JPH0922692A - Cobalt hydroxide and tricobalt tetraoxide for active material of nonaqueous electrolyte battery and manufacture thereof - Google Patents
Cobalt hydroxide and tricobalt tetraoxide for active material of nonaqueous electrolyte battery and manufacture thereofInfo
- Publication number
- JPH0922692A JPH0922692A JP7168489A JP16848995A JPH0922692A JP H0922692 A JPH0922692 A JP H0922692A JP 7168489 A JP7168489 A JP 7168489A JP 16848995 A JP16848995 A JP 16848995A JP H0922692 A JPH0922692 A JP H0922692A
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- tank
- active material
- cobalt hydroxide
- electrolyte battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- 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
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
正極活物質であるリチウム複合コバルト酸化物の合成に
用いる原材料に関するものであり、とくに水酸化コバル
トとこれを熱処理して得られる四酸化三コバルトに関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a raw material used for synthesizing a lithium composite cobalt oxide which is a positive electrode active material for a non-aqueous electrolyte secondary battery, and particularly to a cobalt hydroxide and a material obtained by heat treating the same. The present invention relates to tricobalt tetroxide.
【０００２】[0002]
【従来の技術】近年、民生用電子機器のポータブル化、
コードレス化が急激に進んでいる。現在、これら電子機
器の駆動用電源としての役割を、ニッケル−カドミウム
電池あるいは密閉型小型鉛蓄電池が担っているが、ポー
タブル化、コードレス化が進展し、定着するにしたが
い、駆動用電源となる二次電池の高エネルギー密度化、
小型軽量化の要望が強くなっている。2. Description of the Related Art In recent years, portable electronic devices have become more portable.
Cordless use is rapidly progressing. Currently, nickel-cadmium batteries or sealed small lead-acid batteries play the role of power sources for driving these electronic devices. However, as portable devices and cordless devices have progressed and they have become established, they will become drive power sources. High energy density of secondary batteries,
The demand for smaller and lighter is increasing.
【０００３】このような状況から、高い充放電電圧を示
すリチウム複合遷移金属酸化物例えばＬｉＣｏＯ2を正
極活物質に用い、リチウムイオンの挿入、離脱を利用し
た非水電解液二次電池が提案されている。（例えば特開
昭６３−５９５０７号公報） 特にＬｉＣｏＯ2については例えば特開平１−３０４６
６４号公報、特開平５−１５１９９８号公報、特開平５
−５４８８８号公報に見られるようにその製法や形状、
粒子の大きさ等を検討したものが多数報告されている。Under such circumstances, a non-aqueous electrolyte secondary battery has been proposed in which a lithium composite transition metal oxide exhibiting a high charge / discharge voltage, for example, LiCoO 2 , is used as a positive electrode active material, and insertion and removal of lithium ions are utilized. ing. (For example, Japanese Unexamined Patent Publication No. 63-59507) Particularly, for LiCoO 2 , for example, Japanese Unexamined Patent Publication No. 1-3046.
64, JP-A-5-151998, JP-A-5
The manufacturing method and the shape,
Many reports have been made on the study of particle size and the like.
【０００４】[0004]
【発明が解決しようとする課題】しかし、これまで報告
されているＬｉＣｏＯ2を正極活物質に用いた非水電解
液二次電池では、充放電サイクルを繰り返し行う事によ
り、その電池放電容量が徐々に減少するというサイクル
劣化の問題が明らかとなった。However, in the non-aqueous electrolyte secondary battery using LiCoO 2 as the positive electrode active material, which has been reported so far, the battery discharge capacity is gradually increased by repeating the charge / discharge cycle. It became clear that the problem of cycle deterioration was that the number of cycles decreased.
【０００５】本発明者らが、十分検討を重ねた結果、こ
のような特性劣化は以下のことが原因であることが解っ
た。As a result of thorough investigations by the present inventors, it has been found that such characteristic deterioration is caused by the following.
【０００６】すなわち、サイクル劣化した電池を分解
し、極板の観察を行った結果、充放電サイクルを繰り返
した正極板では、正極活物質の微粉化が起こっている事
が判明した。That is, as a result of disassembling the cycle-deteriorated battery and observing the electrode plate, it was found that in the positive electrode plate after repeated charge and discharge cycles, the positive electrode active material was pulverized.
【０００７】ＬｉＣｏＯ2は電池の充放電にともない、
その格子定数が変化する事が報告されており（Ｊ．Ｎ．
Ｒｅｉｍｅｒｓ ａｎｄ Ｊ．Ｒ．Ｄａｈｎ Ｊ．Ｅｌ
ｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．２０９１，ｖｏｌ．１３
９（１９９２））、特に結晶のＣ軸方向の膨張収縮が大
きい事が知られている。LiCoO 2 is used as the battery is charged and discharged,
It has been reported that the lattice constant changes (J.N.
Reimers and J.M. R. Dahn J. El
electrochem. Soc. 2091, vol. 13
9 (1992)), and it is known that the crystal particularly expands and contracts in the C-axis direction.
【０００８】このように充放電サイクルを繰り返す事に
よって活物質が膨張、収縮し、粒子の微細化や、極板か
らの離脱が生じ、充放電に関与できる活物質量が減少し
た事が原因である事が明かとなった。Due to the fact that the active material expands and contracts by repeating the charge and discharge cycle in this way, the particles become finer and detach from the electrode plate, and the amount of the active material that can participate in the charge and discharge decreases. One thing became clear.
【０００９】本発明の目的は、上記した従来の正極に関
する問題点の解決を図るものであり、特定の原料を用い
て合成することによってより良い、正極活物質を提供
し、充放電特性の優れた非水電解液二次電池を提供する
ものである。An object of the present invention is to solve the above-mentioned problems associated with the conventional positive electrode, to provide a better positive electrode active material by synthesizing using a specific raw material, and to provide excellent charge / discharge characteristics. And a non-aqueous electrolyte secondary battery.
【００１０】[0010]
【課題を解決するための手段】このような問題を解決す
るために、我々は、正極活物質の原料であるコバルト化
合物の製造方法について鋭意検討を行い、粒子内におけ
るコバルト原子の配列、粒子形状、粒子径を制御するこ
とにより、サイクル劣化を完全に防止するに至った。[Means for Solving the Problems] In order to solve such a problem, we have diligently studied a method for producing a cobalt compound, which is a raw material of a positive electrode active material, and have made an arrangement of cobalt atoms in the particle and a shape of the particle. By controlling the particle size, cycle deterioration was completely prevented.
【００１１】具体的に本発明は、ＬｉＣｏＯ2を正極活
物質として合成する際のコバルト源としてコバルト水酸
化物を２００℃〜７００℃の温度範囲で熱処理したもの
を用い、このコバルト水酸化物はｐＨ、温度を調整した
槽内にコバルト塩水溶液とか性アルカリ水溶液をその濃
度、流量を制御しながら連続的に供給、撹拌して得たも
のである。Specifically, the present invention uses a cobalt hydroxide which is heat-treated in a temperature range of 200 ° C. to 700 ° C. as a cobalt source when synthesizing LiCoO 2 as a positive electrode active material. It was obtained by continuously supplying and stirring an aqueous cobalt salt solution and an aqueous alkaline solution while controlling the concentration and flow rate in a tank whose pH and temperature were adjusted.
