JPH10182161A - Production of lithium-manganese double oxide - Google Patents
Production of lithium-manganese double oxideInfo
- Publication number
- JPH10182161A JPH10182161A JP8343162A JP34316296A JPH10182161A JP H10182161 A JPH10182161 A JP H10182161A JP 8343162 A JP8343162 A JP 8343162A JP 34316296 A JP34316296 A JP 34316296A JP H10182161 A JPH10182161 A JP H10182161A
- Authority
- JP
- Japan
- Prior art keywords
- composite oxide
- lithium
- lithium manganese
- manganese composite
- producing
- 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
-
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えばリチウム二
次電池の正極活物質として有用な、リチウムマンガン複
合酸化物の製造方法に関する。The present invention relates to a method for producing a lithium manganese composite oxide useful as, for example, a positive electrode active material of a lithium secondary battery.
【０００２】[0002]
【従来の技術】従来、リチウム二次電池の正極活物質と
して用いられるスピネル型リチウムマンガン複合酸化物
の製造方法としては、次のような種々の方法が提案され
ている。2. Description of the Related Art Conventionally, the following various methods have been proposed for producing a spinel-type lithium manganese composite oxide used as a positive electrode active material of a lithium secondary battery.
【０００３】（ａ）炭酸リチウムと二酸化マンガンのよ
うな粉末同士を混合し、８００℃程度で焼成する、固相
法による方法。(A) A solid phase method in which powders such as lithium carbonate and manganese dioxide are mixed and fired at about 800 ° C.
【０００４】（ｂ）低融点の硝酸リチウムや水酸化リチ
ウムを多孔質の二酸化マンガンに染み込ませて焼成す
る、溶融含浸法による方法。(B) A method using a melt impregnation method in which low melting point lithium nitrate or lithium hydroxide is impregnated into porous manganese dioxide and fired.
【０００５】（ｃ）硝酸リチウムと硝酸マンガンを水に
溶解させ、超音波で霧状に噴霧し熱分解させる、噴霧熱
分解法による方法。(C) A spray pyrolysis method in which lithium nitrate and manganese nitrate are dissolved in water, sprayed in a mist with ultrasonic waves, and thermally decomposed.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
製造方法それぞれにおいて、以下に示すような問題点を
有していた。However, each of the above-described manufacturing methods has the following problems.
【０００７】（ａ）の固相法においては、出発原料とし
て炭酸塩や酸化物などの粉末を使用するため、比較的高
温で焼成する必要がある。このため、酸素過剰のスピネ
ルなどの欠陥スピネルが合成されやすい。又、各々の粉
末を分子レベルで均一に混合することは不可能であり、
例えば目的とするＬｉＭｎ2 Ｏ4 以外にＬｉ2 ＭｎＯ3
やＬｉＭｎＯ2 の生成を伴うことがあり、これらを防ぐ
ために酸素濃度を調整しながら長時間の焼成を数度繰り
返す必要があった。In the solid phase method (a), since powders such as carbonates and oxides are used as starting materials, firing at a relatively high temperature is required. Therefore, a defective spinel such as an oxygen-excess spinel is easily synthesized. Also, it is impossible to mix each powder uniformly at the molecular level,
For example, in addition to the desired LiMn 2 O 4 , Li 2 MnO 3
And LiMnO 2 may be generated, and it is necessary to repeat firing for a long time several times while adjusting the oxygen concentration in order to prevent these.
【０００８】（ｂ）の溶融浸漬法においては、固相法の
場合と比較して、ＬｉとＭｎの均一分散性が向上する。In the melt immersion method (b), the uniform dispersibility of Li and Mn is improved as compared with the case of the solid phase method.
