JP3407594B2 - Method for producing lithium nickel composite oxide - Google Patents
Method for producing lithium nickel composite oxideInfo
- Publication number
- JP3407594B2 JP3407594B2 JP09561797A JP9561797A JP3407594B2 JP 3407594 B2 JP3407594 B2 JP 3407594B2 JP 09561797 A JP09561797 A JP 09561797A JP 9561797 A JP9561797 A JP 9561797A JP 3407594 B2 JP3407594 B2 JP 3407594B2
- Authority
- JP
- Japan
- Prior art keywords
- composite oxide
- lithium
- nickel
- nickel composite
- lithium nickel
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/34—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of sprayed or atomised solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えばリチウム二
次電池の正極活物質として有用なリチウムニッケル複合
酸化物の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a lithium nickel composite oxide useful as, for example, a positive electrode active material of a lithium secondary battery.
【０００２】[0002]
【従来の技術】従来、リチウム二次電池の正極活物質と
して用いられるリチウムニッケル複合酸化物の製造方法
としては、次のような種々の方法が提案されている。2. Description of the Related Art Conventionally, the following various methods have been proposed as a method for producing a lithium nickel composite oxide used as a positive electrode active material of a lithium secondary battery.
【０００３】（イ）炭酸リチウムと酸化ニッケルのよう
な粉末同士を混合し、酸素気流中７５０℃程度で焼成す
る、固相法による方法。(A) A solid-phase method in which powders such as lithium carbonate and nickel oxide are mixed and fired in an oxygen stream at about 750 ° C.
【０００４】（ロ）低融点の硝酸リチウムや水酸化リチ
ウムと水酸化ニッケルとを混合し、酸素気流中、低温で
焼成する方法。(B) A method in which low melting point lithium nitrate or lithium hydroxide and nickel hydroxide are mixed and fired at a low temperature in an oxygen stream.
【０００５】（ハ）硝酸リチウムと硝酸ニッケルを水に
溶解させ、超音波で霧状に噴霧し熱分解させる、噴霧熱
分解法による方法。(C) A method by a spray pyrolysis method in which lithium nitrate and nickel nitrate are dissolved in water and atomized by ultrasonic waves for thermal decomposition.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
製造方法それぞれにおいて、以下に示すような問題点を
有していた。However, each of the above manufacturing methods has the following problems.
【０００７】（イ）の固相法においては、出発原料とし
て炭酸塩や酸化物などの粉末を使用するため、比較的高
温で焼成する必要がある。このため、リチウムの蒸発が
激しく、Ｌｉ／Ｎｉのモル比がズレてしまう。又、各々
の粉末を分子レベルで均一に混合することは不可能であ
り、例えば目的とするＬｉＮｉＯ2 以外にＬｉ2 Ｎｉ8
Ｏ10の生成を伴うことがあり、これらを防ぐために酸素
濃度を調整しながら長時間の焼成を数度繰り返す必要が
あった。In the solid phase method (a), since powders of carbonates and oxides are used as starting materials, it is necessary to calcine at a relatively high temperature. For this reason, the evaporation of lithium is intense and the molar ratio of Li / Ni shifts. Further, it is impossible to uniformly mix the respective powders at the molecular level. For example, in addition to the target LiNiO 2 , Li 2 Ni 8
Occurrence of O 10 may occur, and in order to prevent these, it was necessary to repeat firing for several hours while adjusting the oxygen concentration.
【０００８】（ロ）の方法においては、固相法の場合と
比較して、低温で合成するためＬｉとＮｉ比のズレが少
ない。In the method (b), compared with the case of the solid phase method, since the synthesis is performed at a low temperature, the difference between the Li and Ni ratios is small.