【００１２】コバルト塩としては硫酸コバルトもしくは
硫酸コバルトと塩化コバルトの混合水溶液が好ましく、
混合塩水溶液の濃度、供給量、槽内温度が一定として、
ｐＨ値が１１．０〜１３．５の範囲内に制御する事が望
ましい。The cobalt salt is preferably cobalt sulfate or a mixed aqueous solution of cobalt sulfate and cobalt chloride,
Assuming that the concentration of the mixed salt aqueous solution, the supply amount, and the temperature inside the tank are constant,
It is desirable to control the pH value within the range of 11.0 to 13.5.
【００１３】また、硫酸コバルトと塩化コバルトの混合
塩水溶液における硫酸イオンと塩素イオンのモル比（Ｃ
ｌ-／ＳＯ4 2-）は０より大きく５以下である事が望まし
い。Further, the molar ratio of the sulfate ion to the chloride ion in the mixed salt aqueous solution of cobalt sulfate and cobalt chloride (C
It is desirable that l − / SO 4 2− ) be greater than 0 and 5 or less.
【００１４】更に本発明における製造法のような高いｐ
Ｈ領域では生成したコバルト水酸化物が酸化され易いた
め、安定化のために槽内に添加剤として硫酸アンモニウ
ム、塩化アンモニウム、硫酸ナトリウム、塩化ナトリウ
ム、ヒドラジン、ヒドラジン塩の少なくとも１種を添加
することが好ましい。Furthermore, the high p as in the manufacturing method of the present invention is used.
In the H region, since the generated cobalt hydroxide is easily oxidized, at least one of ammonium sulfate, ammonium chloride, sodium sulfate, sodium chloride, hydrazine and hydrazine salt may be added as an additive in the tank for stabilization. preferable.
【００１５】このような方法で製造されたコバルト水酸
化物は板状をしており、ＳＥＭ写真における定方向径
（Ｆｅｒｅｔ ｄｉａｍｅｔｅｒ）を０．１〜１０μｍ
に制御することが可能となり、このようなコバルト化合
物を熱処理して四酸化三コバルトを得てさらにこの四酸
化三コバルトを用いてＬｉＣｏＯ2を作製し正極活物質
として用いることにより、前記課題を解決することがで
きる。The cobalt hydroxide produced by such a method has a plate-like shape, and the directional diameter (Feret diameter) in the SEM photograph is 0.1 to 10 μm.
The above problem can be solved by heat-treating such a cobalt compound to obtain tricobalt tetroxide, and using this tricobalt tetroxide to prepare LiCoO 2 and using it as a positive electrode active material. can do.
【００１６】なお、定方向径（Ｆｅｒｅｔ ｄｉａｍｅ
ｔｅｒ）とは、ＳＥＭ写真において様々な方向を向いた
粒子の径をある一定方向から読みとり、平均した物であ
る。（参考文献：粉体工学の基礎 ｐ．２８５（日刊工
業新聞社編））It should be noted that the constant direction diameter (Feret diameter)
ter) is an average value obtained by reading the diameters of particles in various directions in a SEM photograph from a certain direction. (Reference: Basics of powder engineering p.285 (edited by Nikkan Kogyo Shimbun))
【００１７】[0017]
【作用】コバルト塩である炭酸コバルト、酸化コバルト
等は粒子中における結晶はランダムに配列したいわゆる
多結晶状態であり、このためこれらを原料に用いたＬｉ
ＣｏＯ2は同様の多結晶状態となる。[Function] Cobalt salts such as cobalt carbonate and cobalt oxide are in a so-called polycrystal state in which crystals are randomly arranged in the particles.
CoO 2 is in the same polycrystalline state.
【００１８】また、特開平５−５４８８８号公報に示す
様に、コバルト塩として水酸化コバルトを原料にした場
合も、単にコバルト塩水溶液にアルカリ溶液を加えて生
成する水酸化コバルトはその反応溶液中におけるｐＨ、
温度、撹拌等が一定でないため水酸化コバルト粒子成長
の条件が不安定となり、生成する水酸化コバルトはやは
り多結晶な物となってしまう。Further, as shown in JP-A-5-54888, even when cobalt hydroxide is used as a raw material as a cobalt salt, cobalt hydroxide produced by simply adding an alkaline solution to an aqueous solution of cobalt salt is present in the reaction solution. PH at
Since the temperature, stirring, etc. are not constant, the conditions for growing the cobalt hydroxide particles become unstable, and the formed cobalt hydroxide is also polycrystalline.
【００１９】そのためこのような多結晶なコバルト化合
物を原料として用いた場合、合成されるＬｉＣｏＯ2も
微細な結晶がランダムに配列した多結晶構造となる。Therefore, when such a polycrystalline cobalt compound is used as a raw material, LiCoO 2 synthesized also has a polycrystalline structure in which fine crystals are randomly arranged.
【００２０】このような多結晶構造を有するＬｉＣｏＯ
2を用いて二次電池を構成し、充放電を行った場合、微
細な結晶が膨張、収縮を繰り返す事によって、多結晶体
粒子中の結晶粒界において構造が破壊され、粒子が微細
化し、電池集電体から脱離する。その結果電池の放電容
量が低下しサイクル劣化を引き起こしている事が明かと
なった。LiCoO having such a polycrystalline structure
When a secondary battery is constructed using 2 , when charging and discharging are performed, fine crystals repeatedly expand and contract, thereby destroying the structure at the crystal grain boundaries in the polycrystalline particles and making the particles finer, Disconnect from the battery current collector. As a result, it became clear that the discharge capacity of the battery was reduced and cycle deterioration was caused.
【００２１】しかし、本発明のコバルト水酸化物の製造
方法を用いた場合、コバルト塩の濃度、槽温度、撹拌速
度、ｐＨ等を制御する事により、槽内で生成した微細な
結晶が成長する形でコバルト水酸化物粒子を形成するた
め、結晶が非常に良好な状態で同一方向に配列してい
る。However, when the method for producing cobalt hydroxide according to the present invention is used, fine crystals produced in the tank grow by controlling the concentration of the cobalt salt, tank temperature, stirring speed, pH and the like. In order to form cobalt hydroxide particles, the crystals are aligned in the same direction in a very good state.
【００２２】そして、このコバルト水酸化物におけるコ
バルト原子の結晶学的な配列が保たれた状態で四酸化三
コバルト（Ｃｏ3Ｏ4）が作製され、この四酸化三コバル
ト（Ｃｏ3Ｏ4）とリチウム塩とを反応させてＬｉＣｏＯ
2を作製すると、結晶粒界の非常に少ないＬｉＣｏＯ2が
得られる。このような構造を有するＬｉＣｏＯ2を用い
て二次電池を構成し、充放電を行った場合、粒子構造破
壊の原因となる結晶粒界が非常に少ない為、粒子の微細
化、脱落が防止でき、良好なサイクル特性を実現する事
ができる。[0022] Then, the tricobalt tetroxide in cobalt hydroxide in a state of crystallographic arrangement is kept cobalt atom (Co 3 O 4) is produced, the tricobalt tetraoxide (Co 3 O 4) To react with lithium salt to form LiCoO
When 2 is produced, LiCoO 2 having very few crystal grain boundaries can be obtained. When a rechargeable battery is constructed using LiCoO 2 having such a structure and charged and discharged, there are very few crystal grain boundaries that cause particle structure destruction, so that it is possible to prevent the particles from becoming fine and falling off. Good cycle characteristics can be realized.
【００２３】また、高いｐＨ領域においては生成したコ
バルト水酸化物が容易に酸化され易く、十分な結晶成長
が阻害され易くなる。Further, in a high pH region, the produced cobalt hydroxide is easily oxidized, and sufficient crystal growth is easily hindered.
