JPH0896809A - Manufacture of tricobalt tetroxide for lithium secondary battery positive electrode material - Google Patents
Manufacture of tricobalt tetroxide for lithium secondary battery positive electrode materialInfo
- Publication number
- JPH0896809A JPH0896809A JP6257296A JP25729694A JPH0896809A JP H0896809 A JPH0896809 A JP H0896809A JP 6257296 A JP6257296 A JP 6257296A JP 25729694 A JP25729694 A JP 25729694A JP H0896809 A JPH0896809 A JP H0896809A
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- aqueous solution
- lithium secondary
- tricobalt tetroxide
- secondary 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム二次電池の正
極用材料として使用されるリチウム含有複合酸化物の原
料となる四酸化三コバルト（Ｃｏ3Ｏ4）、および、その
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to tricobalt tetroxide (Co 3 O 4 ) which is a raw material of a lithium-containing composite oxide used as a material for a positive electrode of a lithium secondary battery, and a method for producing the same.
【０００２】[0002]
【従来の技術】リチウム電池は、自己放電が少なく保存
性に優れた電池として知られ、特に５〜１０年という長
期間使用が要求される電子腕時計や種々のメモリーバッ
クアップ用電源として広く利用されている。このリチウ
ム電池は、負極に対してドープまたは脱ドープ物質とし
てリチウムを使用し、電解質に有機電解液を使用してい
る。従来から使用されているリチウム電池は通常一次電
池であるが、長期間経済的に使用できる電源としての再
充電可能なリチウム二次電池に対する要望が多く、各方
面で研究が進められている。負極にカーボン等を用いた
リチウム二次電池は、その高エネルギー密度電池として
の性能が買われ、携帯電話機やビデオカメラ用などの
他、電気自動車用として急速に期待が高まってきてい
る。2. Description of the Related Art Lithium batteries are known as batteries having less self-discharge and excellent storage stability, and are widely used as power supplies for electronic wrist watches and various memory backups, which are required to be used for a long period of 5 to 10 years. There is. In this lithium battery, lithium is used as a doping or dedoping substance for the negative electrode, and an organic electrolyte solution is used as an electrolyte. Conventionally used lithium batteries are usually primary batteries, but there are many demands for rechargeable lithium secondary batteries as a power source that can be economically used for a long period of time, and research is progressing in various fields. Lithium secondary batteries using carbon or the like for the negative electrode have been expected to have high performance as high energy density batteries, and are rapidly expected to be used not only for mobile phones and video cameras but also for electric vehicles.
【０００３】従来より、リチウムまたはリチウム化合物
を負極とするリチウム二次電池は高電圧で高エネルギー
密度となることが期待されている。特に、これら電池の
正極活物質としてＭｎＯ2 やＴｉＳ2 が提案されている
が、よりエネルギー密度が高い電池を得るため、ＬｉＣ
ｏＯ2 を正極活物質として用いることが提案されている
（例えば、米国特許４５６７０３１号）。上記リチウム
二次電池用の正極活物質として用いられるＬｉＣｏＯ2
は、空気中でＬｉ2ＣＯ3等のＬｉ化合物とＣｏ3Ｏ4等の
Ｃｏ化合物を加熱することによって合成されている。例
えばＬｉ2ＣＯ3とＣｏ3Ｏ4を用いた場合、ＬｉＣｏＯ2
は以下のようにして合成される。It has been conventionally expected that a lithium secondary battery having lithium or a lithium compound as a negative electrode has a high voltage and a high energy density. In particular, MnO 2 and TiS 2 have been proposed as the positive electrode active material for these batteries, but in order to obtain batteries with higher energy density, LiC
It has been proposed to use oO 2 as a positive electrode active material (for example, US Pat. No. 4,567,031). LiCoO 2 used as a positive electrode active material for the lithium secondary battery
Is synthesized by heating a Li compound such as Li 2 CO 3 and a Co compound such as Co 3 O 4 in air. For example, when Li 2 CO 3 and Co 3 O 4 are used, LiCoO 2
Is synthesized as follows.