【０００９】しかしながら、長時間焼成しないと、得ら
れる複合酸化物の結晶性が悪くなる。このため、二次電
池の活物質として用いた場合、電池の充放電サイクルを
繰り返すうちに、結晶構造が崩れ二次電池の容量が低下
するという問題点を有していた。さらに、二次電池の充
放電サイクル特性を改善するために、Ｎｉに近いイオン
半径を持つＦｅ、Ｃｏ、Ｍｎ、Ｍｇ、Ａｌといったカチ
オンでＮｉを置換する場合は、Ｎｉと置換カチオンの分
布が不均一なものとならざるを得なかった。However, if not fired for a long time, the crystallinity of the obtained composite oxide will deteriorate. Therefore, when used as an active material of a secondary battery, there is a problem that the crystal structure collapses and the capacity of the secondary battery decreases during repeated charge / discharge cycles of the battery. Furthermore, in order to improve the charge / discharge cycle characteristics of the secondary battery, when Ni is replaced with a cation having an ionic radius close to that of Ni, such as Fe, Co, Mn, Mg, or Al, the distribution of Ni and the replacement cation is not uniform. It had to be uniform.
【００１０】（ハ）の噴霧熱分解法においては、リチウ
ムニッケル複合酸化物を構成する元素をイオンレベルで
均一に混合できるため、従来法と比較しても、格段に均
一性を増すことができる。又、原料の粉砕工程を必要と
しないため、粉砕工程に起因する不純物の混入を防止で
きるという利点を有している。In the spray pyrolysis method (c), since the elements constituting the lithium nickel composite oxide can be uniformly mixed at the ion level, the uniformity can be remarkably increased as compared with the conventional method. . Moreover, since the raw material crushing step is not required, there is an advantage that impurities can be prevented from being mixed in due to the crushing step.
【００１１】しかしながら、噴霧熱分解法では、脱水、
乾燥及び熱分解の一連の操作が数秒以内の短時間のうち
に行われるため、従来の焼成処理に比べて熱履歴が極め
て短く、合成した複合酸化物の結晶性が悪くなる傾向を
示す。このため、二次電池の活物質として用いた場合、
電池の充放電サイクルを繰り返すうちに、結晶構造が崩
れ二次電池の容量が低下するという問題点を有してい
た。又、合成した複合酸化物の比表面積が数十ｍ2 ／ｇ
と非常に大きいため、この複合酸化物と接触する電解液
が分解して、二次電池の充放電サイクル特性や保存特性
を著しく低下させる場合があるという問題点を有してい
た。However, in the spray pyrolysis method, dehydration,
Since a series of operations of drying and thermal decomposition are performed within a short time within a few seconds, the thermal history is extremely short as compared with the conventional baking treatment, and the crystallinity of the synthesized composite oxide tends to deteriorate. Therefore, when used as the active material of a secondary battery,
There was a problem that the crystal structure collapsed and the capacity of the secondary battery decreased as the charge / discharge cycle of the battery was repeated. In addition, the specific surface area of the synthesized composite oxide is several tens m 2 / g
Therefore, there is a problem in that the electrolytic solution in contact with the composite oxide may be decomposed and the charge / discharge cycle characteristics and storage characteristics of the secondary battery may be significantly deteriorated.
【００１２】そこで、本発明の目的は、上記問題点を解
決し、リチウム二次電池の正極活物質として用いたとき
に、均質で、充放電サイクル特性や保存特性に優れた、
リチウムニッケル複合酸化物の製造方法を提供すること
にある。Therefore, an object of the present invention is to solve the above-mentioned problems, and when used as a positive electrode active material of a lithium secondary battery, it is homogeneous and is excellent in charge / discharge cycle characteristics and storage characteristics.
It is to provide a method for producing a lithium nickel composite oxide.
【００１３】[0013]
【課題を解決するための手段】上記目的を達成するた
め、本発明のリチウムニッケル複合酸化物の製造方法
は、リチウムニッケル複合酸化物を構成する金属元素を
含む化合物の水溶液及びアルコール溶液のうち少なくと
も１種を噴霧熱分解して複合酸化物を得た後、該複合酸
化物をアニールして平均粒径を１〜５μｍに成長させ、
比表面積を２〜１０ｍ2 ／ｇとすることを特徴とする。In order to achieve the above object, the method for producing a lithium-nickel composite oxide of the present invention comprises at least an aqueous solution and an alcohol solution of a compound containing a metal element constituting the lithium-nickel composite oxide. After spray pyrolyzing one type to obtain a composite oxide, the composite oxide is annealed to grow the average particle size to 1 to 5 μm,
The specific surface area is 2 to 10 m 2 / g.