【００２４】このため、槽内への添加剤として硫酸アン
モニウム、塩化アンモニウム、硫酸ナトリウム、塩化ナ
トリウム、ヒドラジン、ヒドラジン塩を用いると生成し
たコバルト水酸化物の結晶核が安定化し、より十分に結
晶の成長した粒子を得る事ができる。Therefore, when ammonium sulfate, ammonium chloride, sodium sulfate, sodium chloride, hydrazine, or hydrazine salt is used as an additive in the bath, the crystal nuclei of the produced cobalt hydroxide are stabilized, and the crystal growth is more sufficiently achieved. The obtained particles can be obtained.
【００２５】[0025]
【実施例】以下、図面とともに本発明の具体的な実施例
を説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of the present invention will be described below with reference to the drawings.
【００２６】図１に本実施例および比較例で用いた円筒
系電池の縦断面図を示す。図１において１は耐有機電解
液性のステンレス鋼板を加工した電池ケース、２は安全
弁を設けた封口板、３は絶縁パッキングを示す。４は極
板群であり、正極板５および負極板６がセパレータ７を
介して複数回渦巻状に巻回されてケース内に収納されて
いる。そして上記正極板５からは正極アルミリード５ａ
が引き出されて封口板２に接続され、負極板６からは負
極ニッケルリード６ａが引き出されて電池ケース１の底
部に接続されている。８は絶縁リングで極板群４の上下
部にそれぞれ設けられている。FIG. 1 shows a vertical cross-sectional view of the cylindrical battery used in this example and the comparative example. In FIG. 1, 1 is a battery case formed by processing a stainless steel plate resistant to organic electrolyte, 2 is a sealing plate provided with a safety valve, and 3 is an insulating packing. Reference numeral 4 denotes an electrode plate group, in which the positive electrode plate 5 and the negative electrode plate 6 are spirally wound a plurality of times via the separator 7 and housed in the case. Then, from the positive electrode plate 5, a positive electrode aluminum lead 5a is formed.
Is drawn out and connected to the sealing plate 2, and the negative electrode nickel lead 6a is drawn out from the negative electrode plate 6 and connected to the bottom portion of the battery case 1. Reference numeral 8 denotes an insulating ring provided on the upper and lower portions of the electrode plate group 4, respectively.
【００２７】以下、負極板６、電解液等について詳しく
説明する。負極板６は、コークスを加熱処理した炭素粉
１００重量部に、フッ素樹脂系結着剤１０重量部を混合
し、カルボキシメチルセルロース水溶液に懸濁させてペ
ースト状にした。そしてこのペーストを厚さ０．０１５
ｍｍの銅箔の表面に塗着し、乾燥後０．２ｍｍに圧延
し、幅３７ｍｍ、長さ２８０ｍｍの大きさに切り出して
負極板とした。The negative electrode plate 6, the electrolytic solution and the like will be described in detail below. The negative electrode plate 6 was made into a paste by mixing 100 parts by weight of carbon powder obtained by heat-treating coke with 10 parts by weight of a fluororesin-based binder and suspending the mixture in an aqueous carboxymethyl cellulose solution. And this paste is 0.015
It was applied to the surface of a copper foil of mm, dried and rolled to 0.2 mm, and cut into a size of width 37 mm and length 280 mm to obtain a negative electrode plate.
【００２８】電解液には炭酸エチレンと炭酸ジエチルの
等容積混合溶媒に、六フッ化リン酸リチウム１モル／ｌ
の割合で溶解したものを用いて極板群４に注入した後、
電池を密封口し、試験電池とした。As the electrolytic solution, 1 mol / l of lithium hexafluorophosphate was mixed in an equal volume mixed solvent of ethylene carbonate and diethyl carbonate.
After injecting into the electrode plate group 4 using the one dissolved at a ratio of
The battery was sealed and used as a test battery.
【００２９】以下、正極活物質の合成法について詳しく
説明する。コバルト水酸化物を製造する析出槽として、
１００ｌのタンクを用い、コバルト塩水溶液として６０
ｇ／ｌのコバルト金属を溶解した硫酸コバルト、か性ア
ルカリ水溶液として２５重量％の水酸化ナトリウム溶液
を用いた。このタンク内へコバルト塩溶液を８ｌ／ｈの
一定流量で導入し、槽内温度を４０℃に保ち、十分撹拌
しながら、水酸化ナトリウム溶液を一定範囲内のｐＨ値
を保持するために間欠的に添加した。The method for synthesizing the positive electrode active material will be described in detail below. As a precipitation tank for producing cobalt hydroxide,
Using a 100 l tank, 60 as a cobalt salt aqueous solution
A 25% by weight sodium hydroxide solution was used as a caustic alkaline aqueous solution of cobalt sulfate in which g / l of cobalt metal was dissolved. The cobalt salt solution was introduced into this tank at a constant flow rate of 8 l / h, the temperature inside the tank was kept at 40 ° C., and the sodium hydroxide solution was intermittently maintained to maintain a pH value within a predetermined range while sufficiently stirring. Was added to.
【００３０】なおｐＨは槽温度において測定を行ってい
る。この一定範囲のｐＨ値として、１０．７５〜１１．
０、１１．０〜１１．２５、１１．２５〜１１．５、１
１．５〜１１．７５、１１．７５〜１２．０、１２．０
〜１２．２５、１２．２５〜１２．５、１２．５〜１
２．７５、１２．７５〜１３．０、１３．０〜１３．２
５、１３．２５〜１３．５、１３．５〜１３．７５の１
２段階に変化させてコバルト水酸化物を生成し、水洗、
乾燥した。The pH is measured at the bath temperature. As the pH value in this certain range, 10.75 to 11.
0, 11.0 to 11.25, 11.25 to 11.5, 1
1.5-11.75, 11.75-12.0, 12.0
~ 12.25, 12.25 ~ 12.5, 12.5 ~ 1
2.75, 12.75 to 13.0, 13.0 to 13.2
5, 13.25 to 13.5, 13.5 to 13.75
Cobalt hydroxide is generated in two steps, washed with water,
Dried.
【００３１】図２に本実施例による方法で製造されたコ
バルト水酸化物のＳＥＭ写真観察における結晶構造の模
式図を示す。図から判るように本実施例の方法で製造し
たコバルト水酸化物は全て図２に示したような板状の粒
子となっている。FIG. 2 shows a schematic diagram of the crystal structure of the cobalt hydroxide produced by the method according to this example, as observed by an SEM photograph. As can be seen from the figure, all the cobalt hydroxides produced by the method of this example are plate-like particles as shown in FIG.
【００３２】なお、ｐＨの測定は４０℃の状態で測定を
行い、例えばｐＨを１１．２５〜１１．５で制御した場
合、析出ｐＨ値は下限値が１１．２５、上限値が１１．
５の範囲で変化している。The pH is measured at 40 ° C. When the pH is controlled at 11.25 to 11.5, for example, the precipitation pH value has a lower limit value of 11.25 and an upper limit value of 11.
It changes in the range of 5.
【００３３】実際にはｐＨ値が１１．２８になると水酸
化ナトリウム水溶液が添加され、ｐＨ値が１１．４２に
なると水酸化ナトリウムの供給ポンプが停止するように
設定されている。In practice, the sodium hydroxide aqueous solution is added when the pH value reaches 11.28, and the sodium hydroxide supply pump is set to stop when the pH value reaches 11.42.