【０００９】しかしながら、出発原料として多孔質のマ
ンガン原料を必要とする。ところが、この多孔質のマン
ガン原料を得るためには粉砕処理が必要であり、この処
理を施すために特別に準備した粉砕装置を必要とし、粉
砕過程での粉砕処理媒体や装置内壁の磨耗などにより不
純物が混入し、得られる正極活物質としての複合酸化物
粉末の品質が低下したり、コストアップにつながるとい
う問題点を有していた。又、低融点のリチウム原料の蒸
発を抑えるため低温で長時間焼成しないと、得られる複
合酸化物の結晶性が悪くなる。このため、二次電池の活
物質として用いた場合、電池の充放電サイクルを繰り返
すうちに、結晶構造が崩れ二次電池の容量が低下すると
いう問題点を有していた。さらに、二次電池のハイレー
ト放電や充放電サイクル特性を改善するために、Ｍｎに
近いイオン半径を持つＦｅ、Ｃｏ、Ｎｉ、Ｍｇといった
低価数カチオンでＭｎを置換する場合は、この溶融含浸
法においても、Ｍｎと置換カチオンの分布が不均一なも
のとならざるを得なかった。However, a porous manganese raw material is required as a starting material. However, in order to obtain this porous manganese raw material, a crushing process is required, and a specially prepared crushing device is required to perform this process. There has been a problem that impurities are mixed and the quality of the obtained composite oxide powder as a positive electrode active material is deteriorated or leads to an increase in cost. Further, unless the material is calcined at a low temperature for a long time in order to suppress the evaporation of the low melting point lithium raw material, the crystallinity of the obtained composite oxide deteriorates. For this reason, when used as an active material of a secondary battery, there has been a problem that the crystal structure is broken and the capacity of the secondary battery is reduced during repeated charge / discharge cycles of the battery. Further, when replacing Mn with a low-valent cation such as Fe, Co, Ni, or Mg having an ionic radius close to Mn in order to improve the high-rate discharge and charge / discharge cycle characteristics of the secondary battery, the melt impregnation method is used. Also, the distribution of Mn and the substituted cation had to be non-uniform.
【００１０】（ｃ）の噴霧熱分解法においては、スピネ
ル型リチウムマンガン複合酸化物を構成する元素をイオ
ンレベルで均一に混合できるため、溶融含浸法と比較し
ても、格段に均一性を増すことができる。又、原料の粉
砕工程を必要としないため、粉砕工程に起因する不純物
の混入を防止できるという利点を有している。In the spray pyrolysis method (c), the elements constituting the spinel-type lithium manganese composite oxide can be uniformly mixed at the ionic level, so that the uniformity is remarkably increased as compared with the melt impregnation method. be able to. Further, since there is no need for a raw material pulverizing step, there is an advantage that contamination of impurities due to the pulverizing step can be prevented.
【００１１】しかしながら、噴霧熱分解法では、脱水、
乾燥及び熱分解の一連の操作が数秒以内の短時間のうち
に行われるため、従来の焼成処理に比べて熱履歴が極め
て短く、合成した複合酸化物の結晶性が悪くなる傾向を
示す。このため、二次電池の活物質として用いた場合、
電池の充放電サイクルを繰り返すうちに、結晶構造が崩
れ二次電池の容量が低下するという問題点を有してい
た。又、合成した複合酸化物の比表面積が数十ｍ2 ／ｇ
と非常に大きいため、この複合酸化物と接触する電解液
が分解して、二次電池の充放電サイクル特性や保存特性
を著しく低下させる場合があるという問題点を有してい
た。However, in the spray pyrolysis method, dehydration,
Since a series of operations of drying and thermal decomposition are performed within a short time within several seconds, the heat history is extremely short as compared with the conventional calcination treatment, and the synthesized composite oxide tends to have poor crystallinity. Therefore, when used as an active material of a secondary battery,
As the charge / discharge cycle of the battery is repeated, the crystal structure is broken and the capacity of the secondary battery is reduced. The specific surface area of the synthesized composite oxide is several tens m 2 / g.
Therefore, there is a problem that the electrolytic solution in contact with the composite oxide is decomposed and the charge / discharge cycle characteristics and storage characteristics of the secondary battery may be significantly reduced.
【００１２】そこで、本発明の目的は、上記問題点を解
決し、リチウム二次電池の正極活物質として用いたとき
に、充放電容量が大きくかつ充放電サイクル特性に優れ
た特性を得ることができるリチウムマンガン複合酸化物
の製造方法を提供することにある。Accordingly, an object of the present invention is to solve the above-mentioned problems and to obtain characteristics having a large charge / discharge capacity and excellent charge / discharge cycle characteristics when used as a positive electrode active material of a lithium secondary battery. An object of the present invention is to provide a method for producing a lithium manganese composite oxide that can be produced.
【００１３】[0013]
【課題を解決するための手段】上記目的を達成するた
め、本発明のリチウムマンガン複合酸化物の製造方法
は、リチウムマンガン複合酸化物を構成する金属元素を
含みかつオキシポリカルボン酸又は水に可溶な化合物
と、ポリオールと、オキシポリカルボン酸とを反応させ
て水溶性の複合カルボン酸エステル錯体オリゴマーを生
成させた後、該生成物を熱分解しその後アニールするこ
とを特徴とする。In order to achieve the above object, a method for producing a lithium manganese composite oxide according to the present invention comprises a metal element constituting the lithium manganese composite oxide, and the manganese composite oxide is soluble in oxypolycarboxylic acid or water. After reacting a soluble compound, a polyol and an oxypolycarboxylic acid to form a water-soluble complex carboxylate complex oligomer, the product is thermally decomposed and then annealed.