【００１４】又、前記噴霧熱分解の温度は５００〜９０
０℃であり、前記アニールの温度は６００〜８５０℃で
あることを特徴とする。The temperature of the spray pyrolysis is 500 to 90.
The temperature is 0 ° C., and the annealing temperature is 600 to 850 ° C.
【００１５】又、前記リチウムニッケル複合酸化物は、
ＬｉＮｉＯ2 であることを特徴とする。The lithium nickel composite oxide is
It is characterized in that it is LiNiO 2 .
【００１６】又、前記金属元素を含む化合物は無機酸塩
であることを特徴とする。Further, the compound containing the metal element is an inorganic acid salt.
【００１７】そして、前記金属元素を含む化合物は、硝
酸リチウム、酢酸リチウム及びギ酸リチウムのうち少な
くとも１種と、硝酸ニッケル、酢酸ニッケル及びギ酸ニ
ッケルのうち少なくとも１種であることを特徴とする。The compound containing the metal element is characterized in that it is at least one of lithium nitrate, lithium acetate and lithium formate, and at least one of nickel nitrate, nickel acetate and nickel formate.
【００１８】上述のように、リチウムニッケル複合酸化
物を構成する金属元素を含む化合物の水溶液及び／又は
アルコール溶液を加熱雰囲気中に噴霧すると、瞬時に熱
分解して自己化学分解作用により微細化が起こり、表面
活性の高い微細な複合酸化物が得られる。その後、この
複合酸化物をアニールすることにより、平均粒径が１〜
５μｍに成長し比表面積が２〜１０ｍ2 ／ｇの、リチウ
ム二次電池用正極活物質として好適な表面活性の高い複
合酸化物を得ることができる。As described above, when an aqueous solution and / or alcohol solution of a compound containing a metal element forming the lithium nickel composite oxide is sprayed into a heating atmosphere, it is instantly decomposed by heat and self-chemically decomposes to reduce the size. Occurs, and a fine composite oxide having high surface activity is obtained. Then, by annealing this composite oxide, the average particle size is 1 to
It is possible to obtain a complex oxide having a high surface activity which grows to 5 μm and has a specific surface area of 2 to 10 m 2 / g, which is suitable as a positive electrode active material for a lithium secondary battery.
【００１９】なお、本発明でいうリチウムニッケル複合
酸化物はＬｉＮｉＯ2 に限定されるものではない。特性
改善を目的としてＮｉの一部をＣｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｍｇ、Ａｌなどで置換したものもリチウムニッケル
複合酸化物に含む。したがって、本発明のリチウムニッ
ケル複合酸化物を構成する金属元素としては、Ｌｉ、Ｎ
ｉに限定されずに、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｍｇ、Ａ
ｌなども含まれる。そして、これらの代表的な水溶性化
合物としては、酢酸塩、ギ酸塩、硝酸塩、塩化物などが
挙げられる。これら酢酸塩、ギ酸塩、硝酸塩、塩化物な
どの化合物は、アルコキシドなどの分子中の水素イオン
を金属イオンで置換した有機化合物に比べて極めて安価
であり、原料コストを低く抑えることができるので工業
的に有利である。The lithium nickel composite oxide referred to in the present invention is not limited to LiNiO 2 . A part of Ni is Cr, Mn, Fe, C for the purpose of improving the characteristics.
Those substituted with o, Mg, Al and the like are also included in the lithium nickel composite oxide. Therefore, as the metal elements constituting the lithium nickel composite oxide of the present invention, Li, N
Not limited to i, Cr, Mn, Fe, Co, Mg, A
1 and the like are also included. And as these typical water-soluble compounds, acetate, formate, nitrate, chloride and the like can be mentioned. Compounds such as acetates, formates, nitrates and chlorides are extremely cheap as compared with organic compounds in which hydrogen ions in the molecule such as alkoxides are replaced with metal ions, and the raw material cost can be kept low. Is advantageous.
【００２０】[0020]
【発明の実施の形態】以下、本発明の実施の形態につい
て、リチウムニッケル複合酸化物がＬｉＮｉＯ2 の場合
を例として、実施例により説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described by way of examples, taking a case where the lithium nickel composite oxide is LiNiO 2 as an example.