【００３４】その後、水洗、脱水処理を行った後、空気
雰囲気下、３００℃で熱処理を行い、四三酸化コバルト
とした後、炭酸リチウムと原子比で１対１になるように
混合し、酸化雰囲気下において９００℃で１０時間焼成
してＬｉＣｏＯ2を合成した。Then, after washing with water and dehydration, heat treatment is carried out at 300 ° C. in an air atmosphere to form cobalt tetraoxide, and then mixed with lithium carbonate in an atomic ratio of 1: 1 and oxidized. LiCoO 2 was synthesized by firing in an atmosphere at 900 ° C. for 10 hours.
【００３５】合成されたＬｉＣｏＯ2は、柔らかい凝集
塊状物として得られ、通常の粉砕機のように強い圧縮力
や、衝撃力、せん断力を印可する必要はなく、弱い加圧
力で容易に粉体状にほぐれる物であり、スクリーンメッ
シュにより容易に微粉体を得る事ができる。The synthesized LiCoO 2 is obtained as a soft agglomerate, and it is not necessary to apply a strong compressive force, impact force or shearing force as in a usual pulverizer, and it is easily powdered with a weak pressing force. It is a loose material, and a fine powder can be easily obtained with a screen mesh.
【００３６】図３に本実施例で合成したＬｉＣｏＯ2の
ＳＥＭ写真観察における結晶構造の模式図を示す。図２
のコバルト水酸化物と同様に板状の粒子が形成されてい
る事が明らかにわかる。FIG. 3 shows a schematic view of the crystal structure of the LiCoO 2 synthesized in this example, observed by an SEM photograph. FIG.
It can be clearly seen that plate-like particles are formed in the same manner as in the cobalt hydroxide of.
【００３７】以後、正極板の製造法を説明する。正極板
は、まず正極活物質であるＬｉＣｏＯ2の粉末１００重
量部に、アセチレンブラック３重量部、フッ素樹脂系結
着剤７重量部を混合し、カルボキシメチルセルロース水
溶液に懸濁させてペースト状にする。このペーストをア
ルミ箔の両面に塗着し、２５０℃で熱処理を行った後、
圧延を行った。Hereinafter, a method for manufacturing the positive electrode plate will be described. The positive electrode plate is prepared by first mixing 100 parts by weight of LiCoO 2 powder, which is a positive electrode active material, with 3 parts by weight of acetylene black and 7 parts by weight of a fluororesin binder and suspending them in an aqueous carboxymethylcellulose solution to form a paste. . After applying this paste to both sides of aluminum foil and heat treating at 250 ° C,
It was rolled.
【００３８】そして正極板と負極板を、セパレータを介
して渦巻き上に巻回し、直径１３．８ｍｍ、高さ５０ｍ
ｍの電池ケース内に収納した。Then, the positive electrode plate and the negative electrode plate were spirally wound with a separator interposed therebetween to have a diameter of 13.8 mm and a height of 50 m.
It was stored in the m battery case.
【００３９】このようにして作成した電池をそれぞれ電
池Ａ〜Ｌとした。 （実施例２）第２実施例として、コバルト塩水溶液とし
て硫酸コバルトと、塩化コバルトの混合塩を使用し、コ
バルト金属として６０ｇ／ｌ、硫酸イオンと塩酸イオン
のモル比をそれぞれ８０：２０、６０：４０、４０：６
０、２０：８０、０：１００（Ｃｌ-／ＳＯ4 2-モル比
０．２５、０．６６、１．５、５．０、∞）とし、槽内
のｐＨを１１．７５〜１２．０に調整する他は（実施例
１）と同様に電池を作成した。The batteries thus produced were designated as batteries A to L, respectively. (Example 2) As a second example, a mixed salt of cobalt sulfate and cobalt chloride was used as an aqueous cobalt salt solution, 60 g / l was used as cobalt metal, and the molar ratio of sulfate ion to hydrochloric acid ion was 80:20 and 60, respectively. : 40, 40: 6
0, 20:80, 0: 100 (Cl − / SO 4 2- molar ratio 0.25, 0.66, 1.5, 5.0, ∞), and the pH in the tank is 11.75 to 12. A battery was prepared in the same manner as in (Example 1) except that the battery was adjusted to 0.
【００４０】上記実施例２における電池をそれぞれＭ、
Ｎ、Ｏ、Ｐ、Ｑとした。 （実施例３）第３実施例として、添加剤として３００ｐ
ｐｍの濃度で槽内に硫酸アンモニウムを添加し、槽内の
ｐＨを１１．７５〜１２．０に調整する他は（実施例
１）と同様に電池を作成した。The batteries in Example 2 were replaced by M,
N, O, P and Q were used. (Example 3) As a third example, 300 p as an additive
A battery was prepared in the same manner as in (Example 1) except that ammonium sulfate was added to the tank at a concentration of pm to adjust the pH in the tank to 11.75 to 12.0.
【００４１】上記実施例３における電池をＲとした。 （実施例４）第４実施例として、添加剤として３００ｐ
ｐｍの濃度で槽内に塩化アンモニウムを用い、槽内のｐ
Ｈを１１．７５〜１２．０に調整する他は（実施例１）
と同様に電池を作成した。The battery in Example 3 was designated as R. (Example 4) As a fourth example, 300 p as an additive
Using ammonium chloride in the tank at a concentration of pm, p in the tank
Except for adjusting H to 11.75 to 12.0 (Example 1)
A battery was created in the same manner as in.
【００４２】上記実施例４における電池をＳとした。 （実施例５）第５実施例として、添加剤として３００ｐ
ｐｍの濃度で槽内に硫酸ナトリウムを用い、槽内のｐＨ
を１１．７５〜１２．０に調整する他は（実施例１）と
同様に電池を作成した。The battery in Example 4 was designated as S. (Example 5) As a fifth example, 300 p as an additive
Using sodium sulfate in the tank at a concentration of pm, pH in the tank
Was prepared in the same manner as in (Example 1) except that the value was adjusted to 11.75 to 12.0.
【００４３】上記実施例５における電池をＴとした。 （実施例６）第６実施例として、添加剤として３００ｐ
ｐｍの濃度で槽内に塩化ナトリウムを用い、槽内のｐＨ
を１１．７５〜１２．０に調整する他は（実施例１）と
同様に電池を作成した。The battery in Example 5 was designated as T. (Example 6) As a sixth example, 300 p as an additive
Using sodium chloride in the tank at a concentration of pm, pH in the tank
Was prepared in the same manner as in (Example 1) except that the value was adjusted to 11.75 to 12.0.
【００４４】上記実施例６における電池をＵとした。 （実施例７）第７実施例として、添加剤として３００ｐ
ｐｍの濃度で槽内にヒドラジンを用い、槽内のｐＨを１
１．７５〜１２．０に調整する他は（実施例１）と同様
に電池を作成した。The battery in Example 6 was designated as U. (Example 7) As a seventh example, 300 p as an additive
Use hydrazine in the tank at a concentration of pm and adjust the pH in the tank to 1
A battery was made in the same manner as in (Example 1) except that the battery was adjusted to 1.75 to 12.0.
【００４５】上記実施例７における電池をＶとした。 （実施例８）第８実施例として、添加剤としてそれぞれ
３００ｐｐｍの濃度で槽内に硫酸アンモニウムと塩化ア
ンモニウムの混合物を用い、槽内のｐＨを１１．７５〜
１２．０に調整する他は（実施例１）と同様に電池を作
成した。The battery in Example 7 was set to V. (Embodiment 8) As an eighth embodiment, a mixture of ammonium sulfate and ammonium chloride was used as an additive at a concentration of 300 ppm in each tank, and the pH in the tank was 11.75 to.