【００１４】又、前記熱分解の方法は、前記複合カルボ
ン酸エステル錯体オリゴマーが生成した反応液を５００
〜９００℃の雰囲気中に噴霧する方法であることを特徴
とする。Further, the method of the thermal decomposition is characterized in that the reaction solution in which the complex carboxylic acid ester complex oligomer is formed
It is a method of spraying in an atmosphere of up to 900 ° C.
【００１５】又、前記熱分解の方法は、前記複合カルボ
ン酸エステル錯体オリゴマーが生成した反応液を固液分
離し、その固形分を５００〜９００℃で熱処理する方法
であることを特徴とする。The thermal decomposition method is characterized in that the reaction solution in which the complex carboxylic acid ester complex oligomer has been formed is subjected to solid-liquid separation, and the solid content is heat-treated at 500 to 900 ° C.
【００１６】又、前記アニールの温度は６００〜８５０
℃であることを特徴とする。Further, the annealing temperature is 600 to 850.
° C.
【００１７】さらに、前記リチウムマンガン複合酸化物
は、一般式：ＬｉＭy Ｍｎ2-y Ｏ4 (但し、ＭはＣｒ，Ｎ
ｉ，Ｆｅ，Ｃｏ，Ｍｇ，Ｌｉからなる群から選ばれた少
なくとも１種であり、０≦ｙ≦０．４である）で表され
ることを特徴とする。Further, the lithium manganese composite oxide has a general formula: LiM y Mn 2-y O 4 ( where M is Cr, N
at least one selected from the group consisting of i, Fe, Co, Mg, and Li, where 0 ≦ y ≦ 0.4).
【００１８】ここで、出発原料として用いるリチウムマ
ンガン複合酸化物を構成する金属元素を含む化合物とし
ては、水又はオキシポリカルボン酸に可溶であれば、任
意のものを使用できる。代表的な水溶性化合物としては
酢酸塩、ギ酸塩、塩化物、硝酸塩などが挙げられる。
又、オキシポリカルボン酸に可溶である代表的な化合物
としては、炭酸塩が挙げられる。これら酢酸塩、ギ酸
塩、塩化物、硝酸塩及び炭酸塩は、アルコキシドなどの
分子中の水素イオンを金属イオンで置換した有機化合物
と比べて極めて安価であり、原料コストを低く抑えるこ
とができるので工業的に極めて有利である。又、これら
化合物の酢酸根、ギ酸根、塩素、硝酸根及び炭酸根は、
熱分解処理時にガスとなって飛散し粉体中に残留するこ
とがないので、不純物を含まない高純度のリチウムマン
ガン複合酸化物が得られる。Here, as the compound containing the metal element constituting the lithium manganese composite oxide used as a starting material, any compound can be used as long as it is soluble in water or oxypolycarboxylic acid. Representative water-soluble compounds include acetate, formate, chloride, nitrate and the like.
Typical compounds soluble in oxypolycarboxylic acid include carbonates. These acetates, formates, chlorides, nitrates and carbonates are extremely inexpensive as compared to organic compounds in which hydrogen ions in molecules such as alkoxides are replaced by metal ions, and the cost of raw materials can be kept low. This is extremely advantageous in terms of efficiency. In addition, acetate, formate, chlorine, nitrate and carbonate of these compounds,
A high purity lithium manganese composite oxide containing no impurities can be obtained because it does not become a gas at the time of the thermal decomposition treatment and scatter and remains in the powder.
【００１９】又、ポリオールとしては、エチレングリコ
ール、プロピレングリコール、ジエチテングリコール、
ジプロピレングリコール、ポリエチレングリコール、ポ
リプロピレングリコール、トリグリコール、テトラエチ
レングリコール、ブタンジオール−１，４−ヘキシレン
グリコール、オクチレングリコールなどのグリコールの
他、グリセリンなどの三価アルコール、四価、五価アル
コールなどの多価アルコールを適宜用いることができ
る。As the polyol, ethylene glycol, propylene glycol, diethylene glycol,
In addition to glycols such as dipropylene glycol, polyethylene glycol, polypropylene glycol, triglycol, tetraethylene glycol, butanediol-1,4-hexylene glycol and octylene glycol, trihydric alcohols such as glycerin, tetrahydric and pentahydric alcohols Such polyhydric alcohols can be used as appropriate.
