JP2000058054A - Manufacture of positive-electrode active material for nonaqueous-electrolyte secondary battery, and positive- electrode active material for nonaqueous-electrolyte secondary battery obtained by the method - Google Patents
Manufacture of positive-electrode active material for nonaqueous-electrolyte secondary battery, and positive- electrode active material for nonaqueous-electrolyte secondary battery obtained by the methodInfo
- Publication number
- JP2000058054A JP2000058054A JP10226848A JP22684898A JP2000058054A JP 2000058054 A JP2000058054 A JP 2000058054A JP 10226848 A JP10226848 A JP 10226848A JP 22684898 A JP22684898 A JP 22684898A JP 2000058054 A JP2000058054 A JP 2000058054A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- secondary battery
- electrode active
- electrolyte secondary
- surface area
- 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
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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は負極にリチウム、リ
チウム合金またはカーボンを用いる非水系電解質二次電
池用の正極活物質の製造方法に関するものであり、特に
電池の生産時において初期不良の少いサイクル安定性に
優れた非水系電解質二次電池用の正極活物質の製造方法
および該方法によって得られた非水系電解質二次電池用
正極活物質に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery using lithium, a lithium alloy or carbon as a negative electrode. The present invention relates to a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery having excellent cycle stability, and a positive electrode active material for a non-aqueous electrolyte secondary battery obtained by the method.
【０００２】[0002]
【従来の技術】近年、携帯電話やノート型パソコンなど
の携帯機器の普及に伴い、高いエネルギー密度を有する
小型、軽量で高い容量を持つ二次電池の開発が強く望ま
れている。このようなものとしてリチウム、リチウム合
金あるいはカーボンを負極として用いるリチウムイオン
二次電池があり、現在その研究開発が盛んに行われてい
る。2. Description of the Related Art In recent years, with the spread of mobile devices such as mobile phones and notebook computers, there is a strong demand for the development of small, lightweight, high capacity secondary batteries having a high energy density. As such a device, there is a lithium ion secondary battery using lithium, a lithium alloy or carbon as a negative electrode, and research and development thereof are being actively carried out at present.
【０００３】リチウムコバルト複酸化物（ＬｉＣｏ
Ｏ２）を正極活物質に用いたリチウムイオン二次電池は
４Ｖ級の高い電圧が得られるため、高エネルギー密度を
持つ電池として期待され、実用化が進んでいる。これま
でリチウムコバルト複酸化物を用いた電池では優れたサ
イクル特性および電子導電率を得るための開発はこれま
で数多く提案されており、すでに多くの成果が報告され
ている。[0003] Lithium-cobalt double oxide (LiCo
Since a lithium ion secondary battery using O 2 ) as a positive electrode active material can obtain a voltage as high as 4 V, it is expected as a battery having a high energy density, and its practical use is progressing. Many developments to obtain excellent cycle characteristics and electronic conductivity of a battery using a lithium-cobalt double oxide have been proposed so far, and many results have already been reported.
【０００４】リチウムコバルト複酸化物（ＬｉＣｏ
Ｏ２）からなる非水系電解質二次電池用の正極活物質の
製造方法の一例を挙げると、炭酸リチウムと酸化コバル
トをＬｉ／Ｃｏモル比で０．９８〜１．０の範囲になる
ように精秤し混合してなる原料粉１００重量部に対して
２０〜３０重量部のバインダーとしてのビニルアルコー
ル樹脂水溶液を加えて混合しつつ造粒し、ついで酸素含
有雰囲気で８５０〜１０００℃の温度範囲で前記造粒物
を焼成した後、該焼成物を粉砕して得られるものであ
る。[0004] Lithium-cobalt double oxide (LiCo
An example of a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery composed of O 2 ) includes lithium carbonate and cobalt oxide in a Li / Co molar ratio of 0.98 to 1.0. To 100 parts by weight of the raw material powder obtained by precisely weighing and mixing, 20 to 30 parts by weight of a vinyl alcohol resin aqueous solution as a binder is added and mixed, and granulation is performed. And baking the granulated material, and then pulverizing the calcined product.
【０００５】[0005]
【発明が解決しようとする課題】しかしながらこれらの
研究開発の成果を踏まえても工業的に量産を考える場合
には、十分とはいえず解決すべき課題が残った。特に量
産工程中に使用する各種処理装置から不純物としてのＦ
ｅが混入し、リチウムコバルト複酸化物の正極活物質と
しての本来の特性が発揮されないことがあった。However, even considering the results of these researches and developments, there is still a problem to be solved when considering industrial mass production, which is not sufficient. In particular, F as impurities from various processing equipment used during the mass production process
e was mixed in, and the original characteristics of the lithium-cobalt double oxide as a positive electrode active material were sometimes not exhibited.