【０００４】 [0004]
【０００５】近年、携帯電話機やビデオカメラの小型化
から、使用されるリチウム二次電池の小型化が求めら
れ、使用される四酸化三コバルトにも粒径が１μｍ以下
の小さなものが望まれている。上記四酸化三コバルトの
製造方法として、２価のコバルト塩水溶液にまたは２価
のコバルト複塩スラリーに対し、その２価コバルトイオ
ン量の１．２倍当量以上の苛性アルカリを作用させて水
酸化コバルトを得て、この水酸化コバルトを水洗・乾燥
し、３００〜９００℃の温度で焼成する方法が提案され
ている（特公昭５８−２５０５２号）。しかしながら、
この方法で製造した水酸化コバルトは粒径が０．０１μ
ｍ程度の非常に細かい粒子であるため、水溶液でゲル状
となり、沈澱による固液分離が容易でなく、水和スラッ
ジ化防止の対策が必要であり、また、水酸化コバルトか
らＣｏ3Ｏ4を得るには、Ｃｏ（ＯＨ）2 を焼成するが、
このようにして得られるＣｏ3Ｏ4は焼結して粒子が１μ
ｍ以上となり、Ｌｉ2ＣＯ3主体のリチウム塩との反応性
を確保、促進するための微粉体を得るためには多段粉砕
が必要となるという欠点がある。In recent years, due to the miniaturization of mobile phones and video cameras, miniaturization of lithium secondary batteries to be used has been demanded, and tricobalt tetroxide to be used has a small particle size of 1 μm or less. There is. As the method for producing the above-mentioned tricobalt tetraoxide, a caustic alkali of 1.2 times the equivalent amount of the divalent cobalt ion is applied to the divalent cobalt salt aqueous solution or to the divalent cobalt double salt slurry to effect the hydroxylation. A method has been proposed in which cobalt is obtained, the cobalt hydroxide is washed with water, dried, and calcined at a temperature of 300 to 900 ° C (Japanese Patent Publication No. 58-25052). However,
Cobalt hydroxide produced by this method has a particle size of 0.01μ
Because it is very fine particles of about m, it gelled in aqueous solution, it is not easy solid-liquid separation by precipitation, measures hydrated sludge prevention is necessary, also the Co 3 O 4 from cobalt hydroxide To obtain, we fire Co (OH) 2 ,
The Co 3 O 4 thus obtained is sintered and the particles are 1 μm.
Since it is more than m, there is a drawback that multistage pulverization is required to obtain fine powder for securing and promoting reactivity with a lithium salt mainly composed of Li 2 CO 3 .
【０００６】また、水溶性Ｃｏ（II）塩を含む溶液に等
量の水溶性炭酸塩の水溶液を１〜３時間にわたって添加
し、不活性雰囲気を維持しながら５４〜６０℃（１３０
〜１４０゜Ｆ）で１〜１０時間加熱して反応させた後、
不活性雰囲気を保持しながら８２〜１００℃（１８０〜
２１２゜Ｆ）に加熱してＣｏＣＯ3 を得る方法が特開昭
６１−９１０１８号に提案されている。しかしながらこ
の方法で得られたＣｏＣＯ3 を空気中等の酸素共存下で
焼成して四酸化三コバルトを得ようとすると、やはり得
られた四酸化三コバルトが焼結し、多段粉砕が必要とな
るという欠点がある。さらに、特開昭６３−１０００２
２号にＮｉ，Ｃｏ，ＣｕおよびＺｎを含有する溶液から
ＣｕおよびＺｎを硫化物として沈澱・分離した後、溶液
を３０〜８０℃に加熱し、Ｎａ2ＣＯ3等の炭酸塩イオン
をｐＨ６．０〜９．０になるまで添加してＮｉＣＯ3 ま
たはＣｏＣＯ3 を沈澱させる方法が提案されている。し
かしこの方法では上記と同様に、得られるＣｏＣＯ3 が
０．０１μｍ以下と非常に細かく、空気中などの酸素共
存下で四酸化三コバルトを得ようとすると、得られた四
酸化三コバルトが焼結し、多段粉砕が必要となり、さら
に、ｐＨを高くするために、反応に必要な炭酸塩イオン
の他に、ｐＨを上げるための炭酸塩イオン供給源が必要
となり、コスト高になるという欠点がある。Further, an equal amount of an aqueous solution of a water-soluble carbonate is added to a solution containing a water-soluble Co (II) salt over 1 to 3 hours, and the temperature is maintained at 54 to 60 ° C. (130
After reacting by heating at ~ 140 ° F) for 1-10 hours,
82-100 ° C (180-
