JP2003272629A - Positive electrode active material for nonaqueous electrolyte secondary battery and its manufacturing method - Google Patents
Positive electrode active material for nonaqueous electrolyte secondary battery and its manufacturing methodInfo
- Publication number
- JP2003272629A JP2003272629A JP2002075919A JP2002075919A JP2003272629A JP 2003272629 A JP2003272629 A JP 2003272629A JP 2002075919 A JP2002075919 A JP 2002075919A JP 2002075919 A JP2002075919 A JP 2002075919A JP 2003272629 A JP2003272629 A JP 2003272629A
- Authority
- JP
- Japan
- Prior art keywords
- particle diameter
- lithium manganate
- positive electrode
- secondary battery
- active material
- 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.)
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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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水電解液二次電池用
の正極活物質として二次電池の充放電サイクル特性に優
れたマンガン酸リチウム粒子粉末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 manganate particle powder having excellent charge / discharge cycle characteristics of a secondary battery as a positive electrode active material for a non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術】近年、ＡＶ機器やパソコン等の電子機器
のポータブル化、コードレス化が急速に進んでおり、こ
れらの駆動用電源として小型、軽量で高エネルギー密度
を有する二次電池への要求が高くなっている。このよう
な状況下において、充放電電圧が高く、充放電容量も大
きいという長所を有するリチウムイオン二次電池が注目
されている。2. Description of the Related Art In recent years, portable and cordless electronic equipment such as AV equipment and personal computers are rapidly advancing, and there is a demand for a secondary battery having a small size, a light weight and a high energy density as a power source for driving them. It's getting higher. Under such circumstances, lithium ion secondary batteries, which have the advantages of high charge / discharge voltage and large charge / discharge capacity, have been receiving attention.
【０００３】従来、４Ｖ級の電圧をもつ高エネルギー型
のリチウムイオン二次電池に有用な正極活物質として
は、スピネル型構造のＬｉＭｎ２Ｏ４、岩塩型構造のＬ
ｉＭｎＯ２、ＬｉＣｏＯ２、ＬｉＣｏ１−ＸＮｉ
ＸＯ２、ＬｉＮｉＯ２等が一般的に知られており、なか
でもＬｉＣｏＯ２は高電圧と高容量を有する点で優れて
いるが、コバルト原料の供給量が少ないことによる製造
コスト高の問題や廃棄電池の環境安全上の問題を含んで
いる。そこで、供給量が多く低コストで環境適性の良い
マンガンを原料として作られるスピネル構造型のマンガ
ン酸リチウム粒子粉末（基本組成：ＬｉＭｎ２Ｏ４−以
下、同じ−）の研究が盛んに行われている。Conventionally, as a positive electrode active material useful for a high energy type lithium ion secondary battery having a voltage of 4V class, LiMn 2 O 4 having a spinel structure and L having a rock salt structure are used.
iMnO 2, LiCoO 2, LiCo 1 -X Ni
X O 2, LiNiO 2 or the like are generally known, inter alia although LiCoO 2 is excellent in that it has a high voltage and high capacity, the manufacturing cost due to the supply amount of the cobalt material less problematic Ya Includes environmental safety issues for waste batteries. Therefore, research on spinel-structured lithium manganate particles (basic composition: LiMn 2 O 4 -hereinafter, the same-) produced from manganese with a large supply amount and low cost and good environmental friendliness has been actively conducted. There is.
【０００４】周知の通り、マンガン酸リチウム粒子粉末
は、マンガン化合物とリチウム化合物とを所定の割合で
混合し、７００〜８００℃の温度範囲で焼成することに
よって得ることができる。As is well known, a lithium manganate particle powder can be obtained by mixing a manganese compound and a lithium compound in a predetermined ratio and firing the mixture in a temperature range of 700 to 800 ° C.
【０００５】しかしながら、マンガン酸リチウム粒子粉
末をリチウムイオン二次電池の正極活物質として用いた
場合、高電圧と高エネルギー密度を有するものの、充放
電サイクル特性が劣るという問題がある。この原因は、
充放電の繰り返しに伴う結晶構造中のリチウムイオンの
脱離・挿入挙動によって結晶格子が伸縮して、結晶の体
積変化によって格子破壊が生じることや電解液中へＭｎ
が溶解することとされている。However, when the lithium manganate particles are used as the positive electrode active material of a lithium ion secondary battery, although they have high voltage and high energy density, they have a problem of poor charge / discharge cycle characteristics. The cause is
The crystal lattice expands and contracts due to the desorption / insertion behavior of lithium ions in the crystal structure due to the repeated charge / discharge, and the lattice change occurs due to the volume change of the crystal.
Is said to dissolve.
【０００６】マンガン酸リチウム粒子粉末を用いたリチ
ウムイオン二次電池にあっては、充放電の繰り返しによ
る充放電容量の劣化を抑制し、充放電サイクル特性を向
上させることが現在最も要求されている。In a lithium ion secondary battery using lithium manganate particles, it is currently most required to suppress deterioration of charge / discharge capacity due to repeated charge / discharge and improve charge / discharge cycle characteristics. .
【０００７】充放電サイクル特性を向上させるために
は、マンガン酸リチウム粒子粉末からなる正極活物質が
充填性に優れ、適度な大きさを有することが必要であ
る。その手段としては、マンガン酸リチウム粒子の粒子
径及び粒度分布を制御する方法、焼成温度を制御して高
結晶のマンガン酸リチウム粒子粉末を得る方法、異種元
素を添加して結晶の結合力を強化する方法、表面処理を
行ってＭｎの溶出を抑制する方法等が行われている。In order to improve the charge / discharge cycle characteristics, it is necessary that the positive electrode active material composed of lithium manganate particles is excellent in filling property and has an appropriate size. As the means, a method of controlling the particle size and the particle size distribution of lithium manganate particles, a method of controlling the firing temperature to obtain highly crystalline lithium manganate particles, and a heterogeneous element are added to strengthen the crystal bonding force. And a method of suppressing elution of Mn by performing surface treatment.
【０００８】適度な大きさのマンガン酸リチウム粒子粉
末を得る方法として、特開平１０−１６２８２６号公
報、特開平１０−１７２５６７号公報、特開平１０−３
２１２２７号公報、特開平１１−１３２３号公報、特開
平１１−４５７１０号公報、特開平１１−７１１１５号
公報、特開平１１−２１９７０５号公報、特開２０００
−１２０３１号公報、特開２０００−１４３２４７号公
報、特開２００１−１２２６２６号公報及び特開２００
１−２４０４１７号公報記載の各方法が知られている。As a method for obtaining a lithium manganate particle powder having an appropriate size, JP-A-10-162826, JP-A-10-172567, and JP-A-10-3 can be used.
No. 21227, No. 11-1323, No. 11-45710, No. 11-71115, No. 11-219705, No. 2000
-12031, JP-A-2000-143247, JP-A-2001-122626, and JP-A-200
Each method described in JP-A 1-240417 is known.
【０００９】[0009]
【発明が解決しようとする課題】非水電解液二次電池用
の正極活物質として二次電池の充放電サイクル特性に優
れたマンガン酸リチウム粒子粉末は未だ得られていな
い。As a positive electrode active material for a non-aqueous electrolyte secondary battery, lithium manganate particles having excellent charge / discharge cycle characteristics of the secondary battery have not been obtained yet.