【０００６】本発明の目的は、生産時において初期不良
の少ないサイクル安定性に優れた非水電解質電池の供給
が可能となるリチウムコバルト複酸化物からなる非水系
電解質二次電池用正極活物質の製造方法およびこの方法
により得られた非水系電解質二次電池用正極活物質を提
供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a positive electrode active material for a non-aqueous electrolyte secondary battery comprising a lithium-cobalt double oxide capable of supplying a non-aqueous electrolyte battery having little initial failure and excellent cycle stability during production. An object of the present invention is to provide a production method and a positive electrode active material for a non-aqueous electrolyte secondary battery obtained by the method.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
本発明の第１の実施態様は、炭酸リチウムと酸化コバル
トを精秤し混合してなる原料粉にバインダーを加えて混
合しつつ造粒し、ついで酸素含有雰囲気下で前記造粒物
を焼成した後、該焼成物を粉砕してリチウムコバルト複
酸化物からなる非水系電解質二次電池用正極活物質を製
造するに際して、前記焼成物の粉砕を超硬合金製のピン
および表面硬化されたステンレス鋼製の円盤より構成さ
れるピンミルを用いて行う非水系電解質二次電池用正極
活物質の製造方法を特徴とするものである。According to a first embodiment of the present invention, a binder is added to raw material powder obtained by precisely weighing and mixing lithium carbonate and cobalt oxide, and granulation is performed while mixing and mixing. Then, after calcining the granulated material under an oxygen-containing atmosphere, when the calcined material is pulverized to produce a positive electrode active material for a non-aqueous electrolyte secondary battery composed of a lithium cobalt double oxide, The method is characterized by a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery in which pulverization is performed using a pin mill composed of a cemented carbide pin and a surface-hardened stainless steel disk.
【０００８】また本発明の第２の実施態様は、平均粒径
が１０μｍ以下、かつ比表面積が１．０ｍ２／ｇ以上の
炭酸リチウム（Ｌｉ２Ｃｏ３）と、比表面積が１．０〜
３．５ｍ２／ｇの酸化コバルト（Ｃｏ３Ｏ４）とを原料
粉として用いて前記第１の実施態様に係る製造方法によ
り得られ、かつ比表面積が０．３〜３．８ｍ２／ｇで、
Ｆｅ含有量が１００ｐｐｍ以下である非水系電解質二次
電池用正極活物質を特徴とするものである。In a second embodiment of the present invention, lithium carbonate (Li 2 Co 3 ) having an average particle diameter of 10 μm or less and a specific surface area of 1.0 m 2 / g or more is used.
It is obtained by the production method according to the first embodiment using 3.5 m 2 / g of cobalt oxide (Co 3 O 4 ) as a raw material powder, and has a specific surface area of 0.3 to 3.8 m 2 / g. so,
A positive electrode active material for a non-aqueous electrolyte secondary battery having an Fe content of 100 ppm or less is characterized.
【０００９】[0009]
【発明の実施の形態】本発明者らはリチウムコバルト複
酸化物の開発を進めるに当たって、初期特性を調べるた
めの電池試験において測定不良の試作電池が活物質の作
製ロットにより異なることがあることを見出した。すな
わち大量に活物質の合成を行う場合、最適と考えられる
同一条件で合成したとしても、容量の確認試験用の試作
電池では不良率が異なる事態が発生することがあった。
この点に関してさらに詳細な検討を加えた結果、これは
工程中に混入するＦｅの活物質中の含有量に依存してい
ることを見出した。DESCRIPTION OF THE PREFERRED EMBODIMENTS In developing a lithium-cobalt double oxide, the inventors of the present invention have found that, in a battery test for examining initial characteristics, a prototype battery having measurement failure may differ depending on the lot of active material produced. I found it. That is, when a large amount of active material is synthesized, even if the synthesis is performed under the same conditions that are considered to be optimal, a situation may occur in which the defective rate differs in a prototype battery for a capacity confirmation test.
As a result of further detailed examination on this point, it was found that this depends on the content of Fe mixed in the process in the active material.