A method for obtaining CoCO 3 by heating to 212 ° F.) is proposed in JP-A-61-91018. However, when the CoCO 3 obtained by this method is calcined in the presence of oxygen such as in the air to obtain tricobalt tetroxide, the obtained tricobalt tetroxide is also sintered and multistage pulverization is required. There are drawbacks. Furthermore, JP-A-63-10002
After precipitation and separation of Cu and Zn as sulfides from a solution containing Ni, Co, Cu and Zn in No. 2, the solution was heated to 30 to 80 ° C., and carbonate ions such as Na 2 CO 3 were added at pH 6. A method has been proposed in which NiCO 3 or CoCO 3 is precipitated by adding it until it becomes 0 to 9.0. However, in this method, similarly to the above, the obtained CoCO 3 is very fine as 0.01 μm or less, and when tricobalt tetroxide is tried to be obtained in the coexistence of oxygen such as in air, the obtained tricobalt tetroxide is burnt. Therefore, in order to raise the pH, a carbonate ion supply source for raising the pH is required in addition to the carbonate ion required for the reaction, which results in a high cost. is there.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記状況に鑑
みなされたものであり、リチウム二次電池の正極用材料
等として使用される、解砕性が良く、かつ、ＢＥＴ法で
測定した平均粒径が０．１〜０．５μｍである四酸化コ
バルトの安価な製造方法に関する。SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and is used as a material for a positive electrode of a lithium secondary battery, has good crushability, and has an average measured by the BET method. It relates to an inexpensive method for producing cobalt tetraoxide having a particle size of 0.1 to 0.5 μm.
【０００８】[0008]
【課題を解決するための手段】すなわち、上記課題を解
決するための本発明は、硫酸コバルト水溶液と、その水
溶液中に含まれるコバルトイオンに対して当量以上の炭
酸水素イオンを含む水溶液を反応させ、反応後さらにア
ンモニアを添加し、ｐＨを７．０〜８．５にして１時間
以上攪拌し、得られた塩基性炭酸コバルトの沈澱を固液
分離・洗浄・乾燥させて、好ましくは空気中など酸素共
存下で６００〜７００℃の温度でばい焼することを特徴
とするリチウム二次電池用四酸化三コバルトの製造方法
である。上記製造方法では、解砕性が良く、かつＢＥＴ
法で測定した平均粒径が０．１〜０．５μｍであるリチ
ウム二次電池用四酸化三コバルトを得られる。[Means for Solving the Problems] That is, according to the present invention for solving the above-mentioned problems, an aqueous cobalt sulfate solution is reacted with an aqueous solution containing an equivalent amount or more of hydrogen carbonate ion to cobalt ion contained in the aqueous solution. After the reaction, further ammonia is added to adjust the pH to 7.0 to 8.5, and the mixture is stirred for 1 hour or more. The obtained basic cobalt carbonate precipitate is solid-liquid separated, washed and dried, preferably in air. A method for producing tricobalt tetroxide for a lithium secondary battery, comprising roasting at a temperature of 600 to 700 ° C. in the presence of oxygen. In the above manufacturing method, the crushability is good and BET
It is possible to obtain tricobalt tetroxide for a lithium secondary battery, which has an average particle size measured by the method of 0.1 to 0.5 μm.