【００２０】又、オキシポリカルボン酸の代表的なもの
としてはクエン酸が挙げられるが、他に林檎酸、メソ酒
石酸、葡萄酸、メコン酸などを適宜用いることができ
る。A typical example of the oxypolycarboxylic acid is citric acid. In addition, malic acid, meso-tartaric acid, grape acid, meconic acid and the like can be used as appropriate.
【００２１】ところで、リチウムマンガン複合酸化物を
構成する金属元素を含みかつオキシポリカルボン酸又は
水に可溶な化合物と、ポリオールと、オキシポリカルボ
ン酸とを反応させると、水溶性の複合カルボン酸エステ
ル錯体オリゴマーが生成し、リチウムマンガン複合酸化
物を構成する金属元素がイオンレベルでオリゴマー分子
中に均一に分散した状態となる。このオリゴマー溶液を
所定温度に維持した雰囲気中、例えば加熱筒内に霧状に
吹き込むと、瞬間的にオリゴマーが熱分解される。即
ち、従来の仮焼処理に比べて熱履歴が極めて短く、しか
も熱処理温度が低いため、凝集の全くない微細な球状の
リチウムマンガン複合酸化物が生成される。したがっ
て、従来法のように粉砕工程を必要とせず、粉砕工程に
起因する不純物の混入を排除できる。又、洗浄工程を必
要とせず、複合酸化物構成元素の洗浄による損失即ち組
成ずれを防止できる。By the way, when a compound containing a metal element constituting a lithium manganese composite oxide and containing a metal element and being soluble in oxypolycarboxylic acid or water, a polyol and oxypolycarboxylic acid are reacted, a water-soluble composite carboxylic acid is obtained. An ester complex oligomer is generated, and the metal elements constituting the lithium manganese composite oxide are uniformly dispersed in the oligomer molecule at the ion level. When this oligomer solution is blown into an atmosphere maintained at a predetermined temperature, for example, into a heating cylinder, the oligomer is instantaneously thermally decomposed. That is, since the heat history is extremely short and the heat treatment temperature is low as compared with the conventional calcination treatment, a fine spherical lithium manganese composite oxide having no aggregation is generated. Therefore, unlike the conventional method, a pulverizing step is not required, and contamination of impurities caused by the pulverizing step can be eliminated. Further, a cleaning step is not required, and loss due to cleaning of the composite oxide constituent elements, that is, composition deviation can be prevented.
【００２２】又、熱分解により得られた微細な複合酸化
物粉末をアニールすることにより、複合酸化物の比表面
積を小さくすることができる。The specific surface area of the composite oxide can be reduced by annealing the fine composite oxide powder obtained by thermal decomposition.
【００２３】[0023]
【発明の実施の形態】以下、本発明のリチウムマンガン
複合酸化物の製造方法の実施の形態について、ＬｉＭｎ
2 Ｏ4 の場合を例として、実施例に基づき説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of a method for producing a lithium manganese composite oxide according to the present invention will be described with reference to LiMn.
The case of 2 O 4 will be described by way of example.
【００２４】（実施例）まず、リチウム化合物として炭
酸リチウムと、マンガン化合物として硝酸マンガンを用
意した。次に、Ｌｉ：Ｍｎのモル比が１：２になるよう
に、炭酸リチウム０．２５モルと硝酸マンガン１モルを
それぞれ正確に秤量分取して反応容器に入れ、これに
１．６モルのクエン酸とクエン酸に対して０．７倍モル
のエチレングリコールを加えた後、さらに純水を加えて
全量を８００ｍｌとした。(Example) First, lithium carbonate was prepared as a lithium compound, and manganese nitrate was prepared as a manganese compound. Next, 0.25 mol of lithium carbonate and 1 mol of manganese nitrate were each accurately weighed and weighed and placed in a reaction vessel so that the molar ratio of Li: Mn was 1: 2. After adding citric acid and ethylene glycol in a molar amount 0.7 times the amount of citric acid, pure water was further added to bring the total amount to 800 ml.