【００１０】本発明による非水系電解質二次電池用正極
活物質の合成法は、従来とほぼ類似した工程を経るもの
で、まず炭酸リチウム（Ｌｉ２Ｃｏ３）および酸化コバ
ルト（Ｃｏ３Ｏ４）をＬｉ／Ｃｏモル比で０．９８〜
１．０の範囲になるように精秤し混合し、得られた原料
粉１００重量部に対して２０〜３０重量部のバインダー
としてのビニルアルコール樹脂水溶液を加えて混合しつ
つ造粒し、ついで酸素含有雰囲気で８５０〜１０００℃
の温度範囲で６時間以上で２０時間以下の時間に亘って
前記造粒物を焼成し、これを粉砕して非水系電解質二次
電池用正極活物質を得るものであって、本発明では前記
焼成物の粉砕に際して超硬合金製のピンおよび表面硬化
されたステンレス鋼製の円盤より構成されるピンミルを
用いて行うことを特徴とするものである。The method for synthesizing the positive electrode active material for a non-aqueous electrolyte secondary battery according to the present invention goes through a process substantially similar to the conventional one. First, lithium carbonate (Li 2 Co 3 ) and cobalt oxide (Co 3 O 4 ) From 0.98 to Li / Co molar ratio
The mixture was precisely weighed and mixed so as to be in the range of 1.0, and 20 to 30 parts by weight of a vinyl alcohol resin aqueous solution as a binder was added to 100 parts by weight of the obtained raw material powder, and the mixture was granulated while mixing. 850-1000 ° C in oxygen-containing atmosphere
The granulated material is fired for 6 hours or more and 20 hours or less in a temperature range of, and crushed to obtain a positive electrode active material for a non-aqueous electrolyte secondary battery. The pulverization of the fired product is performed using a pin mill composed of a cemented carbide pin and a surface-hardened stainless steel disk.
【００１１】このような構成を有するピンミルによる粉
砕工程を含む本発明の製造方法を実施するに際して、リ
チウム原料として平均粒径が１０μｍ以下で、かつ比表
面積が１．０ｍ２／ｇ以上の炭酸リチウム（Ｌｉ２Ｃｏ
３）を用い、さらにコバルト原料として比表面積が１．
０〜３．５ｍ２／ｇの酸化コバルト（Ｃｏ３Ｏ４）を用
いると、得られた非水系電解質二次電池用正極活物質は
比表面積が０．３〜０．８ｍ２／ｇとなり、Ｆｅ含有率
が１００ｐｐｍ以下となるものである。なお非水系電解
質二次電池用正極活物質の比表面積を０．３〜０．８ｍ
２／ｇとした理由は、０．３ｍ２／ｇ未満では該活物質
の反応性が悪化するために電池の容量が低下することと
なり、一方０．８ｍ２／ｇを超えると活物質を電池に組
み込む際の粉体のハンドリング性、具体的には活物質を
スラリー化し基体に塗布して電極にする際のハンドリン
グ性が悪化し、また電池の寿命が劣化することになるか
らである。また非水系電解質二次電池用正極活物質にお
けるＦｅ含有率が１００ｐｐｍを超えると、電池の不良
率が急激に上昇するからである。そして非水系電解質二
次電池用正極活物質の比表面積を０．３〜０．８ｍ２／
ｇとするためにはリチウム原料として平均粒径が１０μ
ｍ以下で、かつ比表面積が１．０ｍ２／ｇ以上の炭酸リ
チウム（Ｌｉ２Ｃｏ３）を用いるとともに、コバルト原
料として比表面積が１．０〜３．５ｍ２／ｇの酸化コバ
ルト（Ｃｏ３Ｏ４）を用いる必要があり、この範囲を外
れると所望の比表面積を得ることができない。In carrying out the production method of the present invention including a pulverizing step using a pin mill having such a constitution, lithium carbonate having an average particle diameter of 10 μm or less and a specific surface area of 1.0 m 2 / g or more is used as a lithium raw material. (Li 2 Co
3 ), and the specific surface area is 1.
When 0 to 3.5 m 2 / g of cobalt oxide (Co 3 O 4 ) is used, the obtained positive electrode active material for a non-aqueous electrolyte secondary battery has a specific surface area of 0.3 to 0.8 m 2 / g, The Fe content is 100 ppm or less. The specific surface area of the positive electrode active material for a non-aqueous electrolyte secondary battery is 0.3 to 0.8 m.
The reason for using 2 / g is that if it is less than 0.3 m 2 / g, the reactivity of the active material deteriorates and the capacity of the battery decreases, while if it exceeds 0.8 m 2 / g, the active material is This is because the handleability of the powder at the time of assembling into the substrate, specifically, the handleability when the active material is slurried and applied to the substrate to form an electrode is deteriorated, and the life of the battery is deteriorated. Also, when the Fe content in the positive electrode active material for a non-aqueous electrolyte secondary battery exceeds 100 ppm, the battery failure rate sharply increases. The specific surface area of the positive electrode active material for a non-aqueous electrolyte secondary battery is 0.3 to 0.8 m 2 /
In order to obtain g, the average particle diameter of the lithium raw material is 10 μm.
m or less, and specific surface area with use of 1.0 m 2 / g or more lithium carbonate (Li 2 Co 3), cobalt oxide specific surface area as cobalt raw material 1.0~3.5m 2 / g (Co 3 It is necessary to use O 4 ), and outside of this range, a desired specific surface area cannot be obtained.