【００１０】即ち、前出特開平１０−１６２８２６号公
報には噴霧熱分解法によって粒度分布に優れたマンガン
酸リチウム粒子粉末を得る製造法が開示されているが、
得られるマンガン酸リチウム粒子粉末は多孔性であり比
表面積が大きくなるため、Ｍｎの溶出を抑制することが
困難となり、結果として、二次電池の充放電サイクル特
性が低下する。また、充填密度についても十分とは言い
難いものである。That is, the above-mentioned Japanese Patent Laid-Open No. 10-162826 discloses a method for producing lithium manganate particles having an excellent particle size distribution by a spray pyrolysis method.
Since the obtained lithium manganate particle powder is porous and has a large specific surface area, it becomes difficult to suppress the elution of Mn, and as a result, the charge / discharge cycle characteristics of the secondary battery deteriorate. Further, it is hard to say that the packing density is sufficient.
【００１１】また、前出特開平１０−１７２５６７号公
報には、マンガン化合物とリチウム化合物とのスラリー
をスプレードライヤーで乾燥した後、焼成する製造法が
開示されているが、多数の一次粒子からなる凝集体を構
成しており、比表面積が大きくなるためＭｎの溶出を抑
制することが困難となり、結果として、二次電池の充放
電サイクル特性が低下する。また、充填密度についても
十分とは言い難いものである。Further, Japanese Unexamined Patent Publication (Kokai) No. 10-172567 mentioned above discloses a manufacturing method in which a slurry of a manganese compound and a lithium compound is dried by a spray dryer and then calcined, but it is composed of a large number of primary particles. Since the agglomerates are formed and the specific surface area becomes large, it becomes difficult to suppress the elution of Mn, and as a result, the charge / discharge cycle characteristics of the secondary battery deteriorate. Further, it is hard to say that the packing density is sufficient.
【００１２】また、前出特開平１０−３２１２２７号公
報には一次粒子と二次粒子の平均粒子径を特定したマン
ガン酸リチウム粒子粉末が開示されているが、一次粒子
が小さいため、二次粒子は多数の一次粒子によって構成
されており、比表面積が大きくなるためＭｎの溶出を抑
制することが困難となり、結果として、二次電池の充放
電サイクル特性が低下する。また、充填密度についても
十分とは言い難いものである。Further, Japanese Patent Laid-Open No. 10-32127 discloses a lithium manganate particle powder in which the average particle size of primary particles and secondary particles is specified. However, since the primary particles are small, the secondary particles are Is composed of a large number of primary particles, and it becomes difficult to suppress the elution of Mn because the specific surface area becomes large, and as a result, the charge / discharge cycle characteristics of the secondary battery deteriorate. Further, it is hard to say that the packing density is sufficient.
【００１３】また、前出特開平１１−１３２３号公報に
は一次粒子と二次粒子の平均粒子径を特定したマンガン
酸リチウム粒子粉末が記載されているが、凝集体であっ
て、比表面積が大きくなるためＭｎの溶出を抑制するこ
とが困難となり、結果として、二次電池の充放電サイク
ル特性が低下する。また実施例では平均一次粒子径２．
０μｍであって平均二次粒子径２．０μｍであるマンガ
ン酸リチウム粒子粉末が記載されているが、平均粒子径
が小さく充填性が十分とは言い難いものである。Further, the above-mentioned JP-A-11-1323 describes a lithium manganate particle powder in which the average particle size of primary particles and secondary particles is specified, but it is an aggregate and has a specific surface area. Since it becomes large, it becomes difficult to suppress the elution of Mn, and as a result, the charge / discharge cycle characteristics of the secondary battery deteriorate. In the examples, the average primary particle diameter is 2.
Although a lithium manganate particle powder having a particle size of 0 μm and an average secondary particle size of 2.0 μm is described, it is difficult to say that the average particle size is small and the filling property is sufficient.
【００１４】また、前出特開平１１−４５７１０号公報
には、Ｆを含有するマンガン酸リチウム粒子粉末が開示
されているが、各種原料を混合、焼成して得られるもの
であり、マンガン酸リチウム粒子粉末の一次粒子につい
ては考慮されておらず、Ｍｎの溶出抑制及び充填性が十
分とは言い難いものである。Further, Japanese Patent Application Laid-Open No. 11-45710 discloses a lithium manganate particle powder containing F, which is obtained by mixing and firing various raw materials. The primary particles of the particle powder are not considered, and it is difficult to say that the elution suppression of Mn and the filling property are sufficient.
【００１５】また、特開平１１−７１１１５号公報には
平均凝集粒子径が１〜５０μｍであって平均一次粒子径
が３．０μｍ以下であるマンガン酸リチウム粒子粉末が
開示されているが、実施例で得られているマンガン酸リ
チウム粒子の平均一次粒子径は１．０μｍ以下と小さく
比表面積が大きくなるため、Ｍｎの溶出を抑制すること
が困難となり、結果として、二次電池の充放電サイクル
特性が低下する。Further, JP-A-11-71115 discloses a lithium manganate particle powder having an average agglomerated particle diameter of 1 to 50 μm and an average primary particle diameter of 3.0 μm or less. The average primary particle size of the lithium manganate particles obtained in 1. is as small as 1.0 μm or less and the specific surface area is large, so that it is difficult to suppress the elution of Mn, and as a result, the charge / discharge cycle characteristics of the secondary battery. Is reduced.
【００１６】また、前出特開平１１−２１９７０５号公
報には平均粒子径が１．０μｍ以下の微細粒子の含有量
が少ないマンガン酸リチウム粒子粉末が開示されている
が、一次粒子については考慮されておらず、マンガン原
料に電解ＭｎＯ２を用いている点及び平均粒子径に対す
る比表面積が大きいことから、凝集粒子であると推測さ
れる。そのため、Ｍｎの溶出を抑制することは困難であ
り、結果として、二次電池の充放電サイクル特性が低下
する。Further, the above-mentioned JP-A-11-219705 discloses a lithium manganate particle powder having a small content of fine particles having an average particle diameter of 1.0 μm or less, but primary particles are considered. However, the fact that electrolytic MnO 2 is used as the manganese raw material and the specific surface area relative to the average particle size are large, so it is presumed that the particles are aggregated particles. Therefore, it is difficult to suppress the elution of Mn, and as a result, the charge / discharge cycle characteristics of the secondary battery deteriorate.
【００１７】また、前出特開２０００−１２０３１号公
報には平均粒子径が１〜４５μｍのマンガン酸リチウム
粒子粉末が開示されているが、一次粒子については考慮
されておらず、得られたマンガン酸リチウム粒子は小さ
な一次粒子が凝集した二次粒子であるため、比表面積が
大きくＭｎの溶出を抑制することが困難となり、結果と
して、二次電池の充放電サイクル特性が低下する。Further, the above-mentioned Japanese Patent Laid-Open No. 2000-12031 discloses a lithium manganate particle powder having an average particle diameter of 1 to 45 μm, but primary particles are not taken into consideration and the obtained manganese is obtained. Since lithium oxide particles are secondary particles formed by aggregating small primary particles, it is difficult to suppress the elution of Mn because of their large specific surface area, and as a result, the charge / discharge cycle characteristics of the secondary battery deteriorate.
【００１８】また、前出特開２０００−１４３２４７号
公報には一次粒子径が０．５〜２．０μｍであるマンガ
ン酸リチウム粒子粉末が開示されているが、一次粒子が
小さいため、充填密度が低くなり、また、比表面積も大
きくなるためＭｎの溶出を抑制することが困難となり、
結果として、二次電池の充放電サイクル特性が低下す
る。Further, the above-mentioned Japanese Patent Laid-Open No. 2000-143247 discloses a lithium manganate particle powder having a primary particle diameter of 0.5 to 2.0 μm, but since the primary particles are small, the packing density is high. It becomes low and the specific surface area becomes large, so it becomes difficult to suppress the elution of Mn,
As a result, the charge / discharge cycle characteristics of the secondary battery deteriorate.