【００２５】その後、反応容器を１１０℃に維持したオ
イルバスにセットし、攪拌しながら２時間反応を行なわ
せて水溶性の複合カルボン酸エステルオリゴマーを生成
させた。反応終了後、反応容器をオイルバスより取り出
して室温まで冷却し、次いで、反応容器に純水を加えて
希釈して全量を１０００ｍｌとした。Thereafter, the reaction vessel was set in an oil bath maintained at 110 ° C., and the reaction was carried out for 2 hours with stirring to produce a water-soluble complex carboxylic acid ester oligomer. After the completion of the reaction, the reaction vessel was taken out of the oil bath and cooled to room temperature. Then, the reaction vessel was diluted with pure water to make the total volume 1000 ml.
【００２６】次に、このオリゴマー溶液を４００〜９０
０℃間の所定温度に調整した縦型熱分解炉中へ１２００
ｍｌ／時間の速度で霧状に吹き込んで熱分解させて複合
酸化物を得た。その後、得られた複合酸化物を５００〜
９００℃間の所定の温度で２時間アニールして、表１の
試料番号１〜８に示すリチウムマンガン複合酸化物の粉
末を得た。Next, this oligomer solution is mixed with
1200 into a vertical pyrolysis furnace adjusted to a predetermined temperature between 0 ° C
A composite oxide was obtained by blowing in a mist at a rate of ml / hour and thermally decomposing. Then, the obtained composite oxide was 500 to
Annealing was performed at a predetermined temperature of 900 ° C. for 2 hours to obtain lithium manganese composite oxide powders shown in Sample Nos. 1 to 8 in Table 1.
【００２７】次に、以上得られた複合酸化物の粉末につ
いて、走査型電子顕微鏡（ＳＥＭ）写真を撮り、それよ
り粒径を求めた。又、窒素吸着法により比表面積を求め
た。さらに、Ｘ線回折（ＸＲＤ）分析法により、複合酸
化物の同定を行なった。結果を表１に示す。なお表１中
のＬＭはＬｉＭｎ2 Ｏ4 を表し、ＭＯはＭｎ2 Ｏ3 を表
す。Next, a scanning electron microscope (SEM) photograph was taken of the composite oxide powder obtained above, and the particle size was determined therefrom. The specific surface area was determined by a nitrogen adsorption method. Further, the composite oxide was identified by X-ray diffraction (XRD) analysis. Table 1 shows the results. In Table 1, LM represents LiMn 2 O 4 and MO represents Mn 2 O 3 .
【００２８】又、得られたＬｉＭｎ2 Ｏ4 粉体を正極活
物質としたボタン型のリチウム二次電池を作製し、充放
電試験を行ないその放電容量を求めた。なお、リチウム
二次電池の正極には、ＬｉＭｎ2 Ｏ4 粉体に導電剤とし
てのアセチレンブラックと結着剤としてのポリテトラフ
ルオロエチレンを加えてシート状に成形した後、ＳＵＳ
メッシュに圧着したものを用いた。負極には金属リチウ
ムを用いた。正極と負極間のスペーサにはポリプロピレ
ン製多孔フィルムを用い、プロピレンカーボネートと
１，１−ジメトキシエタンの混合溶媒に過塩素酸リチウ
ムを溶解させたものを電解液として含浸させた。又、充
放電は４．３〜３．０Ｖ間の電位で０．５ｍＡ／ｃｍ2
の定電流で行なった。これらの結果を表２に示す。Further, a button-type lithium secondary battery using the obtained LiMn 2 O 4 powder as a positive electrode active material was prepared, and a charge / discharge test was performed to determine a discharge capacity thereof. The positive electrode of the lithium secondary battery was formed into a sheet by adding LiMn 2 O 4 powder to acetylene black as a conductive agent and polytetrafluoroethylene as a binder, and then forming a sheet of SUS.
What was crimped to the mesh was used. Metallic lithium was used for the negative electrode. A porous film made of polypropylene was used as a spacer between the positive electrode and the negative electrode, and a solution in which lithium perchlorate was dissolved in a mixed solvent of propylene carbonate and 1,1-dimethoxyethane was impregnated as an electrolytic solution. The charge and discharge were performed at a potential of 4.3 to 3.0 V at 0.5 mA / cm 2.
At a constant current. Table 2 shows the results.