A battery was made in the same manner as in (Example 1) except that the adjustment was made to 12.0.
【００４６】上記実施例８における電池をＷとした。 （実施例９）第９実施例として、添加剤としてそれぞれ
３００ｐｐｍの濃度で槽内に塩化ナトリウムとヒドラジ
ンの混合物を用い、槽内のｐＨを１１．７５〜１２．０
に調整する他は（実施例１）と同様に電池を作成した。The battery in Example 8 was designated as W. (Example 9) As a ninth example, a mixture of sodium chloride and hydrazine was used in the tank at a concentration of 300 ppm as an additive, and the pH in the tank was 11.75 to 12.0.
A battery was prepared in the same manner as in (Example 1) except that the adjustment was made to.
【００４７】上記実施例９における電池をＸとした。 （実施例１０）第１０実施例として、コバルト塩水溶液
として硝酸コバルト塩を使用し、コバルト金属として６
０ｇ／ｌとし、槽内のｐＨを１１．７５〜１２．０に調
整する他は（実施例１）と同様に電池を作成した。The battery in Example 9 was designated as X. (Embodiment 10) As a tenth embodiment, a cobalt nitrate salt is used as an aqueous solution of cobalt salt, and a cobalt metal of 6 is used.
A battery was made in the same manner as in (Example 1) except that the pH in the tank was adjusted to 11.75 to 12.0 and the pH in the tank was adjusted to 0 g / l.
【００４８】上記実施例１０における電池をＹとした。 （比較例１）比較例１として、粒子の形状が塊状である
炭酸コバルトを原材料とする他は（実施例１）と同様に
ＬｉＣｏＯ2を合成した。原料に塊状の物を用いた場
合、合成により得られるＬｉＣｏＯ2も図４に示したよ
うに、ほぼ塊状の物が得られる事が確認できた。The battery in Example 10 was designated as Y. (Comparative Example 1) As Comparative Example 1, LiCoO 2 was synthesized in the same manner as in (Example 1) except that cobalt carbonate having a lumpy particle shape was used as a raw material. It was confirmed that when a lumpy material was used as the raw material, a substantially lumpy material was obtained as shown in FIG. 4 for LiCoO 2 obtained by synthesis.
【００４９】上記比較例１で説明したＬｉＣｏＯ2を正
極活物質として用いる他は実施例１と同様に電池を作成
した。A battery was prepared in the same manner as in Example 1 except that LiCoO 2 described in Comparative Example 1 was used as the positive electrode active material.
【００５０】上記比較例１における電池を電池AAとし
た。 （比較例２）比較例２として、硫酸コバルトを熱処理し
て合成した、粒子の形状が塊状である四酸化三コバルト
を原材料とする他は（実施例１）と同様にＬｉＣｏＯ2
を合成した。この場合においても、合成により得られる
ＬｉＣｏＯ2もほぼ塊状の物が得られる事が確認でき
た。The battery in Comparative Example 1 was designated as battery AA. (Comparative Example 2) As Comparative Example 2, LiCoO 2 was used in the same manner as in (Example 1) except that tricobalt tetraoxide, which was synthesized by heat-treating cobalt sulfate and had a lumpy particle shape, was used as the raw material.
Was synthesized. Also in this case, it was confirmed that LiCoO 2 obtained by the synthesis also had a substantially lumpy form.
【００５１】上記比較例２で説明したＬｉＣｏＯ2を正
極活物質として用いる他は実施例１と同様に電池を作成
した。A battery was prepared in the same manner as in Example 1 except that LiCoO 2 described in Comparative Example 2 was used as the positive electrode active material.
【００５２】上記比較例２における電池を電池ABとし
た。本発明の実施例および比較例の製造条件と粉体物性
を（表１）および（表２）に示す。The battery in Comparative Example 2 was designated as Battery AB. The production conditions and powder physical properties of Examples and Comparative Examples of the present invention are shown in (Table 1) and (Table 2).
【００５３】[0053]
【表１】 [Table 1]
【００５４】[0054]
【表２】 [Table 2]
【００５５】このようにして作成した電池Ａ〜Ｖを２０
℃、充電終止電圧４．１Ｖ、放電終止電圧３．０Ｖ、１
００ｍＡで充放電を繰り返し行い、サイクル充放電試験
を行った。The batteries A to V prepared in this manner were used for 20 times.
℃, charge end voltage 4.1V, discharge end voltage 3.0V, 1
The charging / discharging was repeated at 00 mA to perform a cycle charging / discharging test.
【００５６】また、同時に１Ａでの高率放電試験を行
い、放電容量の測定を行った。本発明の実施例および比
較例の電池のサイクル試験、高率放電試験の結果を（表
３）に示す。At the same time, a high rate discharge test at 1 A was conducted to measure the discharge capacity. The results of the cycle test and the high rate discharge test of the batteries of Examples and Comparative Examples of the present invention are shown in (Table 3).
【００５７】[0057]
【表３】 [Table 3]
【００５８】尚、電池Ａ〜ABはそれぞれ３０個組み立て
て試験を行い、（表３）には平均値を示した。30 batteries A to AB were assembled and tested, and the average values are shown in (Table 3).
【００５９】槽内におけるコバルト水酸化物の核生成速
度ｋは（化１）で示すように、溶液中のコバルト、水酸
化物イオンの濃度によって決定される。The nucleation rate k of the cobalt hydroxide in the tank is determined by the concentrations of cobalt and hydroxide ions in the solution, as shown in (Chemical formula 1).
【００６０】[0060]
【化１】 Embedded image
【００６１】（表１）からわかるように、コバルト水酸
化物の粒径はｐＨが低い領域で生成する程大きくなる。
これはｐＨが低いほど反応槽内のＯＨ-濃度が小さく、
コバルト水酸化物の槽内での核生成速度が小さいため、
核生成よりもわずかに生成したコバルト水酸化物の結晶
核の成長が優先されるためである。As can be seen from (Table 1), the particle size of the cobalt hydroxide becomes larger as it is formed in the low pH region.
The lower the pH, the lower the OH - concentration in the reaction tank,
Since the rate of nucleation of cobalt hydroxide in the tank is low,
This is because the growth of the crystal nuclei of the slightly formed cobalt hydroxide is prioritized over the nucleation.
【００６２】逆にｐＨが高くなると小さな結晶核が多量
に生成するため、得られるコバルト水酸化物の粒径は小
さくなる。このため、反応槽内のｐＨ制御は非常に重要
な品質管理のポイントとなる。On the other hand, when the pH is high, a large amount of small crystal nuclei are produced, so that the particle size of the obtained cobalt hydroxide is small. Therefore, pH control in the reaction tank is a very important quality control point.
【００６３】（実施例１）における電池ＡのようにｐＨ
を１１．０より低い領域でコバルト水酸化物を製造した
場合、得られるコバルト水酸化物の粒径が１０μｍ以上
と非常に大きくなる。このようなコバルト水酸化物を原
料として合成されたＬｉＣｏＯ2も同様に大きな粒径の
物が得られ、電池集電体への充填性は大きくなるため、
（表２）に示したように１００ｍＡ放電での容量は大き
くなり、５００サイクルの充放電を繰り返しても、初期
容量の７０％以上を示し、サイクル特性が良好である事
がわかる。As in the battery A in (Example 1), the pH was
When cobalt hydroxide is produced in a region of less than 11.0, the particle size of the obtained cobalt hydroxide is as large as 10 μm or more. LiCoO 2 synthesized using such a cobalt hydroxide as a raw material also has a large particle size, and the filling property in the battery current collector is increased.