【００１９】また、前出特開２００１−１２２６２６号
公報には粒度分布を特定したマンガン酸リチウム粒子粉
末が開示されているが、一次粒子については考慮されて
おらず、マンガン原料に電解二酸化マンガン（ＥＭＤ）
又はＣＭＤを用いている点及び平均粒子径に対する比表
面積が大きいことから、凝集粒子であると推測される。
従って、Ｍｎの溶出を抑制することが困難となり、結果
として充放電サイクル特性が低下する。Further, the above-mentioned Japanese Patent Laid-Open No. 2001-122626 discloses a lithium manganate particle powder having a specified particle size distribution, but primary particles are not taken into consideration and electrolytic manganese dioxide ( EMD)
Alternatively, since CMD is used and the specific surface area relative to the average particle size is large, it is presumed that the particles are aggregated particles.
Therefore, it becomes difficult to suppress the elution of Mn, and as a result, the charge / discharge cycle characteristics deteriorate.
【００２０】また、前出特開２００１−２４０４１７号
公報にはマンガン水酸化物を酸化して酸化マンガンとし
た後、粒子成長させ、次いで、リチウム化合物と混合し
た後、加熱焼成する製造法が開示されているが、得られ
たマンガン酸リチウム粒子粉末の比表面積が大きいこと
から、Ｍｎの溶出を抑制することが困難となり、結果と
して、二次電池の充放電サイクル特性が低下する。ま
た、水熱合成するため工業的とは言い難い。Further, the above-mentioned Japanese Patent Laid-Open No. 2001-240417 discloses a manufacturing method in which manganese hydroxide is oxidized into manganese oxide, particles are grown, and then mixed with a lithium compound, followed by heating and firing. However, since the obtained lithium manganate particles have a large specific surface area, it is difficult to suppress the elution of Mn, and as a result, the charge / discharge cycle characteristics of the secondary battery deteriorate. Also, since it is hydrothermally synthesized, it cannot be said to be industrial.
【００２１】そこで本発明は、非水電解液二次電池用の
正極活物質として二次電池の充放電サイクル特性に優れ
たマンガン酸リチウム粒子粉末を提供することを技術的
課題とする。Therefore, it is a technical object of the present invention to provide a lithium manganate particle powder having excellent charge / discharge cycle characteristics of a secondary battery as a positive electrode active material for a non-aqueous electrolyte secondary battery.
【００２２】[0022]
【課題を解決するための手段】前記技術的課題は、次の
通りの本発明によって達成できる。The above technical problems can be achieved by the present invention as follows.
【００２３】即ち、本発明は、平均一次粒子径が３．０
〜２０．０μｍであって平均二次粒子径Ｄ５０（マンガ
ン酸リチウム粒子粉末の全体積を１００％として粒子径
に対する累積割合を求めたときの累積割合が５０％とな
る粒子径）が２．５〜４０．０μｍであり、前記平均一
次粒子径と平均二次粒子径との比（平均一次粒子径／平
均二次粒子径）が０．５〜１．２であるマンガン酸リチ
ウム粒子粉末からなることを特徴とする非水電解質二次
電池用正極活物質である。That is, in the present invention, the average primary particle size is 3.0.
.About.20.0 μm and the average secondary particle diameter D 50 (the particle diameter at which the cumulative proportion with respect to the particle diameter when the total volume of the lithium manganate particle powder is 100% is 50%) is 2. From 5 to 40.0 μm, and the ratio of the average primary particle diameter to the average secondary particle diameter (average primary particle diameter / average secondary particle diameter) is 0.5 to 1.2. And a positive electrode active material for a non-aqueous electrolyte secondary battery.
【００２４】また、本発明は、マンガン酸リチウム粒子
粉末の平均二次粒子径Ｄ５０に対するＤ１０（マンガン
酸リチウム粒子粉末の全体積を１００％として粒子径に
対する累積割合を求めたときの累積割合が１０％となる
粒子径）の比（Ｄ１０／Ｄ５ ０）が０．５０以上であっ
てＤ５０に対するＤ９０（マンガン酸リチウム粒子粉末
の全体積を１００％として累積体積で表した粒子径を求
めたときの累積割合が９０％となる粒子径）の比（Ｄ
９０／Ｄ５０）が２．０以下である前記非水電解質二次
電池用正極活物質である。Further, according to the present invention, the cumulative ratio when D 10 (the total volume of the lithium manganate particle powder is 100% and the cumulative ratio with respect to the particle diameter is calculated with respect to the average secondary particle diameter D 50 of the lithium manganate particle powder) particles but expressed in cumulative volume on the total volume of the ratio (D 10 / D 5 0) a is 0.50 or more D 90 for D 50 (lithium manganate particles having a particle diameter) comprising 10% 100% The ratio of the particle diameter at which the cumulative proportion when the diameter is obtained is 90% (D
90 / D 50) is a positive active material for the nonaqueous electrolyte secondary battery is 2.0 or less.
【００２５】また、本発明は、マンガン塩を含有する反
応溶液を中和し、次いで熟成した後、酸化反応を行って
酸化マンガン粒子粉末を得、該酸化マンガン粒子粉末と
リチウム化合物とを混合し、該混合物を７００〜１００
０℃の温度範囲で加熱することを特徴とする前記非水電
解質二次電池用正極活物質の製造法である。In the present invention, the reaction solution containing a manganese salt is neutralized and then aged, and then an oxidation reaction is carried out to obtain manganese oxide particle powder, and the manganese oxide particle powder and a lithium compound are mixed. , 100 to 100 of the mixture
The method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery is characterized by heating in a temperature range of 0 ° C.
【００２６】次に、本発明の構成をより詳しく説明すれ
ば次の通りである。Next, the structure of the present invention will be described in more detail.
【００２７】先ず、本発明に係る非水電解質二次電池用
正極活物質（以下、単に「正極活物質」と言う。）につ
いて述べる。First, the positive electrode active material for a non-aqueous electrolyte secondary battery according to the present invention (hereinafter, simply referred to as "positive electrode active material") will be described.
【００２８】なお、本発明において、「一次粒子」とは
単独で存在することができる最小粒子を表し、「二次粒
子」とは複数の一次粒子が凝集して形成された通常挙動
する上での最小粒子のことを意味する。In the present invention, the term "primary particle" means the smallest particle that can exist alone, and the term "secondary particle" means that a plurality of primary particles are aggregated to behave normally. Means the smallest particle of.
【００２９】本発明に係る正極活物質は、平均一次粒子
径が３．０〜２０．０μｍである。平均一次粒子径が
３．０μｍ未満の場合には、二次電池の正極を製造する
際に充填密度が低くなり、また、バインダ量を増加させ
る必要があるなど、二次電池のエネルギー密度の低下を
招く。一方、２０．０μｍを超える場合には、電流密度
を増加させた場合にＬｉの脱挿入反応が低下する傾向が
ある。好ましくは４．０〜１８．０μｍである。The positive electrode active material according to the present invention has an average primary particle diameter of 3.0 to 20.0 μm. When the average primary particle size is less than 3.0 μm, the packing density becomes low when the positive electrode of the secondary battery is manufactured, and it is necessary to increase the amount of the binder, which lowers the energy density of the secondary battery. Invite. On the other hand, when it exceeds 20.0 μm, the Li insertion / removal reaction tends to decrease when the current density is increased. It is preferably 4.0 to 18.0 μm.