【００２９】（比較例１）まず、リチウムマンガン複合
酸化物を構成する金属元素の化合物として、硝酸リチウ
ムと電解二酸化マンガンを用意した。次に、Ｌｉ：Ｍｎ
のモル比が１：２になるように、硝酸リチウムと電解二
酸化マンガンをそれぞれ正確に秤量分取して容器に入
れ、溶媒にアルコール、玉石にＰＳＺを用いて３０時間
ボールミル粉砕を行った後、エバポレータで溶媒を除去
し、原料粉末を得た。その後、この粉末をアルミナ製の
匣に入れ、６００℃で４８時間焼成して、リチウムを電
解二酸化マンガン内に溶融含浸させることにより複合酸
化物を得た。(Comparative Example 1) First, lithium nitrate and electrolytic manganese dioxide were prepared as compounds of metal elements constituting the lithium manganese composite oxide. Next, Li: Mn
Lithium nitrate and electrolytic manganese dioxide were each accurately weighed and weighed and placed in a container so that the molar ratio of the mixture was 1: 2, and after ball milling for 30 hours using alcohol as a solvent and PSZ as a cobblestone, The solvent was removed with an evaporator to obtain a raw material powder. Thereafter, this powder was placed in a box made of alumina, baked at 600 ° C. for 48 hours, and lithium was melt-impregnated in electrolytic manganese dioxide to obtain a composite oxide.
【００３０】次に、以上得られた複合酸化物の粉末につ
いて、実施例と同様にして、粒径及び比表面積を求める
とともに複合酸化物の同定を行なった。結果を表１に示
す。次に、実施例と同様にして、二次電池を作製し、充
放電試験を行なった。結果を表２に示す。Next, the particle diameter and specific surface area of the obtained composite oxide powder were determined and the composite oxide was identified in the same manner as in the examples. Table 1 shows the results. Next, a secondary battery was fabricated and a charge / discharge test was performed in the same manner as in the example. Table 2 shows the results.
【００３１】（比較例２）まず、リチウムマンガン複合
酸化物を構成する金属元素の化合物として、炭酸リチウ
ムと炭酸マンガンを用意した。次に、Ｌｉ：Ｍｎのモル
比が１：２になるように、炭酸リチウムと炭酸マンガン
をそれぞれ正確に秤量分取して容器に入れ、溶媒にアル
コール、玉石にＰＳＺを用いて３０時間ボールミル粉砕
を行った後、エバポレータで溶媒を除去し、原料粉末を
得た。その後、この粉末をアルミナ製の匣に入れ、９０
０℃で４８時間焼成して複合酸化物を得た。(Comparative Example 2) First, lithium carbonate and manganese carbonate were prepared as compounds of metal elements constituting the lithium manganese composite oxide. Next, lithium carbonate and manganese carbonate were each accurately weighed and dispensed so that the molar ratio of Li: Mn was 1: 2, put in a container, and ball milled for 30 hours using alcohol as a solvent and PSZ as a cobblestone. After that, the solvent was removed with an evaporator to obtain a raw material powder. Then, put this powder in an alumina box,
The mixture was fired at 0 ° C. for 48 hours to obtain a composite oxide.
【００３２】次に、以上得られた複合酸化物の粉末につ
いて、実施例と同様にして、粒径及び比表面積を求める
とともに複合酸化物の同定を行なった。結果を表１に示
す。次に、実施例と同様にして、二次電池を作製し、充
放電試験を行なった。結果を表２に示す。Next, the particle diameter and specific surface area of the obtained composite oxide powder were determined in the same manner as in the examples, and the composite oxide was identified. Table 1 shows the results. Next, a secondary battery was fabricated and a charge / discharge test was performed in the same manner as in the example. Table 2 shows the results.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【表２】 [Table 2]
【００３５】表１及び表２の結果から明らかなように、
本発明の方法により得られたＬｉＭｎ2 Ｏ4 を正極活物
質とすることにより、初期容量及び充放電サイクル特性
に優れたリチウム二次電池が得られる。As is clear from the results in Tables 1 and 2,
By using LiMn 2 O 4 obtained by the method of the present invention as a positive electrode active material, a lithium secondary battery having excellent initial capacity and charge / discharge cycle characteristics can be obtained.
【００３６】なお、熱分解の具体的な温度範囲として
は、５００〜９００℃が好ましい。即ち、この温度範囲
において、ＬｉＭｎ2 Ｏ4 の単相が得られる。上限は、
生成したＬｉＭｎ2 Ｏ4 が熱により再度分解しない温度
以下に限定される。The specific temperature range of the thermal decomposition is preferably from 500 to 900.degree. That is, in this temperature range, a single phase of LiMn 2 O 4 is obtained. The upper limit is
The temperature is limited to a temperature at which the generated LiMn 2 O 4 is not decomposed again by heat.