As shown in (Table 2), the capacity at 100 mA discharge becomes large, and even after repeating 500 cycles of charging and discharging, it shows 70% or more of the initial capacity, indicating that the cycle characteristics are good.
【００６４】しかし、１Ａでの高率放電を行うと、Ａの
電池のように粒径の大きい物では、比表面積が小さいた
めに活物質と電解液の接触できる面積が小さく、放電時
の分極が大きくなり、放電容量が著しく小さくなる。こ
のため、コバルト水酸化物を製造するｐＨは１１．０以
上が望ましく、コバルト水酸化物の粒径は１０μｍ以下
である事が望ましい。However, when high-rate discharge at 1 A is performed, in the case of a battery having a large particle size such as the battery A, the area where the active material and the electrolytic solution can come into contact is small and the polarization during discharge is small. Becomes larger and the discharge capacity becomes significantly smaller. Therefore, the pH for producing cobalt hydroxide is preferably 11.0 or higher, and the particle size of cobalt hydroxide is preferably 10 μm or less.
【００６５】槽内のｐＨが高くなると、逆に粒径が小さ
いために比表面積が大きくなり、１Ａでの高率放電特性
は良好になるが、ｐＨが１３．５以上で製造した電池Ｌ
のような場合、粒径が小さすぎるために集電体への充填
性が悪く、放電容量自体が小さくなる。On the contrary, when the pH in the tank becomes high, the specific surface area becomes large due to the small particle size, and the high rate discharge characteristic at 1 A becomes good, but the battery L manufactured at a pH of 13.5 or higher is obtained.
In such a case, since the particle size is too small, the filling property in the current collector is poor and the discharge capacity itself becomes small.
【００６６】このため、コバルト水酸化物を製造するｐ
Ｈは１３．５以下が望ましく、コバルト水酸化物の粒径
は０．１μｍ以上である事が望ましい。Therefore, p for producing cobalt hydroxide
H is preferably 13.5 or less, and the particle size of cobalt hydroxide is preferably 0.1 μm or more.
【００６７】（実施例２）に示したように、コバルト水
溶液の原料塩として硫酸コバルトと塩化コバルトの混合
塩を用いた場合でも、電池Ｍ，Ｎ，Ｏ，Ｐに示したよう
に硫酸コバルト単独で製造した場合と同様に、サイクル
特性、高率放電特性の良好な電池が実現できた。As shown in (Example 2), even when a mixed salt of cobalt sulfate and cobalt chloride was used as the raw material salt of the cobalt aqueous solution, the cobalt sulfate alone was used as shown in the batteries M, N, O, and P. As in the case of the battery manufactured in 1., a battery having good cycle characteristics and high rate discharge characteristics could be realized.
【００６８】しかし、塩化コバルト単独で用いた場合
は、粒径が大きくなり（表３）の電池Ｑに示すように、
高率放電特性が低下している。However, when cobalt chloride is used alone, the particle size becomes large, as shown in battery Q in (Table 3),
The high rate discharge characteristics are degraded.
【００６９】これは、コバルト水酸化物が生成する際
に、塩素濃度が大きすぎると塩素が特異吸着して核生成
を抑制する効果がある物と考えられ、好ましくない。こ
のため、硫酸コバルトと塩化コバルトの混合塩水溶液に
おける硫酸イオンと塩素イオンのモル比（Ｃｌ-／ＳＯ4
2-）は０〜５の範囲である事が好ましい。This is not preferable since it is considered that when the cobalt hydroxide is produced, if the chlorine concentration is too high, chlorine is specifically adsorbed to suppress the nucleation. Therefore, the molar ratio of sulfate ion to chloride ion (Cl − / SO 4 in a mixed salt aqueous solution of cobalt sulfate and cobalt chloride) is
2- ) is preferably in the range of 0-5.
【００７０】また、（実施例３）〜（実施例７）に示し
たように反応槽内に添加剤として硫酸アンモニウム、塩
化アンモニウム、硫酸ナトリウム、塩化ナトリウム、ヒ
ドラジンをそれぞれ３００ｐｐｍ添加した場合、表２の
電池Ｒ，Ｓ，Ｔ，Ｕ，Ｖに示したようにサイクル特性が
更に向上した。Further, as shown in (Example 3) to (Example 7), when 300 ppm of ammonium sulfate, ammonium chloride, sodium sulfate, sodium chloride and hydrazine were added to the reaction vessel as additives, respectively, The cycle characteristics were further improved as shown in the batteries R, S, T, U and V.
【００７１】これは、これらの添加剤を加える事によっ
て、槽内のコバルトイオンや、コバルト水酸化物が化学
的に安定化するため、添加剤を加えない場合よりもより
結晶性の良好なコバルト水酸化物が得られ、この結果結
晶粒界が少なくなり、よりサイクル特性が向上した物で
ある。This is because the addition of these additives chemically stabilizes the cobalt ions and the cobalt hydroxide in the tank, so that cobalt having better crystallinity than the case where no additives are added is used. A hydroxide is obtained, and as a result, the number of crystal grain boundaries is reduced, and the cycle characteristics are further improved.
【００７２】また、（実施例８）、（実施例９）に示し
たようにこれらの添加剤を複合して添加した電池Ｗ，Ｘ
では更に良好なサイクル特性が得られ、より好ましい事
がわかる。Further, as shown in (Example 8) and (Example 9), batteries W and X to which these additives were added in combination were added.
It can be seen that in the case of (1), even better cycle characteristics are obtained, and it is more preferable.
【００７３】このように本発明における添加剤を用いて
製造したコバルト水酸化物を原料としてＬｉＣｏＯ2を
正極活物質として用いた電池は、よりサイクル特性の良
好な電池が実現できる。As described above, a battery using LiCoO 2 as a positive electrode active material with cobalt hydroxide as a raw material manufactured by using the additive in the present invention can realize a battery having better cycle characteristics.
【００７４】（実施例１０）のように原料塩として硝酸
コバルトを用いた場合においても、同様にサイクル特
性、高率放電特性の良好な電池が実現できる。Even when cobalt nitrate is used as the raw material salt as in (Example 10), a battery having good cycle characteristics and high rate discharge characteristics can be realized.
【００７５】このように、本発明による製造法で得られ
た板状のコバルト水酸化物を原料に用いた電池は、優れ
たサイクル特性を示すのに対し、比較例で示したように
通常の用いられる炭酸コバルトや、硫酸コバルト等の塩
を原料に用いた場合、結晶がランダムに配列した多結晶
体となり、結晶粒界が多数存在し、比較例１、２に示し
た電池AA，ABのようにサイクル特性が著しく悪い結果と
なる。As described above, the battery using the plate-shaped cobalt hydroxide obtained by the manufacturing method according to the present invention as the raw material exhibits excellent cycle characteristics, while the battery obtained by the ordinary method as shown in the comparative example. When a salt such as cobalt carbonate or cobalt sulfate to be used is used as a raw material, it becomes a polycrystalline body in which crystals are randomly arranged, and a large number of crystal grain boundaries exist, so that the batteries AA and AB shown in Comparative Examples 1 and 2 have As a result, the cycle characteristics are extremely poor.
【００７６】以上に示したように、本発明によるＬｉＣ
ｏＯ2の製造方法を用いる事により、サイクル特性、高
率放電特性に優れた電池を実現する事ができる。As shown above, the LiC according to the present invention
By using the oO 2 manufacturing method, a battery having excellent cycle characteristics and high rate discharge characteristics can be realized.