【００２１】（実施例）まず、ＬｉＮｉＯ2 を構成する
金属元素の化合物として、硝酸リチウム、酢酸リチウ
ム、ギ酸リチウム、硝酸ニッケル、酢酸ニッケル及びギ
酸ニッケルを用意した。次に、これら化合物を表１に示
す原料の組み合わせで、ＬｉとＮｉのモル比で１：１と
なるようにそれぞれ正確に秤量分取して容器に入れ、こ
れに水とアルコールの１：１（体積比）混合溶液１００
０ｍｌを加えた後、撹拌して溶解させた。(Examples) First, lithium nitrate, lithium acetate, lithium formate, nickel nitrate, nickel acetate and nickel formate were prepared as compounds of metal elements constituting LiNiO 2 . Next, these compounds were accurately weighed out and put into a container with a combination of the raw materials shown in Table 1 so that the molar ratio of Li and Ni was 1: 1. (Volume ratio) Mixed solution 100
After adding 0 ml, the mixture was stirred and dissolved.
【００２２】次に、この混合溶液を４００〜９００℃間
の所定温度に調整した縦型熱分解炉内へ、１２００ｍｌ
／時間の速度でノズルから霧状に吹き込んで熱分解さ
せ、複合酸化物の粉末を得た。その後、得られた複合酸
化物をアルミナ製の匣に入れ、５００〜９００℃間の所
定温度で２時間アニールして、表１の試料番号１〜１６
に示すＬｉＮｉＯ2 を得た。Next, 1200 ml of this mixed solution was put into a vertical pyrolysis furnace adjusted to a predetermined temperature between 400 and 900 ° C.
It was blown in a mist form from a nozzle at a rate of / hour for thermal decomposition to obtain a composite oxide powder. Then, the obtained composite oxide was put into an alumina box and annealed at a predetermined temperature of 500 to 900 ° C. for 2 hours to obtain sample numbers 1 to 16 in Table 1.
To obtain LiNiO 2 .
【００２３】又、表１の試料番号１７に示す比較例とし
て、他の合成法によりＬｉＮｉＯ2を得た。即ち、ま
ず、出発原料として水酸化リチウムと水酸化ニッケルを
用意した、次に、この水酸化リチウムと水酸化ニッケル
をＬｉとＮｉのモル比で１：１となるようにそれぞれ正
確に秤量分取した後、ボールミルで粉砕・混合後、７５
０℃で２時間酸素気流中で焼成し、複合酸化物を得た。Further, as a comparative example shown in sample No. 17 of Table 1, LiNiO 2 was obtained by another synthesis method. That is, first, lithium hydroxide and nickel hydroxide were prepared as starting materials, and then the lithium hydroxide and nickel hydroxide were accurately weighed and fractionated so that the molar ratio of Li and Ni was 1: 1. After crushing and mixing with a ball mill, 75
The composite oxide was obtained by firing in an oxygen stream at 0 ° C. for 2 hours.
【００２４】次に、以上得られた複合酸化物の粉末につ
いて、走査型電子顕微鏡（ＳＥＭ）写真を撮り、それよ
り粒径を求めた。又、窒素吸着法により複合酸化物の比
表面積を求めた。さらに、Ｘ線回折（ＸＲＤ）分析法に
より、複合酸化物の同定を行なった。以上の結果を表１
に示す。なお表１中のＬＮはＬｉＮｉＯ2 を表し、ＮＯ
はＬｉ2 Ｎｉ8 Ｏ10 を表す。Next, a scanning electron microscope (SEM) photograph was taken of the powder of the composite oxide obtained above, and the particle size was determined from it. Further, the specific surface area of the composite oxide was determined by the nitrogen adsorption method. Further, the composite oxide was identified by an X-ray diffraction (XRD) analysis method. The above results are shown in Table 1.
Shown in. Note that LN in Table 1 represents LiNiO 2 , and NO
Represents Li 2 Ni 8 O 10 .