【００３７】又、アニールの具体的な温度範囲として
は、６００〜８５０℃が好ましい。この温度内におい
て、リチウム二次電池の正極活物質として適した粒径に
成長したリチウムマンガン複合酸化物が得られる。The specific temperature range of the annealing is preferably from 600 to 850 ° C. At this temperature, a lithium manganese composite oxide grown to a particle size suitable as a positive electrode active material of a lithium secondary battery is obtained.
【００３８】なお、上記実施例においては、リチウムマ
ンガン複合酸化物がＬｉＭｎ2 Ｏ4の場合について説明
したが、本発明はこれに限定されるものではない。一般
式ＬｉＭy Ｍｎ2-y Ｏ4 （但し、ＭはＣｒ，Ｎｉ，Ｆ
ｅ，Ｃｏ，Ｍｇ，Ｌｉからなる群から選ばれた少なくと
も１種であり、０≦ｙ≦０．４である）で表されるリチ
ウムマンガン複合酸化物全般について、同様の効果を得
ることができる。In the above embodiment, the case where the lithium manganese composite oxide is LiMn 2 O 4 has been described, but the present invention is not limited to this. General formula LiM y Mn 2-y O 4 (where M is Cr, Ni, F
and at least one selected from the group consisting of e, Co, Mg, and Li, where 0 ≦ y ≦ 0.4). .
【００３９】[0039]
【発明の効果】以上の説明から明らかなように、本発明
の製造方法によれば、ミクロ的に組成が均一でありしか
も不純物の混入を抑えたリチウムマンガン複合酸化物の
粉末を得ることができる。As is apparent from the above description, according to the production method of the present invention, it is possible to obtain a lithium manganese composite oxide powder having a uniform composition microscopically and containing less impurities. .
【００４０】したがって、このリチウムマンガン複合酸
化物を正極活物質として用いることにより、充放電容量
が大きくかつ充放電サイクル特性に優れたリチウム二次
電池を得ることができる。Therefore, by using this lithium manganese composite oxide as a positive electrode active material, a lithium secondary battery having a large charge / discharge capacity and excellent charge / discharge cycle characteristics can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｍ 4/58 Ｈ０１Ｍ 10/40 Ｚ 10/40 Ｃ０４Ｂ 35/00 Ａ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI H01M 4/58 H01M 10/40 Z 10/40 C04B 35/00 A
Claims (5)
金属元素を含みかつオキシポリカルボン酸又は水に可溶
な化合物と、ポリオールと、オキシポリカルボン酸とを
反応させて水溶性の複合カルボン酸エステル錯体オリゴ
マーを生成させた後、該生成物を熱分解しその後アニー
ル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。1. A water-soluble composite carboxylic acid ester obtained by reacting a compound containing a metal element constituting a lithium manganese composite oxide and soluble in oxypolycarboxylic acid or water, a polyol and oxypolycarboxylic acid. A method for producing a lithium manganese composite oxide, comprising: producing a complex oligomer; thermally decomposing the product; and annealing the product.
酸エステル錯体オリゴマーが生成した反応液を５００〜
９００℃の雰囲気中に噴霧する方法であることを特徴と
する、請求項１記載のリチウムマンガン複合酸化物の製
造方法。2. The method of thermal decomposition, wherein the reaction solution in which the complex carboxylate complex oligomer has been formed is 500 to
The method for producing a lithium manganese composite oxide according to claim 1, wherein the method is spraying in an atmosphere at 900 ° C.
酸エステル錯体オリゴマーが生成した反応液を固液分離
し、その固形分を５００〜９００℃で熱処理する方法で
あることを特徴とする、請求項１記載のリチウムマンガ
ン複合酸化物の製造方法。3. The method of thermal decomposition, wherein the reaction solution in which the complex carboxylic acid ester complex oligomer is formed is subjected to solid-liquid separation, and the solid content is heat-treated at 500 to 900 ° C. A method for producing a lithium manganese composite oxide according to claim 1.
であることを特徴とする、請求項１〜３のいずれかに記
載のリチウムマンガン複合酸化物の製造方法。4. The annealing temperature is 600 to 850 ° C.