【００１２】つぎに本発明に係る製造方法を詳述する
と、炭酸リチウム（Ｌｉ２Ｃｏ３）および酸化コバルト
（Ｃｏ３Ｏ４）をＬｉ／Ｃｏモル比で０．９８〜１．０
の範囲になるように精秤し混合し、得られた原料粉１０
０重量部に対して２０〜３０重量部のビニルアルコール
樹脂水溶液を加えて混合した原料粉末を混合造粒機に投
入する際に、炭酸リチウム（Ｌｉ２Ｃｏ３）および酸化
コバルト（Ｃｏ３Ｏ４）をそれぞれ単独で混合槽内に投
入して差し支えないが、より好ましくは予め混合粉とす
る。また造粒工程でのビニルアルコール樹脂からなるバ
インダー添加時は撹拌羽の回転速度を遅くし、さらに少
量づつ滴下して所望の平均粒径（通常５ｍｍ以下程度）
以上の大きな造粒物を生成させないことが望ましい。Next, the production method according to the present invention will be described in detail. Lithium carbonate (Li 2 Co 3 ) and cobalt oxide (Co 3 O 4 ) are mixed at a Li / Co molar ratio of 0.98 to 1.0.
The raw material powder 10 was precisely weighed and mixed so as to be in the range of
When a raw material powder obtained by adding and mixing 20 to 30 parts by weight of a vinyl alcohol resin aqueous solution with respect to 0 part by weight is charged into a mixing granulator, lithium carbonate (Li 2 Co 3 ) and cobalt oxide (Co 3 O 4) ) May be independently charged into the mixing tank, but more preferably, the mixed powder is prepared in advance. In addition, when adding a binder made of a vinyl alcohol resin in the granulation step, the rotation speed of the stirring blade is slowed down, and the mixture is added dropwise little by little to obtain a desired average particle diameter (usually about 5 mm or less).
It is desirable not to generate such large granules.
【００１３】引き続いて前記造粒物を酸素含有雰囲気で
８５０〜１０００℃の温度範囲で焼成し得られた焼成物
を粉砕する際に用いる従来のピンミルは、高速で回転す
る２つの円盤に多数のピンを取り付け、その噛み合わせ
により試料を粉砕するものである。しかし従来ノピンミ
ルでは粉砕時にピンは被粉砕物との衝突により摩耗し、
また円盤は高速で回転しているため被粉砕物との摩擦に
より摩耗する。このため通常の材質のピンミルの場合、
ピンおよび円盤の摩耗により該ピンおよび円盤からの金
属Ｆｅの粉砕物への混入が避けられない。[0013] The conventional pin mill used to pulverize the calcined material obtained by calcining the granulated material in an oxygen-containing atmosphere at a temperature in the range of 850 to 1000 ° C. uses a large number of disks rotating at high speed. A sample is ground by attaching pins and engaging the pins. However, in the conventional Nopin mill, the pins are worn by the collision with the material to be ground during grinding,
Further, since the disk is rotating at a high speed, it is worn by friction with an object to be ground. For this reason, in the case of a pin mill of normal material,
It is inevitable that metal Fe from the pin and the disc is mixed into the pulverized material due to the wear of the pin and the disc.
【００１４】したがって本発明では粉砕工程において使
用するピンミルを以下のように構成した。すなわちピン
を超硬合金製、例えばＷＣ鋼などで形成し、一方円盤は
被粉砕物と接する部分に耐摩耗性に優れた硬化層を持つ
ステンレス鋼で形成する。このようなステンレス鋼は超
硬合金で作製した場合と同様な効果が得られ、かつ経済
性に優れているため最適である。このような構成を有す
るピンミルを用いることにより、非水系電解質二次電池
用正極活物質に含有するＦｅの量を１００ｐｐｍ以下に
することができ、これにより電池の不良率の発生を大幅
に減少させることができるのである。Therefore, in the present invention, the pin mill used in the pulverizing step is constituted as follows. That is, the pin is made of a cemented carbide, for example, WC steel, while the disk is made of stainless steel having a hardened layer having excellent wear resistance at a portion in contact with the object to be ground. Such a stainless steel is optimal because it has the same effect as when it is made of a cemented carbide and is excellent in economy. By using a pin mill having such a configuration, the amount of Fe contained in the positive electrode active material for a non-aqueous electrolyte secondary battery can be reduced to 100 ppm or less, thereby greatly reducing the occurrence of a battery failure rate. You can do it.
