganese oxide with high purity

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