The method for producing a lithium manganese composite oxide according to any one of claims 1 to 3, wherein
般式：ＬｉＭy Ｍｎ2-y Ｏ4 （但し、ＭはＣｒ，Ｎｉ，
Ｆｅ，Ｃｏ，Ｍｇ，Ｌｉからなる群から選ばれた少なく
とも１種であり、０≦ｙ≦０．４である）で表されるこ
とを特徴とする、請求項１〜４のいずれかに記載のリチ
ウムマンガン複合酸化物の製造方法。5. The lithium manganese composite oxide has a general formula: LiM y Mn 2-y O 4 (where M is Cr, Ni,
5. It is at least one selected from the group consisting of Fe, Co, Mg, and Li, and 0 ≦ y ≦ 0.4. Production method of lithium manganese composite oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8343162A JPH10182161A (en) | 1996-12-24 | 1996-12-24 | Production of lithium-manganese double oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8343162A JPH10182161A (en) | 1996-12-24 | 1996-12-24 | Production of lithium-manganese double oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10182161A true JPH10182161A (en) | 1998-07-07 |
Family
ID=18359400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8343162A Pending JPH10182161A (en) | 1996-12-24 | 1996-12-24 | Production of lithium-manganese double oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10182161A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000059830A1 (en) * | 1999-03-30 | 2000-10-12 | Toho Titanium Co., Ltd. | Method for preparing lithium manganate, lithium manganate, positive electrode for lithium secondary cell containing the same as active material and lithium secondary cell |
| EP1382570A1 (en) * | 2002-07-09 | 2004-01-21 | Shoei Chemical Inc. | Method for manufacturing highly-crystallized double oxide powder |
| KR100553738B1 (en) * | 1999-10-26 | 2006-02-20 | 삼성에스디아이 주식회사 | Spraying machine of bonding mixture for cell |
| JP2006188372A (en) * | 2004-12-28 | 2006-07-20 | Japan Fine Ceramics Center | Manufacturing method of ceramic powder |
| JP2007261939A (en) * | 2006-03-29 | 2007-10-11 | Samsung Sdi Co Ltd | Porous metal oxide and method of preparing the same |
| JP2011108406A (en) * | 2009-11-13 | 2011-06-02 | Univ Of Fukui | Method of manufacturing active material for lithium ion secondary battery positive electrode |
-
1996
- 1996-12-24 JP JP8343162A patent/JPH10182161A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4614251B2 (en) * | 1999-03-30 | 2011-01-19 | 東邦チタニウム株式会社 | Method for producing lithium manganate |
| EP1116692A1 (en) * | 1999-03-30 | 2001-07-18 | Toho Titanium Co., Ltd. | Method for preparing lithium manganate, lithium manganate, positive electrode for lithium secondary cell containing the same as active material and lithium secondary cell |
| US6699297B1 (en) | 1999-03-30 | 2004-03-02 | Toho Titanium Co., Ltd. | Method for preparing lithium manganate and positive electrode for lithium secondary cell containing the same |
| WO2000059830A1 (en) * | 1999-03-30 | 2000-10-12 | Toho Titanium Co., Ltd. | Method for preparing lithium manganate, lithium manganate, positive electrode for lithium secondary cell containing the same as active material and lithium secondary cell |
| EP1116692A4 (en) * | 1999-03-30 | 2007-04-04 | Toho Titanium Co Ltd | Method for preparing lithium manganate, lithium manganate, positive electrode for lithium secondary cell containing the same as active material and lithium secondary cell |
| KR100553738B1 (en) * | 1999-10-26 | 2006-02-20 | 삼성에스디아이 주식회사 | Spraying machine of bonding mixture for cell |
| EP1382570A1 (en) * | 2002-07-09 | 2004-01-21 | Shoei Chemical Inc. | Method for manufacturing highly-crystallized double oxide powder |
| JP2004043216A (en) * | 2002-07-09 | 2004-02-12 | Shoei Chem Ind Co | Method for manufacturing highly-crystallized double oxide powder |
| US7138102B2 (en) | 2002-07-09 | 2006-11-21 | Shoei Chemical Inc. | Method for manufacturing highly-crystallized double oxide powder |
| JP2006188372A (en) * | 2004-12-28 | 2006-07-20 | Japan Fine Ceramics Center | Manufacturing method of ceramic powder |
| JP2007261939A (en) * | 2006-03-29 | 2007-10-11 | Samsung Sdi Co Ltd | Porous metal oxide and method of preparing the same |
| US8617510B2 (en) | 2006-03-29 | 2013-12-31 | Samsung Sdi Co., Ltd. | Porous metal oxide and method of preparing the same |
| JP2011108406A (en) * | 2009-11-13 | 2011-06-02 | Univ Of Fukui | Method of manufacturing active material for lithium ion secondary battery positive electrode |
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