【００３０】本発明に係る正極活物質の平均二次粒子径
（Ｄ５０）は２．５〜４０．０μｍである。平均二次粒
子径が３．０μｍ未満の場合には、二次電池の正極を製
造する際に充填密度が低くなり、また、バインダ量を増
加させる必要があるなど、二次電池のエネルギー密度の
低下を招く。一方、２０．０μｍを超える場合には、電
流密度を増加させた場合にＬｉの脱挿入反応が低下する
傾向がある。好ましくは５．０〜３０．０μｍである。The average secondary particle diameter (D 50 ) of the positive electrode active material according to the present invention is 2.5 to 40.0 μm. When the average secondary particle size is less than 3.0 μm, the packing density becomes low when the positive electrode of the secondary battery is manufactured, and it is necessary to increase the binder amount. Cause decline. On the other hand, when it exceeds 20.0 μm, the Li insertion / removal reaction tends to decrease when the current density is increased. The thickness is preferably 5.0 to 30.0 μm.
【００３１】前記平均一次粒子径と前記平均二次粒子径
（Ｄ５０）との比（平均一次粒子径／平均二次粒子径）
は０．５〜１．２であり、０．５未満の場合には、凝集
粒子が多数存在するため充填密度が低下し、１．０であ
れば、一次粒子と二次粒子の粒子径が同一であり凝集し
ておらず一次粒子として挙動しているものであるが、測
定誤差を考慮すると上限値は１．２である。好ましくは
０．５〜１．０である。Ratio of the average primary particle diameter to the average secondary particle diameter (D 50 ) (average primary particle diameter / average secondary particle diameter)
Is 0.5 to 1.2, and when it is less than 0.5, the packing density is lowered due to the large number of aggregated particles, and when it is 1.0, the particle diameters of the primary particles and the secondary particles are The particles are the same and do not aggregate but behave as primary particles, but the upper limit is 1.2 in consideration of measurement error. It is preferably 0.5 to 1.0.
【００３２】レーザー散乱・回折方式により、マンガン
酸リチウム粒子粉末の全体積を１００％として粒子径に
対する体積の累積割合を求めたときの体積の累積割合が
１０％、５０％、９０％となる点の粒子径をそれぞれＤ
１０、Ｄ５０、Ｄ９０として示した場合、本発明に係る
正極活物質の粒度分布は、平均二次粒子径Ｄ５０に対す
るＤ１０の比（Ｄ１０／Ｄ５０）が０．５０以上であっ
てＤ５０に対するＤ９ ０の比（Ｄ９０／Ｄ５０）が２．
０以下である。Ｄ１０／Ｄ５０及びＤ９０／Ｄ ５０が前
記範囲外の場合には、粒度分布が広いことを意味してお
り、充填性が低下する。Ｄ１０／Ｄ５０は０．６以上が
好ましく、より好ましくは０．６４以上である。その上
限値は０．８５程度である。また、Ｄ９０／Ｄ５０は
１．７以下が好ましく、より好ましくは１．６以下であ
る。その下限値は１．１５程度である。Manganese by laser scattering / diffraction system
The total volume of lithium oxide particle powder is 100%
When the cumulative ratio of the volume to the
The particle diameters at 10%, 50%, and 90% are D
10,DFifty, D90, The present invention
The particle size distribution of the positive electrode active material is the average secondary particle diameter D.FiftyAgainst
D10Ratio of (D10/ DFifty) Is 0.50 or more
DFiftyAgainst D9 0Ratio of (D90/ DFifty) Is 2.
It is 0 or less. D10/ DFiftyAnd D90/ D FiftyBefore
Outside the range, it means that the particle size distribution is wide.
Therefore, the filling property decreases. D10/ DFiftyIs 0.6 or more
It is more preferably 0.64 or more. Moreover
The limit value is about 0.85. Also, D90/ DFiftyIs
It is preferably 1.7 or less, more preferably 1.6 or less.
It The lower limit is about 1.15.
【００３３】本発明に係る正極活物質の粒子形状は粒状
である。鋭角部を有する粒子形状の場合には、電解液と
の反応性が高まるため好ましくない。The particle shape of the positive electrode active material according to the present invention is granular. In the case of a particle shape having an acute angle portion, reactivity with an electrolytic solution increases, which is not preferable.
【００３４】本発明に係る正極活物質はＬｉ１＋ｘＭｎ
２−ｘＯ４の組成式で表されるマンガン酸リチウム粒子
粉末であり、Ｌｉ／Ｍｎはモル比で０．５２５〜０．６
２であることが好ましい。０．５２５未満の場合には、
充放電容量は高いがＪａｈｎ−Ｔｅｌｌｅｒ効果による
歪みの発生のためサイクル特性が低下する。また、０．
６２を越える場合には、初期放電容量が十分ではないた
め好ましくない。前記組成式において、原子番号が１１
以上の金属元素又は遷移金属元素をＭｎに対するモル比
で０〜２０％含有してもよい。The positive electrode active material according to the present invention is Li 1 + x Mn.
It is a lithium manganate particle powder represented by a composition formula of 2- xO 4 , and Li / Mn is a molar ratio of 0.525 to 0.6.
It is preferably 2. If less than 0.525,
Although the charge / discharge capacity is high, the cycle characteristics deteriorate due to the occurrence of strain due to the John-Teller effect. Also, 0.
If it exceeds 62, the initial discharge capacity is not sufficient, which is not preferable. In the above composition formula, the atomic number is 11
You may contain the said metal element or transition metal element by 0-20% by molar ratio with respect to Mn.
【００３５】なお、充放電容量及びサイクル特性に寄与
しないＭｎ２Ｏ３、Ｍｎ３Ｏ４、ＭｎＯ２、Ｌｉ２Ｍｎ
Ｏ３等の異相を含んでいても良い。It should be noted that Mn 2 O 3 , Mn 3 O 4 , MnO 2 and Li 2 Mn which do not contribute to the charge / discharge capacity and cycle characteristics.
It may contain a foreign phase such as O 3 .
【００３６】本発明に係る正極活物質のＢＥＴ比表面積
値は、０．０４〜１．５ｍ２／ｇが好ましい。０．０４
ｍ２／ｇ未満の場合には、電流密度を増加させた場合に
Ｌｉの脱挿入反応が低下すると考えられ電池特性が低下
する。１．５ｍ２／ｇを超える場合には、正極活物質の
充填密度が低下することや電解液との反応性が過剰とな
り安全性が低下する。The BET specific surface area value of the positive electrode active material according to the present invention is preferably 0.04 to 1.5 m 2 / g. 0.04
When it is less than m 2 / g, the Li insertion / desorption reaction is considered to decrease when the current density is increased, and the battery characteristics deteriorate. When it exceeds 1.5 m 2 / g, the packing density of the positive electrode active material decreases and the reactivity with the electrolytic solution becomes excessive, so that the safety decreases.
【００３７】本発明に係る正極活物質のタップ密度は
２．０ｇ／ｍｌ以上が好ましい。その上限値は３．０ｇ
／ｍｌ程度である。The tap density of the positive electrode active material according to the present invention is preferably 2.0 g / ml or more. The upper limit is 3.0g
/ Ml.
【００３８】次に、本発明に係る正極活物質の製造法に
ついて述べる。Next, the method for producing the positive electrode active material according to the present invention will be described.
【００３９】本発明におけるマンガン塩としては、硫酸
マンガン、硝酸マンガン、蓚酸マンガン、酢酸マンガン
等が挙げられ、これらは単独で又は必要に応じて２種以
上組み合わせて用いてもよい。Examples of the manganese salt in the present invention include manganese sulfate, manganese nitrate, manganese oxalate, manganese acetate, etc. These may be used alone or in combination of two or more as required.