【００１５】そして上記の耐摩耗性に優れた硬化層は、
例えば特開平８−３５０７５号公報記載のアンモニアガ
スと水素ガスの雰囲気中でグロー放電を行いイオン窒化
を行って、この窒化層上にＰＶＤ法で硬質被膜を形成さ
せる方法によりステンレス鋼上に形成することが可能で
ある。[0015] The cured layer having excellent abrasion resistance is
For example, glow discharge is performed in an atmosphere of ammonia gas and hydrogen gas described in Japanese Patent Application Laid-Open No. 8-35075 to perform ion nitriding, and a hard film is formed on the nitrided layer by PVD to form on a stainless steel. It is possible.
【００１６】[0016]
【実施例】以下本発明の実施例を、比較例とともに説明
する。 ［実施例］ （合成）リチウム／コバルトのモル比を１．０となるよ
うに、一次粒子を平均粒径が１０μｍ以下に粉砕した炭
酸リチウム（Ｌｉ２Ｃｏ３：純度９９％、比表面積１．
３ｍ２／ｇ）を２．５８８ｋｇ、酸化コバルト（ＣＯ３
Ｏ４；Ｃｏ含有量：７３．３重量％、比表面積３．４ｍ
２／ｇ）を５．５５４ｋｇを精秤、混合して混合粉とし
た後、混合造粒機「ハイスピードミキサー」（深江工業
株式会社製）を用いて底部回転羽の回転数を１８０ｒｐ
ｍとし５分間予備混合を行った。さらに前記回転数を１
２０ｒｐｍとし４重量％のＰＶＡ（ポリビニルアルコー
ル）水溶液を２．４ｋｇを加え、滴下後回転数を１８０
ｒｐｍに上げ、１ｍｍ程度の種粒子を作った。さらに回
転数を１２０ｒｐｍに下げ造粒し、１〜３ｍｍの造粒物
を作製した。この造粒物を１００℃で２時間乾燥し、さ
らにマグネシアセッターを用いて酸素流量３リットル／
分で加熱速度５℃／分により９００℃まで昇温し、１５
時間程度保持して焼成した。このように焼成したリチウ
ムコバルト複酸化物を３０μｍ以下に超硬合金製ピンお
よび硬化層を有する円盤により構成されるピンミルによ
り解砕し、ＢＥＴ吸着等温法により比表面積を測定し、
かつ含有するＦｅの量を求めた。EXAMPLES Examples of the present invention will be described below along with comparative examples. [Examples] (Synthesis) Lithium carbonate (Li 2 Co 3 : purity 99%, specific surface area 1: 1) obtained by pulverizing primary particles to an average particle diameter of 10 μm or less so that the molar ratio of lithium / cobalt becomes 1.0.
3m 2 / g), 2.588 kg of cobalt oxide (CO 3
O 4 ; Co content: 73.3% by weight, specific surface area 3.4 m
2 / g) was precisely weighed and mixed to obtain a mixed powder, and the number of rotations of the bottom rotary blade was set to 180 rpm using a mixing granulator “High Speed Mixer” (manufactured by Fukae Industry Co., Ltd.).
m and premixed for 5 minutes. Further, the rotation speed is set to 1
At 20 rpm, 2.4 kg of a 4% by weight aqueous solution of PVA (polyvinyl alcohol) was added.
rpm and seed particles of about 1 mm were made. The number of revolutions was further reduced to 120 rpm, and granulation was performed to produce a granulated product of 1 to 3 mm. The granulated product is dried at 100 ° C. for 2 hours, and further subjected to an oxygen flow rate of 3 L / m 2 using a magnesia setter.
In 5 minutes at a heating rate of 5 ° C./minute to 900 ° C.
It was baked while being held for about an hour. The thus-calcined lithium-cobalt double oxide is crushed by a pin mill composed of a hard metal pin and a disk having a hardened layer to 30 μm or less, and the specific surface area is measured by a BET adsorption isothermal method.
And the amount of Fe contained was determined.