【００７７】本実施例では反応槽温度を４０℃で制御し
たが、２０〜６０℃の範囲内であれば同様の効果が得ら
れる。In the present embodiment, the reaction tank temperature was controlled at 40 ° C., but the same effect can be obtained if it is within the range of 20-60 ° C.
【００７８】本実施例７では反応槽への添加剤としてヒ
ドラジンを用いたが、塩酸ヒドラジンや、硫酸ヒドラジ
ンなどのヒドラジン塩でも同様の効果が得られる。In Example 7, hydrazine was used as an additive to the reaction tank, but hydrazine salts such as hydrazine hydrochloride and hydrazine sulfate can also provide the same effect.
【００７９】また、（実施例８）、（実施例９）では複
合添加剤の組み合わせとして硫酸アンモニウムと塩化ア
ンモニウム、塩化ナトリウムとヒドラジンの混合物をそ
れぞれ示したが、その他本発明に明示した添加剤であれ
ばどの組み合わせでも同様の効果が得られる。Further, in (Example 8) and (Example 9), a mixture of ammonium sulfate and ammonium chloride and a mixture of sodium chloride and hydrazine were shown as the combination of the composite additives, but any other additive specified in the present invention may be used. The same effect can be obtained with any combination.
【００８０】更に３種類以上の複合系でも同様の効果が
得られる事は言うまでもない。本実施例ではアルカリ溶
液として水酸化ナトリウムを使用したが、水酸化リチウ
ム、水酸化カリウムを用いても同様の効果が得られる事
を確認した。Needless to say, the same effect can be obtained with a composite system of three or more types. Although sodium hydroxide was used as the alkaline solution in this example, it was confirmed that the same effect can be obtained by using lithium hydroxide or potassium hydroxide.
【００８１】また、上記実施例においては円筒型の電池
を用いて評価を行ったが、角型やコイン型など電池形状
が異なっても同様の効果が得られる。Further, in the above-mentioned embodiment, the evaluation was carried out using a cylindrical battery, but the same effect can be obtained even if the battery shape is different such as a prismatic type or a coin type.
【００８２】更に、上記実施例において負極には炭素質
材料を用いたが、本発明における効果は正極板において
作用するため、リチウム金属や、リチウム合金、Ｆｅ2
Ｏ3、ＷＯ2、ＷＯ3等の酸化物など、他の負極材料を用
いても同様の効果が得られる。Further, although a carbonaceous material was used for the negative electrode in the above examples, since the effect of the present invention works on the positive electrode plate, lithium metal, lithium alloy, Fe 2
Similar effects can be obtained by using other negative electrode materials such as oxides of O 3 , WO 2 , WO 3 and the like.
【００８３】また、上記実施例において電解質として六
フッ化リン酸リチウムを使用したが、他のリチウム含有
塩、例えば過塩素酸リチウム、四フッ化ホウ酸リチウ
ム、トリフルオロメタンスルホン酸リチウム、六フッ化
ヒ酸リチウムなどでも同様の効果が得られた。Further, although lithium hexafluorophosphate was used as the electrolyte in the above examples, other lithium-containing salts such as lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and hexafluorofluoride were used. Similar effects were obtained with lithium arsenate and the like.
【００８４】さらに、上記実施例では炭酸エチレンと炭
酸ジエチルの混合溶媒を用いたが、他の非水溶媒例え
ば、プロピレンカーボネートなどの環状エステル、テト
ラヒドロフランなどの環状エーテル、ジメトキシエタン
などの鎖状エーテル、プロピオン酸メチルなどの鎖状エ
ステルなどの非水溶媒や、これらの多元系混合溶媒を用
いても同様の効果が得られた。Furthermore, although a mixed solvent of ethylene carbonate and diethyl carbonate was used in the above examples, other non-aqueous solvents such as cyclic ester such as propylene carbonate, cyclic ether such as tetrahydrofuran, chain ether such as dimethoxyethane, Similar effects were obtained using a non-aqueous solvent such as a chain ester such as methyl propionate or a multi-component mixed solvent thereof.
【００８５】[0085]
【発明の効果】以上のように、本発明では非水電解液電
池用活物質の原料であるコバルト水酸化物の製造時に供
給塩濃度、供給塩流量、槽内温度を一定にして槽内のｐ
Ｈ値を１１．０〜１３．５にすることにより、結晶構造
の良好なコバルト水酸化物を得ることができ、このコバ
ルト水酸化物を用いて四酸化三コバルトを経てＬｉＣｏ
Ｏ2を得ることにより放電特性、サイクル特性に優れた
非水電解液電池を提供することができる。As described above, according to the present invention, the concentration of the supplied salt, the flow rate of the supplied salt, and the temperature in the tank are kept constant during the production of the cobalt hydroxide, which is the raw material of the active material for the non-aqueous electrolyte battery. p
By setting the H value to 11.0 to 13.5, a cobalt hydroxide having a good crystal structure can be obtained. Using this cobalt hydroxide, tricobalt tetroxide and LiCo
By obtaining O 2 , it is possible to provide a non-aqueous electrolyte battery having excellent discharge characteristics and cycle characteristics.
【図１】円筒型電池の縦断面図FIG. 1 is a vertical sectional view of a cylindrical battery.
【図２】本発明による製造法で作成したコバルト水酸化
物の結晶構造図FIG. 2 is a crystal structure diagram of cobalt hydroxide prepared by the manufacturing method according to the present invention.
【図３】本発明による製造法で作成したＬｉＣｏＯ2の
結晶構造図FIG. 3 is a crystal structure diagram of LiCoO 2 prepared by a manufacturing method according to the present invention.
【図４】炭酸コバルトを原料として比較例１の方法で合
成したＬｉＣｏＯ2の結晶構造図FIG. 4 is a crystal structure diagram of LiCoO 2 synthesized by the method of Comparative Example 1 using cobalt carbonate as a raw material.
１ 電池ケース ２ 封口板 ３ 絶縁パッキング ４ 極板群 ５ 正極板 ５ａ 正極リード ６ 負極板 ６ａ 負極リード ７ セパレータ ８ 絶縁リング DESCRIPTION OF SYMBOLS 1 Battery case 2 Sealing plate 3 Insulating packing 4 Electrode plate group 5 Positive electrode plate 5a Positive electrode lead 6 Negative electrode plate 6a Negative electrode lead 7 Separator 8 Insulating ring
───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉本 豊次 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 北 秀行 福井県福井市白方町45字砂浜割５番10号 株式会社田中化学研究所内 (72)発明者 飯田 得代志 福井県福井市白方町45字砂浜割５番10号 株式会社田中化学研究所内 (72)発明者 宮川 敏夫 兵庫県尼崎市道意町５丁目30番地 株式会 社田中化学研究所内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toyoji Sugimoto 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor Hideyuki Kita 45-10 Sunahama, 45, Shirakata, Fukui, Fukui Prefecture Issue Tanaka Chemical Research Institute Co., Ltd. (72) Inventor Tokuyo Iida 45-10 Shirakata-cho, Fukui City, Fukui Prefecture, No. 5-10 Sand Beach Division, Tanaka Chemical Research Institute Co., Ltd. (72) Toshio Miyagawa Amagasaki City, Hyogo 5-30, Machi Stock Company Tanaka Chemical Research Institute
Claims (10)
を同一槽内に連続的に供給、撹拌し、供給塩濃度、供給
塩流量、槽内温度を一定にして槽内のｐＨ値を１１．０
〜１３．５の範囲に制御することによりコバルト水酸化
物を得る非水電解液電池活物質用コバルト水酸化物の製
造法。1. A cobalt salt aqueous solution and a caustic alkaline solution are continuously supplied and stirred in the same tank, and the pH value of the tank is adjusted to 11 by keeping the supplied salt concentration, the supplied salt flow rate and the tank temperature constant. .0
The manufacturing method of the cobalt hydroxide for nonaqueous electrolyte battery active materials which obtains a cobalt hydroxide by controlling in the range of 13.5.
水電解液電池活物質用四酸化三コバルトを得る工程にお
いて、前記コバルト水酸化物としてコバルト塩の水溶液
と、か性アルカリ溶液を同一槽内に連続的に供給、撹拌
し、供給塩濃度、供給塩流量、槽内温度を一定にして槽
内のｐＨ値を１１．０〜１３．５の範囲に制御すること
により得たものを用いる非水電解液電池活物質用四酸化
三コバルトの製造法。2. In the step of heat-treating cobalt hydroxide in air to obtain tricobalt tetroxide for a non-aqueous electrolyte battery active material, an aqueous solution of a cobalt salt as the cobalt hydroxide and a caustic alkaline solution are used. Obtained by continuously supplying and stirring in the same tank and controlling the pH value in the tank within the range of 11.0 to 13.5 while keeping the supplied salt concentration, the supplied salt flow rate and the tank temperature constant. Method for producing tricobalt tetroxide for non-aqueous electrolyte battery active material using.
温度範囲で熱処理する請求項２記載の非水電解液電池活
物質用四酸化三コバルトの製造法。3. The method for producing tricobalt tetroxide for a non-aqueous electrolyte battery active material according to claim 2, wherein the cobalt hydroxide is heat-treated in a temperature range of 200 ° C. to 700 ° C.
溶液または硫酸コバルトと塩化コバルトの混合水溶液で
ある請求項２記載の非水電解液電池活物質用四酸化三コ
バルトの製造法。4. The method for producing tricobalt tetraoxide for a non-aqueous electrolyte battery active material according to claim 2, wherein the aqueous solution of the cobalt salt is an aqueous solution of cobalt sulfate or a mixed aqueous solution of cobalt sulfate and cobalt chloride.
において、硫酸イオンと塩素イオンのモル比（Ｃｌ-／
ＳＯ4 2-）が０より大きく５以下である請求項４記載の
非水電解液電池活物質用四酸化三コバルトの製造法。5. In a mixed aqueous solution of cobalt sulfate and cobalt chloride, the molar ratio of sulfate ion to chloride ion (Cl − /
The method for producing tricobalt tetroxide for a non-aqueous electrolyte battery active material according to claim 4, wherein SO 4 2− ) is greater than 0 and 5 or less.
ヒドラジン，ヒドラジン塩，硫酸アンモニウム，塩化ア
ンモニウムからなる群のうちの少なくとも１種類以上を
添加する請求項２記載の非水電解液電池活物質用四酸化
三コバルト（Ｃｏ3Ｏ4）の製造法。6. A sodium chloride, sodium sulfate,
The method for producing tricobalt tetroxide (Co 3 O 4 ) for a non-aqueous electrolyte battery active material according to claim 2, wherein at least one selected from the group consisting of hydrazine, hydrazine salts, ammonium sulfate and ammonium chloride is added.
を同一槽内に連続的に供給、撹拌し、供給塩濃度、供給
塩流量、槽内温度を一定にして槽内のｐＨ値を１１．０
〜１３．５の範囲に制御することにより得た粒子であ
り、ＳＥＭ写真観察における定方向径（Ｆｅｒｅｔ ｄ
ｉａｍｅｔｅｒ）が０．１〜１０μｍの範囲にある非水
電解液電池活物質用コバルト水酸化物。7. An aqueous solution of cobalt salt and a caustic alkaline solution are continuously supplied and stirred in the same tank, and the pH value of the tank is adjusted to 11 by keeping the supplied salt concentration, the supplied salt flow rate and the tank temperature constant. .0
The particles are particles obtained by controlling the particle size in the range of 13.5 to 13.5, and have a fixed diameter (Feret d) in SEM photograph observation.
cobalt hydroxide for a non-aqueous electrolyte battery active material having an iatter) of 0.1 to 10 μm.
電解液活物質用コバルト水酸化物。8. The cobalt hydroxide for a non-aqueous electrolyte active material according to claim 7, wherein the particle shape is a plate shape.
を同一槽内に連続的に供給、撹拌し、供給塩濃度、供給
塩流量、槽内温度を一定にして槽内のｐＨ値を１１．０
〜１３．５の範囲に制御することにより得たコバルト水
酸化物を空気中で熱処理することによって得た粒子であ
り、ＳＥＭ写真観察における定方向径（Ｆｅｒｅｔ ｄ
ｉａｍｅｔｅｒ）が０．１〜１０μｍの範囲にある非水
電解液電池活物質用四酸化三コバルト。9. An aqueous solution of cobalt salt and a caustic alkaline solution are continuously supplied and stirred in the same tank, and the pH value of the tank is adjusted to 11 by keeping the supplied salt concentration, the supplied salt flow rate and the tank temperature constant. .0
Particles obtained by heat-treating cobalt hydroxide obtained by controlling in the range of 13.5 to 13.5, and having a unidirectional diameter (Feret d) in SEM photograph observation.
tricobalt tetroxide for a non-aqueous electrolyte battery active material having an iatter) in the range of 0.1 to 10 μm.
の温度範囲で熱処理して得た請求項９記載の非水電解液
活物質用四酸化三コバルト。10. Cobalt hydroxide at 200 ° C. to 700 ° C.
The tricobalt tetroxide for a non-aqueous electrolyte active material according to claim 9, which is obtained by heat treatment in the temperature range of 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16848995A JP3394364B2 (en) | 1995-07-04 | 1995-07-04 | Cobalt hydroxide and tricobalt tetroxide as raw materials for non-aqueous electrolyte battery active material LiCoO2 and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16848995A JP3394364B2 (en) | 1995-07-04 | 1995-07-04 | Cobalt hydroxide and tricobalt tetroxide as raw materials for non-aqueous electrolyte battery active material LiCoO2 and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0922692A true JPH0922692A (en) | 1997-01-21 |
| JP3394364B2 JP3394364B2 (en) | 2003-04-07 |
Family
ID=15869043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16848995A Expired - Fee Related JP3394364B2 (en) | 1995-07-04 | 1995-07-04 | Cobalt hydroxide and tricobalt tetroxide as raw materials for non-aqueous electrolyte battery active material LiCoO2 and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3394364B2 (en) |
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| WO2018198967A1 (en) * | 2017-04-27 | 2018-11-01 | 株式会社村田製作所 | Positive electrode active material, positive electrode, battery, battery pack, electronic apparatus, electric vehicle, electricity storage device, and electric power system |
| CN110546795A (en) * | 2017-04-27 | 2019-12-06 | 株式会社村田制作所 | Positive electrode active material, positive electrode, battery pack, electronic device, electric vehicle, power storage device, and power system |
| JPWO2018198967A1 (en) * | 2017-04-27 | 2020-02-27 | 株式会社村田製作所 | Positive electrode active material, positive electrode, battery, battery pack, electronic equipment, electric vehicle, power storage device and power system |
| CN113292106A (en) * | 2020-02-24 | 2021-08-24 | 荆门市格林美新材料有限公司 | Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide |
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