【００２５】[0025]
【表１】 [Table 1]
【００２６】次に、以上得られた複合酸化物を正極活物
質として、二次電池を作製した。即ち、上記複合酸化物
の粉末と導電剤としてのアセチレンブラックと、結着剤
としてのポリ４フッ化エチレンを混練し、シート状に成
形し、ＳＵＳメッシュに圧着して正極とした。Next, a secondary battery was prepared using the composite oxide obtained above as a positive electrode active material. That is, the powder of the above complex oxide, acetylene black as a conductive agent, and polytetrafluoroethylene as a binder were kneaded, molded into a sheet, and pressed onto a SUS mesh to obtain a positive electrode.
【００２７】その後、図１に示すように、ポリプロピレ
ン製のセパレータ５を介して、上記正極３と負極４とし
てのリチウム金属を正極３のＳＵＳメッシュ側が外側に
なるように重ね、正極３を下にしてステンレス製の正極
缶１内に収容した。そして、セパレータ５に電解液を染
み込ませた。なお、電解液としては、プロピレンカーボ
ネートと１，１−ジメトキシエタンの混合溶媒に過塩素
酸リチウムを溶解させたものを用いた。その後、正極缶
１の口を絶縁パッキング６を介してステンレス製の負極
板２で封止し、表２に示す種類のリチウム二次電池を完
成させた。After that, as shown in FIG. 1, the positive electrode 3 and the lithium metal as the negative electrode 4 are stacked with the SUS mesh side of the positive electrode 3 on the outside through the separator 5 made of polypropylene, and the positive electrode 3 is placed downward. And stored in a positive electrode can 1 made of stainless steel. Then, the separator 5 was impregnated with the electrolytic solution. As the electrolytic solution, a solution prepared by dissolving lithium perchlorate in a mixed solvent of propylene carbonate and 1,1-dimethoxyethane was used. Then, the mouth of the positive electrode can 1 was sealed with a negative electrode plate 2 made of stainless steel through an insulating packing 6 to complete a lithium secondary battery of the type shown in Table 2.
【００２８】次に、得られたリチウム二次電池につい
て、充放電電流密度０．５ｍＡ／ｃｍ2 、充電終止電圧
が４．２Ｖ、放電終止電圧が３．０Ｖの条件下で１００
サイクルの充放電試験を行なった。その後、充放電試験
終了後の二次電池を解体し、正極の状態（剥離の有無）
を目視で確認した。以上の結果を表２に示す。Next, the obtained lithium secondary battery was charged under conditions of a charge / discharge current density of 0.5 mA / cm 2 , a charge end voltage of 4.2 V, and a discharge end voltage of 3.0 V.
A cycle charge / discharge test was performed. After that, disassemble the secondary battery after completion of the charge / discharge test and check the state of the positive electrode (presence or absence of peeling)
Was visually confirmed. The above results are shown in Table 2.
【００２９】[0029]
【表２】 [Table 2]
【００３０】表１の結果より、リチウムニッケル複合酸
化物を構成する金属元素の溶液を噴霧熱分解した後、ア
ニールすることにより、平均粒径を１〜５μｍに成長さ
せ、比表面積を２〜１０ｍ2 ／ｇとした複合酸化物が得
られる。又、この複合酸化物はＬｉＮｉＯ2 の単相を示
している。そして、この複合酸化物を正極活物質として
用いることにより、表２に示すように、充放電サイクル
特性に優れた電極の剥離などの劣化のないリチウム二次
電池が得られる。From the results shown in Table 1, the solution of the metal element constituting the lithium nickel composite oxide was sprayed and pyrolyzed and then annealed to grow the average particle size to 1 to 5 μm and the specific surface area to 2 to 10 m. A composite oxide of 2 / g is obtained. Further, this composite oxide shows a single phase of LiNiO 2 . Then, by using this composite oxide as a positive electrode active material, as shown in Table 2, a lithium secondary battery having excellent charge / discharge cycle characteristics without deterioration such as peeling of electrodes can be obtained.