【００１７】（電池評価）得られた活物質を用いて以下
のように電池を作製し、充放電容量を測定した。活物質
粉末１２０ｍｇにアセチレンブラック２２ｍｇおよびポ
リテトラフルオロエチレン樹脂（ＰＴＦＥ）８ｍｇを混
合し、２００ＭＰａの圧力で直径１１ｍｍにプレス成型
し、これを真空乾燥器中１２０℃で真空乾燥を行い正極
とした。そして図１にように正極ペレット５と、負極と
してＬｉメタルのペレット２を用い、さらに電解液には
１ＭのＬｉＰＦ６を支持塩とするエチレンカーボネイト
（ＥＣ）とジエチルカーボネート（ＤＥＣ）の等量混合
溶液を用いた。なおセパレータ３には膜厚２５μｍのポ
リエチレン多孔膜を２枚重ねて用いてガスケット４によ
りシールして２０３２型コイン電池をＡｒ雰囲気のグロ
ーブボックス中で組み立てた。なお図１において１は負
極缶、６は正極缶であり、図示していないが電解液は電
池内部の空隙に存在する。(Evaluation of Battery) Using the obtained active material, a battery was prepared as follows, and the charge / discharge capacity was measured. The active material powder (120 mg) was mixed with acetylene black (22 mg) and polytetrafluoroethylene resin (PTFE) (8 mg) and press-molded to a diameter of 11 mm at a pressure of 200 MPa, followed by vacuum drying at 120 ° C. in a vacuum dryer to obtain a positive electrode. As shown in FIG. 1, a positive electrode pellet 5 and a Li metal pellet 2 are used as a negative electrode, and an equal amount of ethylene carbonate (EC) and diethyl carbonate (DEC) using 1M LiPF 6 as a supporting salt is used as an electrolytic solution. The solution was used. The separator 3 was sealed with a gasket 4 using two 25 μm-thick polyethylene porous membranes, and a 2032 type coin battery was assembled in a glove box in an Ar atmosphere. In FIG. 1, reference numeral 1 denotes a negative electrode can and 6 denotes a positive electrode can. Although not shown, the electrolytic solution is present in a void inside the battery.
【００１８】このように作製した電池を１０時間程度放
電し、開回路電圧（ＯＣＶ）が安定した後、正極に対す
る電流密度を１．０ｍＡ／ｃｍ２として、カットオフ電
圧４．３〜３．０Ｖの条件で充放電試験を行った。電池
は全部で１００個作製して充放電試験を行って、充放電
サイクル数が２０回以下で内部短絡などにより試験でき
なくなった電池を不良電池として数えた。その結果を下
記する表１に示す。The battery thus manufactured was discharged for about 10 hours, and after the open circuit voltage (OCV) was stabilized, the current density with respect to the positive electrode was set to 1.0 mA / cm 2 , and the cutoff voltage was 4.3 to 3.0 V. A charge / discharge test was performed under the following conditions. A total of 100 batteries were manufactured and subjected to a charge / discharge test. A battery that could not be tested due to an internal short circuit or the like when the number of charge / discharge cycles was 20 or less was counted as a defective battery. The results are shown in Table 1 below.
【００１９】［比較例１］実施例と同様に作製し、焼成
後のピンミル粉砕時に超硬合金製ピンと表面硬化層を持
たないステンレス鋼製の円盤により構成されるピンミル
を用いて粉砕した。得られた活物質の比表面積およびＦ
ｅ含有量を求め、さらに実施例と同様に電池を作製し、
電池試験を行い不良電池の数を求め、その結果を表１に
示す。[Comparative Example 1] A pin mill made of a cemented carbide and a stainless steel disk having no hardened layer was used for pulverization using a pin mill after pulverization. Specific surface area and F of the obtained active material
e content was determined, and a battery was prepared in the same manner as in the example.
A battery test was performed to determine the number of defective batteries, and the results are shown in Table 1.
【００２０】［比較例２］実施例と同様に作製し、焼成
後のピンミル粉砕時にステンレス製ピンと表面硬化層を
持たないステンレス鋼製の円盤により構成されるピンミ
ルを用いて粉砕した。得られた活物質の比表面積および
Ｆｅ含有量を求め、さらに実施例と同様に電池を作製
し、電池試験を行い不良電池の数を求め、その結果を表
１に示す。Comparative Example 2 A pin mill made of a stainless steel pin and a stainless steel disk having no hardened layer was used for pulverization using a pin mill after firing. The specific surface area and Fe content of the obtained active material were determined. Further, batteries were prepared in the same manner as in the examples, and a battery test was performed to determine the number of defective batteries. The results are shown in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】以上の結果から本発明による製造方法によ
り合成されたリチウムコバルト複酸化物はＦｅの含有量
が低いため、活物質として用いた場合は初期不良の少な
い優れた電池を得られることが分かった。From the above results, it can be seen that the lithium-cobalt double oxide synthesized by the production method according to the present invention has a low Fe content, so that when used as an active material, an excellent battery with little initial failure can be obtained. Was.
【００２３】[0023]
【発明の効果】以上述べた通り本発明の非水系電解質二
次電池用正極活物質の製造方法および該方法により得ら
れた非水系電解質二次電池用正極活物質によれば、好ま
しい比表面積を有し、かつＦｅの含有量の低い非水系電
解質二次電池の正極活物質を得ることができ、また初期
不良の少ない電池の作製が可能である。As described above, according to the method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery of the present invention and the positive electrode active material for a non-aqueous electrolyte secondary battery obtained by the method, a preferable specific surface area is obtained. Thus, a positive electrode active material of a nonaqueous electrolyte secondary battery having a low Fe content can be obtained, and a battery with few initial defects can be manufactured.