【０００９】[0009]
【作用】リチウム二次電池正極材料用四酸化三コバルト
（Ｃｏ3Ｏ4）の平均粒径をＢＥＴ法の測定で０．１〜
０．５μｍとする理由は、次の通りである。すなわち、
０．１μｍ未満であると、Ｌｉ2ＣＯ3主体のリチウム化
合物との混合時に四酸化三コバルト粒子が舞い上がって
しまい、収率が悪くなる。また、リチウム化合物との粒
度が違いすぎて均一混合が困難になる。逆に、０．５μ
ｍを超えると、リチウム化合物と混合したときに均一混
合が困難となり、ＬｉＣｏＯ2 の収率が悪くなり、特性
の低下を招くおそれがある。[Function] The average particle size of tricobalt tetroxide (Co 3 O 4 ) for the positive electrode material of the lithium secondary battery is 0.1 to 0.1 by the BET method.
The reason why the thickness is 0.5 μm is as follows. That is,
If it is less than 0.1 μm, tricobalt tetroxide particles fly up when mixed with a lithium compound mainly composed of Li 2 CO 3 and the yield deteriorates. Further, the particle size of the lithium compound is too different, which makes uniform mixing difficult. On the contrary, 0.5μ
If it exceeds m, uniform mixing becomes difficult when mixed with a lithium compound, the yield of LiCoO 2 may be deteriorated, and the characteristics may be deteriorated.
【００１０】以下に本発明の製造方法の詳細について説
明する。使用する硫酸コバルト水溶液のコバルト濃度に
ついては特に限定するものではないが、余りに低くする
と生産性が悪化するため、コバルトイオンとして１０ｇ
／リットルとすることが望ましい。また上限に次いては
硫酸コバルトの水への溶解度からおのずと決定される。
また炭酸水素イオンを含む水溶液としては、例えば炭酸
水素ナトリウムまたは炭酸水素アンモニウム等の水溶液
を用いることができる。その炭酸水素イオンは、本発明
方法の条件下においては、コバルトと反応し、塩基性炭
酸塩を生成する。よって反応させる炭酸水素イオンの量
は溶液中に含有されるコバルトイオンの量の当量以上あ
ればよい。しかし、余りに多くするとコスト高になるの
で、好ましくはコバルトイオンの量の１．０１〜１．０
５当量とすることが望ましい。The details of the manufacturing method of the present invention will be described below. The cobalt concentration of the cobalt sulfate aqueous solution to be used is not particularly limited, but if it is too low, the productivity deteriorates.
It is desirable to set it to / liter. Next to the upper limit, it is naturally determined from the solubility of cobalt sulfate in water.
As the aqueous solution containing hydrogen carbonate ions, for example, an aqueous solution of sodium hydrogen carbonate or ammonium hydrogen carbonate can be used. Under the conditions of the method of the present invention, the hydrogen carbonate ion reacts with cobalt to form a basic carbonate. Therefore, the amount of hydrogen carbonate ions to be reacted may be equal to or more than the amount of cobalt ions contained in the solution. However, if the amount is too large, the cost becomes high. Therefore, the amount of cobalt ion is preferably 1.01 to 1.0.
It is desirable that the amount be 5 equivalents.
【００１１】次に硫酸コバルト水溶液と炭酸水素イオン
を含む水溶液を反応後、スラリーのｐＨを７．０〜８．
５とするが、ｐＨが７．０より低いと、塩基性炭酸塩の
平均粒径が沈澱分離に長時間かかるように小さくなり、
また、ｐＨが８．５より高いと塩基性炭酸塩中の水酸化
物量が多くなりすぎて、スラリーの固液分離に非常に時
間がかかるという欠点がある。上記のｐＨ調整剤として
は、アンモニア水が望ましい。アンモニア水の場合、通
常１０〜２８％程度の濃度のものを使用することが適当
である。反応温度は室温でも充分反応するが、反応速度
を速めるためには加温する方が良い。しかし反応温度が
低く攪拌時間が短いとスラリーを固液分離・洗浄・乾燥
した塩基性炭酸塩が凝集し作業性の悪いものになってし
まい、これを回避するためには１２時間以上の攪拌時間
が必要となる。また液温が高すぎると、液中の炭酸水素
イオンが炭酸ガスとなって系外に逃げてしまいコバルト
イオンが残存して生産性が悪化するため反応温度は２０
〜８０℃とすることが必要であり、好ましくは４０〜６
０℃とすることが望ましい。Next, after reacting the aqueous solution of cobalt sulfate with the aqueous solution containing hydrogen carbonate ions, the pH of the slurry is adjusted to 7.0 to 8.
However, if the pH is lower than 7.0, the average particle size of the basic carbonate becomes small so that precipitation separation takes a long time,
On the other hand, if the pH is higher than 8.5, the amount of hydroxide in the basic carbonate becomes too large, and it takes a very long time for solid-liquid separation of the slurry. Ammonia water is desirable as the pH adjuster. In the case of aqueous ammonia, it is usually suitable to use one having a concentration of about 10 to 28%. Although the reaction temperature is sufficient even at room temperature, it is better to heat it to increase the reaction rate. However, if the reaction temperature is low and the stirring time is short, the basic carbonate obtained by solid-liquid separation / washing / drying of the slurry will agglomerate, resulting in poor workability. To avoid this, stirring time of 12 hours or more is required. Is required. If the liquid temperature is too high, hydrogen carbonate ions in the liquid become carbon dioxide gas and escape to the outside of the system, leaving cobalt ions and deteriorating the productivity.
It is necessary to set the temperature to -80 ° C, preferably 40 to 6
It is desirable to set it to 0 ° C.
【００１２】また、攪拌時間は短すぎるとスラリーを固
液分離・洗浄・乾燥した塩基性炭酸塩が凝結し作業性の
悪いものになってしまうため、１時間以上が必要であ
り、好ましくは２〜６時間が望ましい。このようにして
得られた沈澱中には液中に存在する各種イオンを含んで
いるため、これをそのままばい焼すると得られる四酸化
三コバルト中の不純物が上昇するので、純水を用いて洗
浄する必要がある。ばい焼温度を６００〜７００℃とし
たのは、高すぎると四酸化三コバルトが焼結し、ＢＥＴ
法で測定した平均粒径が０．１〜０．５μｍのリチウム
塩との反応性のよい、かつ反応のかたよりのない四酸化
三コバルトを得るためには長時間の微粉砕が必要とな
る。逆に低すぎると、中間物である塩基性炭酸塩が残存
する危険性がある。If the stirring time is too short, the basic carbonate obtained by solid-liquid separation / washing / drying of the slurry will condense, resulting in poor workability, so that one hour or more is required, and preferably 2 ~ 6 hours is desirable. Since the precipitate thus obtained contains various ions existing in the liquid, the impurities in tricobalt tetroxide obtained by roasting it as it is will increase, so wash with pure water. There is a need to. The roasting temperature was set to 600-700 ° C because tricobalt tetroxide sinters when it is too high, and BET
In order to obtain tricobalt tetroxide having good reactivity with a lithium salt having an average particle size of 0.1 to 0.5 μm measured by the method and having no reaction tendency, it is necessary to pulverize for a long time. On the other hand, if it is too low, there is a risk that the intermediate basic carbonate will remain.
【００１３】なお、ばい焼時間は用いる炉、雰囲気、そ
して温度により異なるため一義的に特定できないが、し
かし、例えば沈澱を厚さ４０ｍｍの層としてマッフル炉
中で、６００〜７００℃にてばい焼する場合には２〜４
時間が必要とされる。このように、硫酸コバルト水溶液
と炭酸水素イオンを含む水溶液とを反応し、その後ｐＨ
を７．０〜８．５とし、１時間以上攪拌することによ
り、得られる塩基性炭酸コバルトは粉砕が必要でなく、
平均粒径が０．１〜０．５μｍの四酸化三コバルトを得
るためのばい焼温度を６００〜７００℃に低下させるこ
とができる。The roasting time cannot be uniquely specified because it depends on the furnace used, the atmosphere, and the temperature. However, for example, the roasting is carried out at 600 to 700 ° C. in a muffle furnace as a layer having a thickness of 40 mm. If you do 2-4
Time is needed. In this way, the aqueous solution of cobalt sulfate is reacted with the aqueous solution containing hydrogen carbonate ions, and then the pH
To 7.0-8.5 and stirred for 1 hour or more, the basic cobalt carbonate obtained does not need to be pulverized,
The roasting temperature for obtaining tricobalt tetraoxide having an average particle size of 0.1 to 0.5 μm can be lowered to 600 to 700 ° C.
【００１４】[0014]
【実施例】以下、実施例および比較例を挙げて、本発明
を詳細に説明する。 （実施例１）炭酸水素アンモニウム３４４．３ｇを純水
２．２リットルに溶解した溶液を４０℃に維持した状態
で攪拌しながら、コバルトとして６０ｇ／リットルの硫
酸コバルト水溶液２リットルを全量添加して反応させ、
ついで２８％アンモニア水を６０ミリリットル添加して
スラリーとした。このときの液中のｐＨは７．３であっ
た。その後該スラリーを４０℃に維持した状態で攪拌し
ながら４時間保持して沈澱させた。沈澱は容易に行われ
た。この沈澱を固液分離し、洗浄し、乾燥し、塩基性炭
酸コバルトの粉末２３６．４ｇを得た。この塩基性炭酸
コバルトをマッフル炉を用いて大気中６３０℃で４時間
ばい焼して１４５．３ｇの四酸化三コバルトを得た。こ
の四酸化三コバルトのＢＥＴ法で測定した平均粒径は
０．２５μｍであった。The present invention will be described in detail below with reference to examples and comparative examples. (Example 1) While stirring a solution prepared by dissolving 344.3 g of ammonium hydrogen carbonate in 2.2 liters of pure water at 40 ° C., 2 liters of a 60 g / liter cobalt sulfate aqueous solution as cobalt was added in total. Let it react,
Then, 60 ml of 28% aqueous ammonia was added to form a slurry. The pH in the liquid at this time was 7.3. Then, the slurry was maintained at 40 ° C. for 4 hours while stirring to precipitate the slurry. The precipitation was done easily. The precipitate was solid-liquid separated, washed, and dried to obtain 236.4 g of basic cobalt carbonate powder. This basic cobalt carbonate was roasted in a muffle furnace in the atmosphere at 630 ° C. for 4 hours to obtain 145.3 g of tricobalt tetraoxide. The average particle size of this tricobalt tetroxide measured by the BET method was 0.25 μm.
【００１５】（実施例２、３および比較例１、２）実施
例１と同一条件によって塩基性炭酸コバルトを得て、ば
い焼温度について調査した。調査の結果を表１に示す。(Examples 2 and 3 and Comparative Examples 1 and 2) Basic cobalt carbonate was obtained under the same conditions as in Example 1 and the roasting temperature was investigated. The results of the investigation are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】上記表１から明らかなように、塩基性炭酸
コバルトのばい焼温度が低い比較例１（５００℃）の場
合は、生成される四酸化三コバルトが微粒すぎて焼結し
やすくなり、また、ばい焼温度が高い比較例２（７３０
℃）の場合は、生成される四酸化三コバルトの解砕が必
要となる。これに対し、本発明による実施例２、３で
は、リチウム二次電池の正極用材料として使用可能な四
酸化三コバルトが得られた。As is apparent from Table 1 above, in the case of Comparative Example 1 (500 ° C.) in which the basic cobalt carbonate has a low roasting temperature, the produced tricobalt tetroxide is too fine and is easily sintered, In addition, Comparative Example 2 (730
In the case of (° C.), It is necessary to disintegrate the produced tricobalt tetroxide. On the other hand, in Examples 2 and 3 according to the present invention, tricobalt tetroxide that can be used as the material for the positive electrode of the lithium secondary battery was obtained.
【００１８】（実施例４）炭酸水素ナトリウム３４９．
１ｇを純水２．２リットルに溶解した溶液を６０℃に維
持した状態で攪拌しながら、コバルトとして６０ｇ／リ
ットルの硫酸コバルト水溶液２リットルを全量添加して
反応させ、ついで２８％アンモニア水を６０ミリリット
ル添加してスラリーを得た。このときの液中のｐＨは
７．１であった。その後該スラリーを４０℃に維持した
状態で攪拌しながら４時間保持して沈澱させた。沈澱は
容易に行われた。この沈澱を固液分離し、洗浄し、乾燥
し、塩基性炭酸コバルトの粉末２３５．７ｇを得た。こ
の塩基性炭酸コバルトをマッフル炉を用いて大気中６６
０℃で４時間ばい焼して１４４．５ｇの四酸化三コバル
トを得た。この四酸化三コバルトのＢＥＴ法で測定した
平均粒径は０．２２μｍであった。(Example 4) Sodium hydrogencarbonate 349.
While stirring a solution prepared by dissolving 1 g in 2.2 liters of pure water at 60 ° C., 2 liters of cobalt sulfate aqueous solution of 60 g / liter as cobalt was added and reacted, and then 28% ammonia water was added to 60%. A milliliter was added to obtain a slurry. The pH in the liquid at this time was 7.1. Then, the slurry was maintained at 40 ° C. for 4 hours while stirring to precipitate the slurry. The precipitation was done easily. The precipitate was subjected to solid-liquid separation, washed and dried to obtain 235.7 g of basic cobalt carbonate powder. This basic cobalt carbonate was used in a muffle furnace in the atmosphere 66
The mixture was roasted at 0 ° C. for 4 hours to obtain 144.5 g of tricobalt tetroxide. The average particle size of this tricobalt tetroxide measured by the BET method was 0.22 μm.
【００１９】（比較例３）炭酸水素アンモニウム３４
４．３ｇを純水２．２リットルに溶解した溶液を４０℃
に維持した状態で攪拌しながら、コバルトとして６０ｇ
／リットルの硫酸コバルト水溶液２リットルを全量添加
して反応させスラリーを得た。このときの液中のｐＨは
６．７であった。その後該スラリーを４０℃に維持した
状態で攪拌しながら４時間保持して沈澱させた。この沈
澱の固液分離には実施例１の場合の５倍の時間を必要と
した。そして洗浄し、乾燥し、塩基性炭酸の粉末コバル
ト２２８．８ｇを得た。この塩基性炭酸コバルトをマッ
フル炉を用いて大気中６５０℃で４時間ばい焼して１４
２．１ｇの四酸化三コバルトを得た。この四酸化三コバ
ルトは電子顕微鏡写真を観察すると１次粒子の焼結が進
んでおり、ＢＥＴ法で測定した平均粒径は０．１μｍ未
満であった。Comparative Example 3 Ammonium hydrogen carbonate 34
A solution prepared by dissolving 4.3 g in 2.2 liters of pure water is 40 ° C.
60g as cobalt while stirring while maintaining
2 liter of cobalt sulfate aqueous solution of 1 liter / liter was added and reacted to obtain a slurry. The pH in the liquid at this time was 6.7. Then, the slurry was maintained at 40 ° C. for 4 hours while stirring to precipitate the slurry. The solid-liquid separation of this precipitate required 5 times as long as in Example 1. Then, it was washed and dried to obtain 228.8 g of basic carbonate powder cobalt. This basic cobalt carbonate was roasted in the atmosphere at 650 ° C. for 4 hours in a muffle furnace to obtain 14
2.1 g of tricobalt tetroxide was obtained. Observation of electron micrographs revealed that the primary particles of this tricobalt trioxide were sintered, and the average particle diameter measured by the BET method was less than 0.1 μm.
【００２０】（比較例４）実施例１で攪拌を行わなかっ
た以外は同一の条件で塩基性炭酸コバルトを得た。なお
このときの固液分離時間は実施例１の時の６倍の時間を
必要とした。得た塩基性炭酸コバルトをマッフル炉を用
いて大気中６５０℃で４時間ばい焼して四酸化三コバル
トを得た。この四酸化三コバルトは電子顕微鏡写真を観
察すると１次粒子の焼結が進んでおり、ＢＥＴ法で測定
した平均粒径は０．１μｍ未満であった。Comparative Example 4 Basic cobalt carbonate was obtained under the same conditions as in Example 1 except that stirring was not performed. The solid-liquid separation time at this time required 6 times as long as that in Example 1. The obtained basic cobalt carbonate was roasted in the atmosphere at 650 ° C. for 4 hours using a muffle furnace to obtain tricobalt tetroxide. Observation of electron micrographs revealed that the primary particles of this tricobalt trioxide were sintered, and the average particle diameter measured by the BET method was less than 0.1 μm.
【００２１】[0021]
【発明の効果】本発明によれば、塩基性炭酸コバルト中
の水酸化物量を多くしたものをばい焼するので、解砕性
が良く、かつ、ＢＥＴ法で測定した平均粒径が０．１〜
０．５μｍであり、リチウム二次電池の正極用材料とし
て使用可能な四酸化コバルトを容易に得ることができ
る。According to the present invention, since basic cobalt carbonate having a large amount of hydroxide is roasted, the crushability is good and the average particle diameter measured by the BET method is 0.1. ~
It is 0.5 μm, and cobalt tetraoxide that can be used as a material for a positive electrode of a lithium secondary battery can be easily obtained.
Claims (3)
れるコバルトイオンに対して当量以上の炭酸水素イオン
を含む水溶液を反応させ、反応後さらにアンモニアを添
加し、ｐＨを７．０〜８．５にして１時間以上攪拌した
後沈澱させ、得られた沈澱を固液分離、洗浄、乾燥させ
て、塩基性炭酸コバルトの粉末を得て、該粉末を酸素含
有雰囲気でばい焼することを特徴とするリチウム二次電
池正極材料用四酸化三コバルトの製造方法。1. A cobalt sulfate aqueous solution is reacted with an aqueous solution containing an equivalent amount or more of hydrogen carbonate ions with respect to cobalt ions contained in the aqueous solution. After the reaction, ammonia is further added to adjust the pH to 7.0 to 8.5. After stirring for 1 hour or more, the resulting precipitate is solid-liquid separated, washed and dried to obtain a powder of basic cobalt carbonate, and the powder is roasted in an oxygen-containing atmosphere. Method for producing tricobalt tetroxide for lithium secondary battery positive electrode material.
度が６００〜７００℃である請求項１に記載の製造方
法。2. The method according to claim 1, wherein the oxygen-containing atmosphere is air and the roasting temperature is 600 to 700 ° C.
バルトの平均粒径がＢＥＴ法の測定で０．１〜０．５μ
ｍである請求項１に記載の製造方法。3. The average particle size of tricobalt tetroxide for a lithium secondary battery positive electrode material is 0.1 to 0.5 μm as measured by the BET method.
The manufacturing method according to claim 1, wherein m is m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6257296A JPH0896809A (en) | 1994-09-28 | 1994-09-28 | Manufacture of tricobalt tetroxide for lithium secondary battery positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6257296A JPH0896809A (en) | 1994-09-28 | 1994-09-28 | Manufacture of tricobalt tetroxide for lithium secondary battery positive electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0896809A true JPH0896809A (en) | 1996-04-12 |
Family
ID=17304405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6257296A Pending JPH0896809A (en) | 1994-09-28 | 1994-09-28 | Manufacture of tricobalt tetroxide for lithium secondary battery positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0896809A (en) |
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