【００３１】なお、噴霧熱分解温度の具体的な温度範囲
としては、５００〜９００℃が好ましい。即ち、５００
℃以上ではリチウムニッケル複合酸化物の単相が得られ
る。又、上限は、生成したリチウムニッケル複合酸化物
が熱により再度分解しない温度以下に限定される。The specific temperature range of the spray pyrolysis temperature is preferably 500 to 900 ° C. That is, 500
A single phase of a lithium nickel composite oxide is obtained at a temperature of ℃ or above. Further, the upper limit is limited to a temperature not higher than the temperature at which the produced lithium nickel composite oxide is not decomposed again by heat.
【００３２】又、アニール温度の具体的な温度範囲とし
ては、６００〜８５０℃が好ましい。即ち、６００℃未
満では熱分解で得たリチウムニッケル複合酸化物の結晶
性や粒径の成長が不十分で、二次電池としたときのサイ
クル特性や保存特性の改善がみられない。一方、アニー
ル温度が８５０℃を超えると粒径が成長しすぎて、リチ
ウムニッケル複合酸化物を正極活物質としたときに得ら
れる二次電池の容量が低下してしまう。The specific temperature range of the annealing temperature is preferably 600 to 850 ° C. That is, when the temperature is lower than 600 ° C., the crystallinity and particle size of the lithium nickel composite oxide obtained by thermal decomposition are insufficiently grown, and the cycle characteristics and storage characteristics cannot be improved in the secondary battery. On the other hand, when the annealing temperature exceeds 850 ° C., the grain size grows too much, and the capacity of the secondary battery obtained when the lithium nickel composite oxide is used as the positive electrode active material decreases.
【００３３】なお、上記実施例においては、ＬｉＮｉＯ
2 を構成する金属元素の化合物が硝酸塩、酢酸塩又はギ
酸塩の場合について説明したが、本発明はこれのみに限
定されるものではない。即ち、これら以外に塩化物など
の水又はアルコールに溶解する化合物を適宜用いること
ができる。In the above embodiment, LiNiO
Although the case where the compound of the metal element constituting 2 is nitrate, acetate or formate has been described, the present invention is not limited to this. That is, other than these, compounds such as chlorides that are soluble in water or alcohol can be used as appropriate.
【００３４】又、試料番号１４に示すように、これらＬ
ｉＮｉＯ2 を構成する金属元素の化合物のうち、Ｌｉ化
合物として硝酸リチウムを用いＮｉ化合物としてギ酸ニ
ッケルを用いることにより、試料番号１０に示す酢酸リ
チウムと酢酸ニッケルを用いた場合や、試料番号１１に
示すギ酸リチウムとギ酸ニッケルを用いた場合と比較し
て放電容量が高く、試料番号４に示す硝酸リチウムと硝
酸ニッケルを用いた場合と同等の高い放電容量を得るこ
とができる。そして、この硝酸リチウムとギ酸ニッケル
を用いた場合には、式（１）に示すような反応が起こ
り、式（２）の反応が起こる硝酸リチウムと硝酸ニッケ
ルと比較して、ＮＯ2 の発生量が１／３となり、反応後
の廃ガス処理が容易となる。したがって、ＬｉＮｉＯ2
を構成する金属元素の化合物としては、硝酸リチウムと
ギ酸ニッケルを用いるのが最も好ましい。Further, as shown in sample No. 14, these L
When lithium nitrate is used as the Li compound and nickel formate is used as the Ni compound among the compounds of the metal elements constituting iNiO 2 , the case of using lithium acetate and nickel acetate shown in Sample No. 10 or shown in Sample No. 11 is shown. The discharge capacity is higher than that when lithium formate and nickel formate are used, and the same high discharge capacity as when using lithium nitrate and nickel nitrate shown in Sample No. 4 can be obtained. When this lithium nitrate and nickel formate are used, a reaction as shown in formula (1) occurs, and the amount of NO 2 generated is greater than that of lithium nitrate and nickel nitrate in which the reaction of formula (2) occurs. Becomes 1/3, and the waste gas treatment after the reaction becomes easy. Therefore, LiNiO 2
It is most preferable to use lithium nitrate and nickel formate as the compound of the metal element constituting the.
【００３５】 ＬｉＮＯ3 ＋Ｎｉ（ＨＣＯＯ）2 ＋Ｏ2 → ＬｉＮｉＯ2 ＋２ＣＯ2 ＋ＮＯ2 ＋Ｈ2 Ｏ ・・（１） ＬｉＮＯ3 ＋Ｎｉ（ＮＯ3 ）2 → ＬｉＮｉＯ2 ＋３ＮＯ2 ＋０．５Ｏ2 ・・（２）。LiNO 3 + Ni (HCOO) 2 + O 2 → LiNiO 2 + 2CO 2 + NO 2 + H 2 O .. (1) LiNO 3 + Ni (NO 3 ) 2 → LiNiO 2 + 3NO 2 + 0.5O 2. (2).
【００３６】又、リチウムニッケル複合酸化物が、Ｌｉ
ＮｉＯ2 以外の、ＬｉＮｉＯ2 のＮｉサイトの一部をＣ
ｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｍｇ、Ａｌなどで置換したもの
などの場合にも、同様の効果を得ることができる。The lithium nickel composite oxide is Li
Except for NiO 2 , a part of Ni site of LiNiO 2 is C
Similar effects can be obtained also in the case of substituting with r, Mn, Fe, Co, Mg, Al or the like.
【００３７】[0037]
【発明の効果】以上の説明で明らかなように、本発明の
製造方法によれば、均質で、粒径が１〜５μｍであって
比表面積が２〜１０ｍ2 ／ｇのリチウムニッケル複合酸
化物を得ることができる。As is apparent from the above description, according to the production method of the present invention, a lithium nickel composite oxide that is homogeneous, has a particle size of 1 to 5 μm and a specific surface area of 2 to 10 m 2 / g. Can be obtained.
【００３８】したがって、この複合酸化物を二次電池の
正極活物質として用いることにより、充放電サイクル特
性や保存特性に優れたリチウム二次電池を得ることがで
きる。Therefore, by using this composite oxide as a positive electrode active material of a secondary battery, a lithium secondary battery having excellent charge / discharge cycle characteristics and storage characteristics can be obtained.
【図１】リチウム二次電池の一例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of a lithium secondary battery.
１ 正極缶 ２ 負極板 ３ 正極 ４ 負極 ５ セパレータ ６ 絶縁パッキング 1 positive electrode can 2 Negative electrode plate 3 positive electrode 4 Negative electrode 5 separator 6 Insulating packing
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平10−69910（ＪＰ，Ａ) 特開 平３−80118（ＪＰ，Ａ) 特開 平８−306358（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 25/00 - 57/00 H01M 4/02 H01M 4/58 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-10-69910 (JP, A) JP-A-3-80118 (JP, A) JP-A-8-306358 (JP, A) (58) Field (Int.Cl. 7 , DB name) C01G 25/00-57/00 H01M 4/02 H01M 4/58
Claims (5)
金属元素を含む化合物の水溶液及びアルコール溶液のう
ち少なくとも１種を噴霧熱分解して複合酸化物を得た
後、該複合酸化物をアニールして平均粒径を１〜５μｍ
に成長させ、比表面積を２〜１０ｍ2 ／ｇとすることを
特徴とする、リチウムニッケル複合酸化物の製造方法。1. A composite oxide is obtained by subjecting at least one of an aqueous solution of a compound containing a metal element constituting a lithium nickel composite oxide and an alcohol solution to spray pyrolysis to obtain the composite oxide, and then annealing the composite oxide. Average particle size 1-5 μm
And a specific surface area of 2 to 10 m 2 / g.
℃であり、前記アニールの温度は６００〜８５０℃であ
ることを特徴とする、請求項１記載のリチウムニッケル
複合酸化物の製造方法。2. The temperature of the spray pyrolysis is 500 to 900.
C., and the annealing temperature is 600 to 850.degree. C., The method for producing a lithium-nickel composite oxide according to claim 1, wherein the annealing temperature is 600 to 850.degree.
ｉＮｉＯ2 であることを特徴とする、請求項１又は請求
項２記載のリチウムニッケル複合酸化物の製造方法。3. The lithium nickel composite oxide is L
characterized in that it is a INiO 2, The method according to claim 1 or claim 2 lithium nickel composite oxide according.
あることを特徴とする、請求項１〜３のうちいずれかに
記載のリチウムニッケル複合酸化物の製造方法。4. The method for producing a lithium nickel composite oxide according to claim 1, wherein the compound containing the metal element is an inorganic acid salt.
ウム、酢酸リチウム及びギ酸リチウムのうち少なくとも
１種と、硝酸ニッケル、酢酸ニッケル及びギ酸ニッケル
のうち少なくとも１種であることを特徴とする、請求項
１〜３のうちいずれかに記載のリチウムニッケル複合酸
化物の製造方法。5. The compound containing a metal element is at least one selected from lithium nitrate, lithium acetate and lithium formate, and at least one selected from nickel nitrate, nickel acetate and nickel formate. Item 4. A method for producing a lithium nickel composite oxide according to any one of Items 1 to 3.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09561797A JP3407594B2 (en) | 1996-08-13 | 1997-04-14 | Method for producing lithium nickel composite oxide |
| DE69700687T DE69700687T2 (en) | 1996-08-13 | 1997-07-17 | Process for the preparation of lithium complex containing cobalt or nickel |
| EP97112289A EP0824087B1 (en) | 1996-08-13 | 1997-07-17 | Manufacturing method of lithium complex oxide comprising cobalt or nickel |
| CA002212824A CA2212824C (en) | 1996-08-13 | 1997-08-12 | Manufacturing method of lithium complex oxide comprising cobalt or nickel |
| US08/910,753 US6187282B1 (en) | 1996-08-13 | 1997-08-13 | Manufacturing method of lithium complex oxide comprising cobalt or nickel |
| KR1019970038609A KR100282720B1 (en) | 1996-08-13 | 1997-08-13 | Manufacturing method of lithium complex oside comprising cobalt or nickel |
| CN97117612A CN1091545C (en) | 1996-08-13 | 1997-08-13 | Mannufacturing method of lithium complex oxide comprising cobalt or nickel |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21343596 | 1996-08-13 | ||
| JP8-213435 | 1996-08-13 | ||
| JP09561797A JP3407594B2 (en) | 1996-08-13 | 1997-04-14 | Method for producing lithium nickel composite oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10114528A JPH10114528A (en) | 1998-05-06 |
| JP3407594B2 true JP3407594B2 (en) | 2003-05-19 |
Family
ID=26436838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09561797A Expired - Fee Related JP3407594B2 (en) | 1996-08-13 | 1997-04-14 | Method for producing lithium nickel composite oxide |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3407594B2 (en) |
| KR (1) | KR100282720B1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0986117B1 (en) * | 1997-05-27 | 2007-08-29 | TDK Corporation | Method for producing electrode for non-aqueous electrolyte battery |
| JP4872164B2 (en) * | 2001-06-13 | 2012-02-08 | 三菱化学株式会社 | Layered lithium nickel manganese composite oxide |
| KR100564744B1 (en) | 2003-05-07 | 2006-03-27 | 한국전자통신연구원 | Li-Co-Mn oxides as cathode material for lithium batteries and synthesis of the same |
| JP2006339092A (en) * | 2005-06-06 | 2006-12-14 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery and its negative electrode |
| JP2010108928A (en) * | 2008-10-01 | 2010-05-13 | Daiken Chemical Co Ltd | Process of producing lithium cell active material, lithium cell active material, and lithium system secondary battery |
| WO2022076280A1 (en) * | 2020-10-05 | 2022-04-14 | Northwestern University | Composites with surface refining and conformal graphene coating, electrodes, and fabricating methods of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4567031A (en) * | 1983-12-27 | 1986-01-28 | Combustion Engineering, Inc. | Process for preparing mixed metal oxides |
| FR2704216A1 (en) * | 1993-04-23 | 1994-10-28 | Centre Nat Rech Scient | Electrode materials for rechargeable lithium batteries and their method of synthesis |
-
1997
- 1997-04-14 JP JP09561797A patent/JP3407594B2/en not_active Expired - Fee Related
- 1997-08-13 KR KR1019970038609A patent/KR100282720B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR100282720B1 (en) | 2001-02-15 |
| KR19980018644A (en) | 1998-06-05 |
| JPH10114528A (en) | 1998-05-06 |
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