【図１】電池試験に用いた２０３２型コイン電池の一部
破断斜視図である。FIG. 1 is a partially broken perspective view of a 2032 type coin battery used for a battery test.
１ 負極缶 ２ リチウム金属ペレット ３ セパレータ ４ ガスケット ５ 正極ペレット ６ 正極缶 DESCRIPTION OF SYMBOLS 1 Negative electrode can 2 Lithium metal pellet 3 Separator 4 Gasket 5 Positive electrode pellet 6 Positive electrode can
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G048 AA04 AB05 AC06 AD04 AE05 5H003 BA01 BA03 BA04 BB05 BC01 BD02 BD03 BD04 BD05 5H014 AA02 BB00 BB01 BB06 HH00 HH01 HH06 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G048 AA04 AB05 AC06 AD04 AE05 5H003 BA01 BA03 BA04 BB05 BC01 BD02 BD03 BD04 BD05 5H014 AA02 BB00 BB01 BB06 HH00 HH01 HH06
Claims (2)
合してなる原料粉にバインダーを加えて混合しつつ造粒
し、ついで酸素含有雰囲気下で前記造粒物を焼成した
後、該焼成物を粉砕してリチウムコバルト複酸化物から
なる非水系電解質二次電池用正極活物質を製造するに際
して、前記焼成物の粉砕を超硬合金製のピンおよび表面
硬化されたステンレス鋼製の円盤より構成されるピンミ
ルを用いて行うことを特徴とする非水系電解質二次電池
用正極活物質の製造方法。A raw material powder obtained by precisely weighing and mixing lithium carbonate and cobalt oxide is mixed with a binder and granulated, and then the granulated material is calcined in an oxygen-containing atmosphere. Pulverized to produce a positive electrode active material for a non-aqueous electrolyte secondary battery comprising a lithium-cobalt double oxide, the pulverization of the fired material is made up of a cemented carbide pin and a surface-hardened stainless steel disk. A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery, wherein the method is carried out using a pin mill.
が１．０ｍ２／ｇ以上の炭酸リチウム（Ｌｉ２Ｃｏ３）
と、比表面積が１．０〜３．５ｍ２／ｇの酸化コバルト
（Ｃｏ３Ｏ４）とを原料粉として用いて請求項１記載の
製造方法により得られ、かつ比表面積が０．３〜３．８
ｍ２／ｇで、Ｆｅ含有量が１００ｐｐｍ以下であること
を特徴とする非水系電解質二次電池用正極活物質。 2. Lithium carbonate (Li 2 Co 3 ) having an average particle size of 10 μm or less and a specific surface area of 1.0 m 2 / g or more.
And cobalt oxide (Co 3 O 4 ) having a specific surface area of 1.0 to 3.5 m 2 / g as a raw material powder, obtained by the production method according to claim 1, and having a specific surface area of 0.3 to 0.3 m 2 / g. 3.8
A positive electrode active material for a non-aqueous electrolyte secondary battery, characterized in that the Fe content is 100 ppm or less at m 2 / g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22684898A JP3560220B2 (en) | 1998-08-11 | 1998-08-11 | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery and positive electrode active material for non-aqueous electrolyte secondary battery obtained by the method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22684898A JP3560220B2 (en) | 1998-08-11 | 1998-08-11 | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery and positive electrode active material for non-aqueous electrolyte secondary battery obtained by the method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000058054A true JP2000058054A (en) | 2000-02-25 |
| JP3560220B2 JP3560220B2 (en) | 2004-09-02 |
Family
ID=16851521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22684898A Expired - Fee Related JP3560220B2 (en) | 1998-08-11 | 1998-08-11 | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery and positive electrode active material for non-aqueous electrolyte secondary battery obtained by the method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3560220B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002040154A1 (en) | 2000-11-15 | 2002-05-23 | Daicel Chemical Industries, Ltd. | Catalysts comprising n-substituted cyclic imides and processes for preparing organic compounds with the catalysts |
| JP2002198051A (en) * | 2000-12-27 | 2002-07-12 | Matsushita Electric Ind Co Ltd | Manufacturing method of positive electrode active material for nonaqueous electrolyte secondary battery |
| JP2002298846A (en) * | 2001-03-30 | 2002-10-11 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery and method for manufacturing the same |
| WO2002084765A1 (en) * | 2001-04-10 | 2002-10-24 | Mitsui Mining & Smelting Co., Ltd. | Lithium secondary battery-use active matter |
| WO2003003488A1 (en) * | 2001-06-27 | 2003-01-09 | Kabushiki Kaisha Toshiba | Positive electrode active material for secondary cell and nonaqueous electrolyte secondary cell using the same, and method for analysis of positive electrode active material for secondary cell |
| US20170098817A1 (en) * | 2014-05-21 | 2017-04-06 | GM Global Technology Operations LLC | Distributing conductive carbon black on active material in lithium battery electrodes |
-
1998
- 1998-08-11 JP JP22684898A patent/JP3560220B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002040154A1 (en) | 2000-11-15 | 2002-05-23 | Daicel Chemical Industries, Ltd. | Catalysts comprising n-substituted cyclic imides and processes for preparing organic compounds with the catalysts |
| JP2002198051A (en) * | 2000-12-27 | 2002-07-12 | Matsushita Electric Ind Co Ltd | Manufacturing method of positive electrode active material for nonaqueous electrolyte secondary battery |