【００４０】前記の各種マンガン塩を含有する反応溶液
を中和する場合には、水酸化ナトリウム水溶液、水酸化
カリウム水溶液、アンモニア等のアルカリ溶液を使用す
ることができる。アルカリ溶液はマンガン塩の当量より
も過剰に添加することによって粒子サイズの大きな酸化
マンガンを容易に得ることができる。前記マンガン塩の
中和分を除くアルカリ溶液の添加量は０〜２０モル／Ｌ
で行え、１．０から１０モル／Ｌが好ましい。When the reaction solution containing various manganese salts described above is neutralized, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide or an alkaline solution such as ammonia can be used. Manganese oxide having a large particle size can be easily obtained by adding an alkaline solution in excess of the equivalent amount of manganese salt. The addition amount of the alkaline solution excluding the neutralized portion of the manganese salt is 0 to 20 mol / L.
Can be carried out in the following manner, and preferably 1.0 to 10 mol / L.
【００４１】熟成反応は、中和反応後の懸濁液に対し
て、２０〜１００℃の温度範囲、好ましくは５０〜９０
℃の温度範囲で行う。熟成反応を行うことによって粒度
分布の狭い酸化マンガンが得られ、よって粒度分布の狭
いマンガン酸リチウム粒子粉末を得ることができる。熟
成時間は０．１〜１０時間が好ましく、より好ましくは
１〜３時間である。The aging reaction is carried out in a temperature range of 20 to 100 ° C., preferably 50 to 90, with respect to the suspension after the neutralization reaction.
Perform in the temperature range of ° C. By carrying out the aging reaction, manganese oxide having a narrow particle size distribution can be obtained, and thus a lithium manganate particle powder having a narrow particle size distribution can be obtained. The aging time is preferably 0.1 to 10 hours, more preferably 1 to 3 hours.
【００４２】酸化反応は、反応溶液に酸化性ガスを通気
するか、或いは、酸化剤を添加することによって行うこ
とができ、例えば空気の通気が好ましい。The oxidation reaction can be carried out by passing an oxidizing gas through the reaction solution or by adding an oxidizing agent, for example, aeration of air is preferable.
【００４３】酸化反応の終了後、水洗、乾燥を行って酸
化マンガン粒子粉末とする。After completion of the oxidation reaction, washing with water and drying are performed to obtain manganese oxide particle powder.
【００４４】得られる酸化マンガン粒子粉末はＭｎ３Ｏ
４からなり、粒子形状は粒状であり、平均粒子径が２．
０〜２０．０μｍであり、ＢＥＴ比表面積値が０．０４
〜２．０ｍ２／ｇであることが好ましい。また、Ｍｎ２
Ｏ３を含んでいてもよい。The obtained manganese oxide particle powder is Mn 3 O.
4 and the particle shape is granular, and the average particle diameter is 2.
0 to 20.0 μm, BET specific surface area value is 0.04
It is preferably about 2.0 m 2 / g. Also, Mn 2
It may contain O 3 .
【００４５】リチウム原料としては炭酸リチウム、水酸
化リチウム、硝酸リチウム、塩化リチウムなどが使用出
来るが、炭酸リチウムが好ましい。As the lithium raw material, lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride and the like can be used, but lithium carbonate is preferred.
【００４６】酸化マンガン粒子粉末とリチウム原料との
混合割合は、モル比でＬｉ／Ｍｎ＝０．５２５〜０．６
２程度とするのが好ましい。０．５２５以下の場合には
容量は高いがＪａｈｎ―Ｔｅｌｌｅｒ効果による歪みの
発生のため充放電サイクル特性が低下する。また、０．
６２を越える場合には初期容量が十分ではない。The manganese oxide particle powder and the lithium raw material are mixed in a molar ratio of Li / Mn = 0.525 to 0.6.
It is preferably about 2. When it is 0.525 or less, the capacity is high, but the charge-discharge cycle characteristics deteriorate due to the occurrence of strain due to the John-Teller effect. Also, 0.
If it exceeds 62, the initial capacity is not sufficient.
【００４７】酸化マンガン粒子粉末とリチウム原料は均
一な混合状態とする必要がある。均一に混合されていな
いと、部分的に組成比のズレが生じ容量及び可逆性の異
なるマンガン酸リチウムが合成されることになり、ま
た、マンガン酸リチウム以外の異相の発生原因にもな
る。The manganese oxide particle powder and the lithium raw material must be in a uniform mixed state. If they are not mixed homogeneously, the composition ratio will be partially shifted, and lithium manganate having different capacities and reversibility will be synthesized, and it will also be a cause of generation of a different phase other than lithium manganate.
【００４８】混合物の焼成温度は７００〜１０００℃で
ある。７００℃未満の場合には、高い結晶性を有するマ
ンガン酸リチウム粒子粉末を得ることができない。１０
００℃以上では一次粒子の平均粒子径が大きくなりすぎ
Ｌｉイオンの脱挿入が生じ難くなる。The firing temperature of the mixture is 700 to 1000 ° C. When the temperature is lower than 700 ° C., lithium manganate particles having high crystallinity cannot be obtained. 10
At a temperature of 00 ° C. or higher, the average particle size of the primary particles becomes too large and it becomes difficult for Li ions to be de-inserted.
【００４９】焼成雰囲気は、酸素含有ガス、例えば空気
中でよい。焼成時間は反応が均一に進行するように選択
すればよいが、１〜４８時間が好ましく、より好ましく
は１０〜２４時間である。The firing atmosphere may be an oxygen-containing gas such as air. The firing time may be selected so that the reaction proceeds uniformly, but is preferably 1 to 48 hours, more preferably 10 to 24 hours.
【００５０】焼成後、粉砕してマンガン酸リチウム粒子
粉末を得る。After firing, the powder is pulverized to obtain lithium manganate particles.
【００５１】本発明に係るマンガン酸リチウム粒子粉末
を非水電解液二次電池用の正極活物質として用いて正極
材を製造する場合には、アセチレンブラック、カーボン
ブラック等の導電剤及びポリテトラフルオロエチレン、
ポリフッ化ビニリデン等の結着材などと混合して、所定
の形状に成形して正極材とする。When a positive electrode material is manufactured by using the lithium manganate particles according to the present invention as a positive electrode active material for a non-aqueous electrolyte secondary battery, a conductive agent such as acetylene black or carbon black and polytetrafluorocarbon are used. ethylene,
It is mixed with a binder such as polyvinylidene fluoride and molded into a predetermined shape to obtain a positive electrode material.
【００５２】また、負極活物質は特に制限されないが、
例えば、リチウム金属、リチウム合金、リチウムを吸蔵
放出可能な物質を用いることができ、例えば、リチウム
／アルミニウム合金、リチウム／スズ合金、グラファイ
トや黒鉛等が挙げられる。The negative electrode active material is not particularly limited,
For example, a lithium metal, a lithium alloy, a substance capable of inserting and extracting lithium can be used, and examples thereof include a lithium / aluminum alloy, a lithium / tin alloy, graphite, and graphite.
【００５３】また、電解質も特に制限されないが、例え
ば、炭酸プロピレン、炭酸ジエチル、炭酸ジメチル等の
カーボネート類やジメトキシエタン等のエーテル類の少
なくとも１種類の有機溶媒中に、過塩素酸リチウム、四
フッ化ホウ酸リチウム、六フッ化リン酸リチウム等のリ
チウム塩の少なくとも１種を溶解したものを用いること
ができる。The electrolyte is also not particularly limited, but for example, in at least one organic solvent such as carbonates such as propylene carbonate, diethyl carbonate, dimethyl carbonate and ethers such as dimethoxyethane, lithium perchlorate, tetrafluoride and tetrafluoride are used. What melt | dissolved at least 1 sort (s) of lithium salt, such as lithium borate and lithium hexafluorophosphate, can be used.
【００５４】本発明に係る正極活物質を用いて製造した
二次電池は、初期放電容量が８５〜１３５ｍＡｈ／ｇ、
６０℃での５０サイクル後の容量維持率が９３％以上で
ある。The secondary battery manufactured using the positive electrode active material according to the present invention has an initial discharge capacity of 85 to 135 mAh / g,
The capacity retention rate after 50 cycles at 60 ° C. is 93% or more.
【００５５】[0055]
【発明の実施の形態】本発明の代表的な実施の形態は次
の通りである。BEST MODE FOR CARRYING OUT THE INVENTION A typical embodiment of the present invention is as follows.
【００５６】正極活物質の粒子径は下記２種類の方法で
測定した。The particle size of the positive electrode active material was measured by the following two methods.
【００５７】レーザー散乱・回折方式「ＮＩＫＫＩＳＯ
ＭＩＣＲＯＴＲＡＣ ＨＲＡ、ＭＯＤＥＬ９３２０−
Ｘ１００：日機装社製」を用いて各粒子粉末の体積換算
の粒度分布から二次粒子のＤ１０、Ｄ５０、Ｄ９０を測
定した。平均二次粒子径はＤ ５０の値とした。Laser scattering / diffraction system "NIKKISO
MICROTRAC HRA, MODEL9320-
X100: manufactured by Nikkiso Co., Ltd.
Of secondary particles from the particle size distribution of10, DFifty, D90Measure
Decided Average secondary particle size is D FiftyThe value of
【００５８】平均一次粒子径は走査型電子顕微鏡（日立
製作所製）で測定した。走査型電子顕微鏡写真の対角線
上に存在する粒子から任意に一次粒子を１０個選び、粒
径を測定して、その平均値を平均一次粒子径とした。走
査型電子顕微鏡写真は対角線上に２０〜４０個の粒子が
存在する倍率が粒径を測定精度の点から好ましい。The average primary particle diameter was measured with a scanning electron microscope (manufactured by Hitachi Ltd.). Ten primary particles were arbitrarily selected from the particles existing on the diagonal line of the scanning electron microscope photograph, the particle size was measured, and the average value was defined as the average primary particle size. In the scanning electron micrograph, a magnification at which 20 to 40 particles are present on the diagonal line is preferable from the viewpoint of measuring accuracy of the particle size.
【００５９】正極活物質の同定及び結晶構造及び結晶子
サイズは、Ｘ線回折（ＲＩＧＡＫＵＣｕ−Ｋα ４０ｋ
Ｖ ４０ｍＡ）により調べた。The positive electrode active material was identified and its crystal structure and crystallite size were determined by X-ray diffraction (RIGAKUCu-Kα 40k).
V 40 mA).
【００６０】また、前駆体の粒子の形態については走査
型電子顕微鏡（日立製作所製）により観察した。The morphology of the precursor particles was observed with a scanning electron microscope (Hitachi Ltd.).
【００６１】ＢＥＴ比表面積はＢＥＴ法により測定し
た。The BET specific surface area was measured by the BET method.
【００６２】タップ密度は、「ＳＥＩＳＨＩＮ ＴＡＰ
ＤＥＮＳＥＲ ＫＹＴ−３０００：（株）セイシン企業
製」を用いて測定した。The tap density is "SEISHIN TAP".
DENSER KYT-3000: manufactured by Seishin Enterprise Co., Ltd. ”.
【００６３】＜正極の作製＞マンガン酸リチウム粒子粉
末と導電剤であるアセチレンブラックと結着材であるポ
リフッ化ビニリデンとを重量比８５：１０：５の割合で
混合し、Ｎ−メチル−２−ピロリドンを加えペースト化
し、該ペーストをアルミニウム箔に０．１５ｍｍ厚で塗
布し、乾燥後、直径１６ｍｍの円盤に打ち抜いて正極を
作製した。<Production of Positive Electrode> Lithium manganate particle powder, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder were mixed at a weight ratio of 85: 10: 5, and N-methyl-2- Pyrrolidone was added to form a paste, the paste was applied to an aluminum foil with a thickness of 0.15 mm, dried and punched into a disk having a diameter of 16 mm to produce a positive electrode.
【００６４】負極にはリチウム箔を用い、これを１６ｍ
ｍの円盤状に打ち抜いた。Lithium foil was used for the negative electrode,
It was punched into a disk shape of m.
【００６５】＜二次電池の作製＞セパレータはポリエチ
レン製からなり、これを１９ｍｍの円盤状に打ち抜い
た。電解液にはＬｉＰＦ６を支持塩とするエチレンカー
ボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）を
体積比１：１で混合したものを用いた。そして、アルゴ
ン雰囲気のグローブボックス中でコイン型セル電池を作
製した。<Preparation of Secondary Battery> The separator was made of polyethylene and was punched into a 19 mm disk shape. The electrolyte used was a mixture of ethylene carbonate (EC) with LiPF 6 as a supporting salt and diethyl carbonate (DEC) at a volume ratio of 1: 1. Then, a coin-type cell battery was manufactured in a glove box in an argon atmosphere.
【００６６】二次電池の充放電サイクル試験は、前記コ
イン型電池セルを用いて、正極に対する電流密度を０．
５ｍＡ／ｃｍ２とし、カットオフ電圧が４．５Ｖから
３．０Ｖの間、６０℃の温度下で充放電を５０サイクル
繰り返した後、放電容量を測定して初期放電容量に対す
る割合を求めた。In the charge / discharge cycle test of the secondary battery, the current density with respect to the positive electrode was 0.
After charging / discharging was repeated 50 cycles at a temperature of 60 ° C. at a cutoff voltage of 4.5 V to 3.0 V at 5 mA / cm 2 , the discharge capacity was measured and the ratio to the initial discharge capacity was obtained.
【００６７】＜マンガン酸リチウム粒子粉末の製造＞窒
素通気のもと、３．５モルの水酸化ナトリウムに０．５
モルの硫酸マンガンを加え全量を１Ｌとし、得られた水
酸化マンガンを９０℃で１時間熟成させた。熟成後、空
気を通気させ９０℃で酸化させ、水洗、乾燥後、酸化マ
ンガン粒子粉末を得た。<Production of Lithium Manganese Oxide Particle Powder> 0.5 mol of 3.5 mol sodium hydroxide was added under nitrogen aeration.
Molar manganese sulfate was added to make the total amount 1 L, and the obtained manganese hydroxide was aged at 90 ° C. for 1 hour. After aging, air was ventilated to oxidize at 90 ° C., and after washing with water and drying, manganese oxide particle powder was obtained.
【００６８】得られた酸化マンガン粒子粉末はＭｎ３Ｏ
４であり、粒子形状は粒状であり、平均粒子径４．８μ
ｍ、ＢＥＴ比表面積が０．６ｍ２／ｇであった。The obtained manganese oxide particle powder was Mn 3 O.
4 , the particle shape is granular, and the average particle diameter is 4.8 μm.
m, BET specific surface area was 0.6 m 2 / g.
【００６９】前記Ｍｎ３Ｏ４粒子粉末と炭酸リチウムと
をＬｉ／Ｍｎが０．５５の割合になるように１時間混合
し、均一な混合物を得た。得られた混合物５０ｇをアル
ミナるつぼに入れ、７５０℃、空気雰囲気で１０時間保
持してマンガン酸リチウム粒子粉末を得た。得られたマ
ンガン酸リチウム粒子粉末をボールミルで１時間解砕し
た。The Mn 3 O 4 particle powder and lithium carbonate were mixed for 1 hour at a Li / Mn ratio of 0.55 to obtain a uniform mixture. 50 g of the obtained mixture was put in an alumina crucible and kept in an air atmosphere at 750 ° C. for 10 hours to obtain lithium manganate particles. The obtained lithium manganate particle powder was crushed with a ball mill for 1 hour.
【００７０】得られたマンガン酸リチウム粒子粉末は平
均一次粒子径５．０μｍであって平均二次粒子径（Ｄ
５０）７．０μｍであって平均一次粒子径／平均二次粒
子径が０．７１であり、Ｄ１０／Ｄ５０が０．７４であ
ってＤ９０／Ｄ５０が１．３９であり、ＢＥＴ比表面積
値が０．４ｍ２／ｇ、タップ密度が２．１ｇ／ｍｌであ
った。得られたマンガン酸リチウム粒子粉末の走査型電
子顕微鏡写真の観察結果を図１に示す。同図に示す通
り、その粒子形状は鋭角部を有していない粒状であっ
た。The obtained lithium manganate particles had an average primary particle diameter of 5.0 μm and an average secondary particle diameter (D
50 ) 7.0 μm, the average primary particle diameter / average secondary particle diameter is 0.71, D 10 / D 50 is 0.74, D 90 / D 50 is 1.39, and BET The specific surface area value was 0.4 m 2 / g and the tap density was 2.1 g / ml. The observation result of the scanning electron micrograph of the obtained lithium manganate particle powder is shown in FIG. As shown in the figure, the particle shape was granular without sharp corners.
【００７１】ここで得たマンガン酸リチウム粒子粉末か
らなる正極活物質を用いて作製したコイン型電池は、初
期放電容量が１２０ｍＡｈ／ｇ、６０℃での５０サイク
ル後の容量維持率が９７％／５０ｃｙｃｌｅであった。The coin-type battery prepared by using the positive electrode active material composed of the lithium manganate particles powder obtained here had an initial discharge capacity of 120 mAh / g and a capacity retention rate of 97% / after 50 cycles at 60 ° C. It was 50 cycles.
【００７２】[0072]
【作用】本発明において最も重要な点は、本発明に係る
正極活物質は、大きな一次粒子径を有し、しかも、凝集
せず分散性に優れているという点である。The most important point in the present invention is that the positive electrode active material according to the present invention has a large primary particle size and is excellent in dispersibility without agglomeration.
【００７３】本発明においては、マンガン塩を中和した
後、熟成工程を設けたこと、高アルカリ、且つ、高温下
で酸化反応を行ったことによって、粒度分布が均一で大
きな酸化マンガン粒子を得ることができる。In the present invention, a manganese oxide particle having a uniform particle size distribution and large size is obtained by providing a aging step after neutralizing the manganese salt and performing an oxidation reaction at a high alkali and a high temperature. be able to.
【００７４】マンガン酸リチウム粒子の粒径は前駆体に
なる酸化マンガン粒子の粒径に大きく依存するから、前
記酸化マンガン粒子を用いることによって、マンガン酸
リチウム粒子粉末からなる正極活物質も大きな一次粒子
となり、粒度分布も優れている。Since the particle size of the lithium manganate particles largely depends on the particle size of the manganese oxide particles used as the precursor, by using the manganese oxide particles, the positive electrode active material composed of the lithium manganate particles is also a large primary particle. The particle size distribution is also excellent.
【００７５】本発明に係る正極活物質を用いた二次電池
の充放電サイクル特性が優れているのは、正極活物質の
比表面積が小さく、また、粒状であり鋭角部を有さない
粒子形状であるため電解液との反応性が押さえられ、塗
料化時の分散性及び充填性に優れることによるものと推
定している。The secondary battery using the positive electrode active material according to the present invention has excellent charge / discharge cycle characteristics because the positive electrode active material has a small specific surface area and is in the form of particles having no sharp corners. Therefore, it is presumed that this is because the reactivity with the electrolytic solution is suppressed, and the dispersibility and filling property at the time of forming a coating are excellent.
【００７６】[0076]
【実施例】次に、実施例及び比較例を示す。EXAMPLES Next, examples and comparative examples will be shown.
【００７７】実施例１〜６：実施例１は反応温度を８０
℃とした以外は、前記発明の実施の形態と同様にして、
マンガン酸リチウム粒子粉末を得た。実施例２は水酸化
ナトリウムの添加量を４．０モルとした以外は前記発明
の実施の形態と同様にして、マンガン酸リチウム粒子粉
末を得た。実施例３はＬｉ／Ｍｎ比を０．６０とした以
外は実施例２と同様にしてマンガン酸リチウム粒子粉末
を得た。実施例４はボールミル解砕時間を２０分とした
以外は、実施例２と同様にしてマンガン酸リチウム粒子
粉末を得た。実施例５は水酸化ナトリウムの添加量を
６．０モルとした以外は前記発明の実施の形態と同様に
して、マンガン酸リチウム粒子粉末を得た。実施例６は
ボールミル解砕時間を２０分とした以外は、実施例５と
同様にしてマンガン酸リチウム粒子粉末を得た。Examples 1 to 6: In Example 1, the reaction temperature was 80.
Except for the temperature was set in the same manner as in the embodiment of the invention,
Lithium manganate particles were obtained. In Example 2, lithium manganate particles were obtained in the same manner as in the embodiment of the present invention except that the amount of sodium hydroxide added was 4.0 mol. Lithium manganate particles were obtained in the same manner as in Example 2 except that the Li / Mn ratio was changed to 0.60. In Example 4, lithium manganate particles were obtained in the same manner as in Example 2 except that the ball mill crushing time was 20 minutes. In Example 5, lithium manganate particle powder was obtained in the same manner as in the embodiment of the present invention except that the amount of sodium hydroxide added was 6.0 mol. In Example 6, lithium manganate particles were obtained in the same manner as in Example 5 except that the ball mill crushing time was 20 minutes.
【００７８】比較例１〜４：比較例１として、前駆体の
Ｍｎ３Ｏ４粒子の代わりに電解ＭｎＯ２を用いた以外
は、前記発明の実施の形態と同様にして、マンガン酸リ
チウム粒子粉末を得た。比較例２として、水酸化ナトリ
ウムの添加量を１．０５モルとした以外は、前記発明の
実施の形態と同様にして、マンガン酸リチウム粒子粉末
を得た。比較例３として、熟成及び酸化反応温度を６０
℃とした以外は、比較例２と同様にして、マンガン酸リ
チウム粒子粉末を得た。比較例４として、水酸化ナトリ
ウムの添加量を２．０モルとした以外は、比較例２と同
様にして、マンガン酸リチウム粒子粉末を得た。Comparative Examples 1 to 4 As Comparative Example 1, lithium manganate particle powder was obtained in the same manner as in the embodiment of the present invention except that electrolytic MnO 2 was used in place of the precursor Mn 3 O 4 particles. Got As Comparative Example 2, lithium manganate particle powder was obtained in the same manner as the embodiment of the present invention except that the amount of sodium hydroxide added was 1.05 mol. As Comparative Example 3, the aging and oxidation reaction temperatures were set to 60.
Lithium manganate particles were obtained in the same manner as in Comparative Example 2 except that the temperature was changed to ° C. As Comparative Example 4, lithium manganate particles were obtained in the same manner as Comparative Example 2 except that the amount of sodium hydroxide added was 2.0 mol.
【００７９】このときの製造条件を表１に、得られたマ
ンガン酸リチウム粒子粉末の諸特性及び前記発明の実施
の形態と同様にして行った電池評価の結果を表２に示
す。The production conditions at this time are shown in Table 1, and various characteristics of the obtained lithium manganate particles and the results of battery evaluation conducted in the same manner as the embodiment of the invention are shown in Table 2.
【００８０】[0080]
【表１】 [Table 1]
【００８１】[0081]
【表２】 [Table 2]
【００８２】表２から明らかなように、比較例１〜４の
電池は充放電サイクル時の容量が大きく劣化しているの
に対して、前記発明の実施の形態の電池及び実施例１〜
６の各電池は容量の劣化が押さえられ、より良好な充放
電サイクル維持率を示している。また、充填密度に関し
ても、比較例１〜４では低いのに対して、前記発明の実
施の形態及び実施例１〜６では２．０ｇ／ｍｌより高
く、良好な充填密度を示している。これは、大粒子で分
散性の良い粒子であるため、比表面積が小さく粒状であ
ることが影響しているものと考えられる。As is clear from Table 2, the batteries of Comparative Examples 1 to 4 had a large deterioration in capacity during charge / discharge cycles, whereas the batteries of the embodiment of the invention and Examples 1 to
In each of the batteries of No. 6, deterioration of the capacity was suppressed, and a better charge / discharge cycle maintenance rate was shown. Further, the packing density is low in Comparative Examples 1 to 4, whereas it is higher than 2.0 g / ml in the embodiments and Examples 1 to 6 of the present invention, showing a good packing density. It is considered that this is because the particles are large particles and have good dispersibility, and thus have a small specific surface area and are granular.
【００８３】[0083]
【発明の効果】本発明に係る正極活物質は分散性及び充
填性が優れているので、充放電サイクル特性に優れた非
水電解液二次電池を提供することができる。Since the positive electrode active material according to the present invention has excellent dispersibility and filling properties, it is possible to provide a non-aqueous electrolyte secondary battery having excellent charge / discharge cycle characteristics.
【図１】発明の実施の形態で得られたマンガン酸リチウ
ム粒子粉末からなる正極活物質の電子顕微鏡写真（１５
００倍）を示す。FIG. 1 is an electron micrograph (15) of a positive electrode active material composed of lithium manganate particles obtained according to an embodiment of the invention.
00 times).
【図２】比較例１で作製したマンガン酸リチウム粒子粉
末の電子顕微鏡写真（３５００倍）を示す。FIG. 2 shows an electron micrograph (3500 times) of the lithium manganate particles powder produced in Comparative Example 1.
【図３】比較例３で作製したマンガン酸リチウム粒子粉
末の電子顕微鏡写真（３００００倍）を示す。FIG. 3 shows an electron micrograph (30000 times) of the lithium manganate particles powder produced in Comparative Example 3.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 前田 英明 山口県小野田市新沖１丁目１番１号 戸田 工業株式会社小野田工場内 (72)発明者 貞村 英昭 山口県小野田市新沖１丁目１番１号 戸田 工業株式会社小野田工場内 Ｆターム(参考） 4G048 AA04 AB02 AB06 AC06 AD04 AD06 AE05 5H029 AJ05 AK03 AL07 AL12 AM03 AM04 AM05 AM07 CJ02 CJ08 CJ11 CJ14 DJ16 EJ04 EJ12 HJ05 HJ14 5H050 AA07 BA16 BA17 CA09 CB08 CB12 EA10 EA24 FA17 GA02 GA10 GA14 GA15 HA05 HA14 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hideaki Maeda 1-1-1 Shinoki, Onoda City, Yamaguchi Prefecture Industrial Co., Ltd. Onoda Factory (72) Inventor Hideaki Sadamura 1-1-1 Shinoki, Onoda City, Yamaguchi Prefecture Industrial Co., Ltd. Onoda Factory F-term (reference) 4G048 AA04 AB02 AB06 AC06 AD04 AD06 AE05 5H029 AJ05 AK03 AL07 AL12 AM03 AM04 AM05 AM07 CJ02 CJ08 CJ11 CJ14 DJ16 EJ04 EJ12 HJ05 HJ14 5H050 AA07 BA16 BA17 CA09 CB08 CB12 EA10 EA24 FA17 GA02 GA10 GA14 GA15 HA05 HA14
Claims (3)
であって平均二次粒子径Ｄ５０（マンガン酸リチウム粒
子粉末の全体積を１００％として粒子径に対する累積割
合を求めたときの累積割合が５０％となる粒子径）が
２．５〜４０．０μｍであり、前記平均一次粒子径と前
記平均二次粒子径との比（平均一次粒子径／平均二次粒
子径）が０．５〜１．２であるマンガン酸リチウム粒子
粉末からなることを特徴とする非水電解質二次電池用正
極活物質。1. The average primary particle diameter is 3.0 to 20.0 μm.
And the average secondary particle diameter D 50 (the particle diameter at which the cumulative proportion with respect to the particle diameter is 50% when the total volume of the lithium manganate particle powder is 100%) is 2.5 to 40. And a ratio of the average primary particle diameter to the average secondary particle diameter (average primary particle diameter / average secondary particle diameter) of 0.5 to 1.2, which is composed of lithium manganate particle powder. A characteristic positive electrode active material for a non-aqueous electrolyte secondary battery.
粒子径Ｄ５０に対するＤ１０（マンガン酸リチウム粒子
粉末の全体積を１００％として粒子径に対する累積割合
を求めたときの累積割合が１０％となる粒子径）の比
（Ｄ１０／Ｄ５ ０）が０．５０以上であってＤ５０に対
するＤ９０（マンガン酸リチウム粒子粉末の全体積を１
００％として粒子径に対する累積割合を求めたときの累
積割合が９０％となる粒子径）の比（Ｄ９０／Ｄ５０）
が２．０以下である請求項１記載の非水電解質二次電池
用正極活物質。Cumulative percentage of time of obtaining the cumulative ratio wherein the particle diameter on the total volume of the D 10 (lithium manganate particles to the average secondary particle diameter D 50 of the lithium manganate particles as 100% and 10% Ratio (D 10 / D 5 0 ) of 0.50 or more and the total volume of D 90 (lithium manganate particle powder) to D 50 is 1
The ratio (D 90 / D 50 ) of the particle diameter at which the cumulative proportion is 90% when the cumulative proportion is calculated as 00%.
Is 2.0 or less, The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1.
し、次いで熟成した後、酸化反応を行って酸化マンガン
粒子粉末を得、該酸化マンガン粒子粉末とリチウム化合
物とを混合し、該混合物を７００〜１０００℃の温度範
囲で加熱することを特徴とする請求項１又は請求項２記
載の非水電解質二次電池用正極活物質の製造法。3. A manganese salt-containing reaction solution is neutralized and then aged, and then an oxidation reaction is performed to obtain manganese oxide particle powder. The manganese oxide particle powder and a lithium compound are mixed, and the mixture is mixed. The method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein heating is performed in a temperature range of 700 to 1000 ° C.
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| WO2006095594A1 (en) * | 2005-03-09 | 2006-09-14 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
| WO2007011053A1 (en) | 2005-07-21 | 2007-01-25 | Sumitomo Chemical Company, Limited | Positive electrode active material for nonaqueous electrolyte secondary battery |
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