| JP4604347B2 (en) * | 2000-12-27 | 2011-01-05 | パナソニック株式会社 | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery |
| JP2002298846A (en) * | 2001-03-30 | 2002-10-11 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery and method for manufacturing the same |
| WO2002084765A1 (en) * | 2001-04-10 | 2002-10-24 | Mitsui Mining & Smelting Co., Ltd. | Lithium secondary battery-use active matter |
| WO2003003488A1 (en) * | 2001-06-27 | 2003-01-09 | Kabushiki Kaisha Toshiba | Positive electrode active material for secondary cell and nonaqueous electrolyte secondary cell using the same, and method for analysis of positive electrode active material for secondary cell |
| US8409754B2 (en) | 2001-06-27 | 2013-04-02 | Kabushiki Kaisha Toshiba | Positive electrode active material for secondary cell and nonaqueous electrolyte secondary cell using the same, and method for analysis of positive electrode active material for secondary cell |
| US20170098817A1 (en) * | 2014-05-21 | 2017-04-06 | GM Global Technology Operations LLC | Distributing conductive carbon black on active material in lithium battery electrodes |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3560220B2 (en) | 2004-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6617073B1 (en) | Active material of positive electrode for non-aqueous electrode secondary battery and method for preparing the same and non-aqueous electrode secondary battery using the same | |
| KR101021991B1 (en) | Positive electrode material for lithium secondary battery and process for producing the same | |
| JP4794833B2 (en) | Positive electrode material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery | |
| JP3355126B2 (en) | Positive electrode active material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery | |
| US20050019662A1 (en) | Particulate positive electrode active material for a lithium secondary cell | |
| KR101487468B1 (en) | Spinel type lithium-manganese-nickel-containing composite oxide | |
| JP2012079464A (en) | Positive electrode active material for nonaqueous electrolyte secondary battery and manufacturing method thereof and nonaqueous electrolyte secondary battery using positive electrode active material | |
| KR100734595B1 (en) | Positive electrode material for lithium secondary cell and process for producing the same | |
| JP2006318929A (en) | Cathode active substance for lithium secondary battery, and nonaqueous lithium secondary battery | |
| JP2001110420A (en) | Manufacturing method for substance for activating positive electrode for nonaqueous electrolyte secondary battery and substance for activating positive electrode for the nonaqueous electrolyte secondary battery obtainable by the manufacturing method | |
| JP2006318928A (en) | Cathode active substance for lithium secondary battery, and nonaqueous lithium secondary battery | |
| JP2004311427A (en) | Positive electrode active material for lithium secondary battery and its manufacturing method and non-aqueous lithium secondary battery | |
| JPWO2020022305A1 (en) | Positive electrode active material | |
| JP3560220B2 (en) | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery and positive electrode active material for non-aqueous electrolyte secondary battery obtained by the method | |
| JP2016051548A (en) | Positive electrode material for nonaqueous electrolyte secondary battery, manufacturing method thereof, and nonaqueous electrolyte secondary battery arranged by use of positive electrode material | |
| JP2001297761A (en) | Positive electrode activator for nonaqueous electrolyte secondary cell | |
| JP7274125B2 (en) | Positive electrode active material for all-solid-state lithium-ion secondary battery and all-solid-state lithium-ion secondary battery | |
| JP2001185142A (en) | Positive electrode active material for lithium ion secondary battery and manufacturing method therefor | |
| JP6633161B1 (en) | Positive electrode active material, method for producing the same, positive electrode, and lithium ion battery | |
| JP3620744B2 (en) | Method for producing active material for lithium secondary battery | |
| KR102563295B1 (en) | Positive electrode active material by solid phase synthesis and method for manufacturing the same | |
| CN116022858B (en) | Lithium cobaltate powder and positive electrode material | |
| JP2003331843A (en) | Positive active material for nonaqueous electrolyte secondary battery and its manufacturing method | |
| JP3344853B2 (en) | Positive active material for non-aqueous lithium secondary battery and lithium secondary battery | |
| WO2020175552A1 (en) | Positive electrode active material for lithium ion secondary battery, method for manufacturing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040305 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040507 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040520 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |