JPH1160243A - Nickel hydroxide, lithium nickelate, their production and lithium ion secondary battery using the lithium nickelate - Google Patents
Nickel hydroxide, lithium nickelate, their production and lithium ion secondary battery using the lithium nickelateInfo
- Publication number
- JPH1160243A JPH1160243A JP9218792A JP21879297A JPH1160243A JP H1160243 A JPH1160243 A JP H1160243A JP 9218792 A JP9218792 A JP 9218792A JP 21879297 A JP21879297 A JP 21879297A JP H1160243 A JPH1160243 A JP H1160243A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- aqueous solution
- nickel hydroxide
- nickel
- lithium nickelate
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水酸化ニッケル、ニ
ッケル酸リチウム及びこれらの製造方法、並びに該水酸
化ニッケルを原料として焼成したニッケル酸リチウムを
用いたリチウムイオン二次電池に関する。なお、本発明
でいう水酸化ニッケルとは、ニッケルの一部がコバルト
又はマンガンによって置換されたものも包含するものと
する。また、本発明でいうニッケル酸リチウムも、ニッ
ケルの一部がコバルト又はマンガンによって置換された
ものも包含するものとする。The present invention relates to nickel hydroxide, lithium nickelate and a method for producing the same, and a lithium ion secondary battery using lithium nickelate fired from the nickel hydroxide as a raw material. In addition, the nickel hydroxide in the present invention includes those in which a part of nickel is replaced by cobalt or manganese. Further, the lithium nickelate referred to in the present invention also includes those in which a part of nickel is replaced by cobalt or manganese.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年の
電話やパソコン等のポータブル化、コードレス化の急速
な進歩により、それらの駆動用電源としての二次電池の
需要が高まっている。その中でも小型、かつ軽量で高エ
ネルギー密度を有するリチウムイオン二次電池は特に期
待されている。上記の要望を満たすリチウムイオン二次
電池の正極活物質（正極材料）としてリチウムを脱離、
挿入可能なコバルト酸リチウム（ＬｉＣｏＯ2 ）、ニッ
ケル酸リチウム（ＬｉＮｉＯ2 ）等のリチウム複合酸化
物の研究が盛んに行われている。これらのリチウム複合
酸化物はリチウムに対し４Ｖ以上の電位を有し、正極材
料として用いると１５０ｍＡｈ／ｇ以上の放電容量が得
られることから高エネルギー密度を有する二次電池の実
現が期待されていた。2. Description of the Related Art With the rapid progress of portable and cordless telephones and personal computers in recent years, a demand for a secondary battery as a power source for driving them is increasing. Among them, a lithium ion secondary battery having a small size, light weight and high energy density is particularly expected. Lithium is desorbed as a positive electrode active material (positive electrode material) for lithium ion secondary batteries satisfying the above demands,
Research on lithium composite oxides such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO 2 ) that can be inserted has been actively conducted. These lithium composite oxides have a potential of 4 V or more with respect to lithium, and when used as a positive electrode material, a discharge capacity of 150 mAh / g or more can be obtained. Therefore, the realization of a secondary battery having a high energy density was expected. .
【０００３】しかし、近年、リチウムイオン二次電池に
は、さらに高い放電容量が期待されている。また、経済
性の点から安価な正極材料が要求されている。In recent years, however, higher discharge capacities have been expected for lithium ion secondary batteries. In addition, inexpensive cathode materials are required from the viewpoint of economy.
【０００４】このような要求に応える正極材料としてＬ
ｉＮｉ1-x Ｃｏx Ｏ2 （ｘ＞０）が提案されている。こ
のＬｉＮｉ1-x Ｃｏx Ｏ2 （ｘ＞０）を用いたリチウム
イオン二次電池は、従来のＬｉＣｏＯ2 を用いたリチウ
ムイオン二次電池に比べ高容量であり、しかも原料が豊
富であり安価であるため、次期正極材料として有望であ
る。[0004] As a positive electrode material that meets such demands, L
iNi 1-x Co x O 2 (x> 0) has been proposed. A lithium ion secondary battery using LiNi 1-x Co x O 2 (x> 0) has a higher capacity than a conventional lithium ion secondary battery using LiCoO 2 , and is rich in raw materials and inexpensive. Therefore, it is promising as the next positive electrode material.
【０００５】しかるに、このＬｉＮｉ1-x Ｃｏx Ｏ
2 （ｘ＞０）を正極材料として用いたリチウムイオン二
次電池は、充電状態での熱的安定性が悪く、大きな問題
となっている。これは、充電でリチウムが脱インターカ
レートするにつれ構造が不安定になり、周囲の温度上昇
により構造が崩壊して有機電解液と反応し、発熱、発火
するために起こる。このように、ＬｉＮｉ1-x Ｃｏx Ｏ
2 （ｘ＞０）はＬｉＣｏＯ 2 よりも低温で発熱、発火反
応が起こるために電池としての安全性に問題があり、改
善が強く求められている。However, this LiNi1-xCoxO
Two(X> 0) as a positive electrode material
Secondary batteries have poor thermal stability in the charged state, which is a major problem
It has become. This is because lithium deintercalates on charging.
As the rate increases, the structure becomes unstable and the surrounding temperature rises.
The structure collapses and reacts with the organic electrolyte, generating heat and igniting
Happens to do. Thus, LiNi1-xCoxO
Two(X> 0) is LiCoO TwoHeat generation at lower temperature
Response to the battery, there is a problem with the safety of the battery.
Good is strongly sought.
【０００６】この熱特性改善の一つに比表面積低下によ
る熱分解反応の抑制が挙げられる。即ち、正極材料と有
機電解液の接触面積を低減することで発熱反応速度を抑
制し、発熱開始温度を高めることを目的としている。こ
れには、一次粒子の増大が必要であり、具体的にはＬｉ
Ｎｉ1-x Ｃｏx Ｏ2 （ｘ＞０）一次粒子が２μｍ以上の
正極材料を得ることが必要と考えられる。One of the improvements in the thermal characteristics is suppression of a thermal decomposition reaction due to a decrease in specific surface area. That is, an object of the present invention is to reduce the contact area between the positive electrode material and the organic electrolyte to suppress the exothermic reaction rate and increase the exothermic onset temperature. This requires an increase in primary particles, specifically Li
It is considered necessary to obtain a positive electrode material having Ni 1-x Co x O 2 (x> 0) primary particles of 2 μm or more.
【０００７】ＬｉＮｉ1-x Ｃｏx Ｏ2 （ｘ＞０）は、一
般的にＮｉ（ＯＨ)2、Ｃｏ（ＯＨ)2又は（Ｎｉ，Ｃｏ）
（ＯＨ)2の微粉状又は球状の粉末を原料に用い、ＬｉＯ
Ｈ粉末と混合し、焼成により得ている。これらの水酸化
物は一次粒子が０．５μｍ未満の凝集体であるために、
焼成時の焼結で一次粒子を増大させる必要がある。しか
し、この方法では粒子同士の凝集のために放電容量が大
きく低下してしまい、要求される粉末特性と電池特性が
両立できない。従って、電池特性を低下させることな
く、一次粒子の増大した正極材料を焼成し、電池の充電
時の熱特性を改善することが必要である。LiNi 1-x Co x O 2 (x> 0) is generally Ni (OH) 2 , Co (OH) 2 or (Ni, Co)
Using fine or spherical powder of (OH) 2 as a raw material, LiO
It is obtained by mixing with H powder and firing. Since these hydroxides are aggregates in which primary particles are less than 0.5 μm,
It is necessary to increase the primary particles by sintering during firing. However, in this method, the discharge capacity is greatly reduced due to aggregation of the particles, and the required powder characteristics and battery characteristics cannot be compatible. Therefore, it is necessary to sinter the positive electrode material in which the primary particles are increased without deteriorating the battery characteristics, and to improve the thermal characteristics during charging of the battery.
【０００８】従って、本発明の目的は、電池特性を低下
させることなく、充電時の熱特性を改善したリチウムイ
オン二次電池、該電池の正極材料の原料となる水酸化ニ
ッケル、リチウム酸ニッケル及びこれらの製造方法を提
供することを目的とする。Accordingly, it is an object of the present invention to provide a lithium ion secondary battery having improved thermal characteristics during charging without deteriorating battery characteristics, nickel hydroxide, nickel lithium oxide, which is a raw material for a positive electrode material of the battery, and An object is to provide these manufacturing methods.
【０００９】[0009]
【課題を解決するための手段】本発明者等は、鋭意検討
の結果、リチウムイオン二次電池の正極活物質の原料と
して用いられる水酸化ニッケルの一次粒子の増大を、焼
成時の焼結ではなく原料の段階で達成することによっ
て、上記目的を達成し得ることを知見した。Means for Solving the Problems As a result of diligent studies, the present inventors have found that primary particles of nickel hydroxide used as a raw material of a positive electrode active material of a lithium ion secondary battery are increased in sintering during firing. It has been found that the above object can be achieved by achieving the above at the raw material stage.
【００１０】本発明は、上記知見に基づいてなされたも
ので、下記組成式（１） Ｎｉ1-x Ａx （ＯＨ)2 （１） （Ａはコバルト又はマンガン、０．１０＜ｘ＜０．５）
で示され、結晶方位の揃った積層体または単結晶からな
り、その一次粒子径が０．５〜５μｍ、最も配向しやす
いサンプリングをして得られたＸ線回折による半値全幅
が（００１）＜０．３ｄｅｇ．、（１０１）＜０．４ｄ
ｅｇ．、かつピーク強度比Ｉ（１０１）／Ｉ（００１）
＜０．５であることを特徴とする水酸化ニッケルを提供
するものである。The present invention has been made based on the above findings, and has the following compositional formula (1): Ni 1-x A x (OH) 2 (1) (A is cobalt or manganese, 0.10 <x <0 .5)
And has a primary particle size of 0.5 to 5 μm and a full width at half maximum by X-ray diffraction obtained by sampling which is most easily oriented (001) < 0.3 deg. , (101) <0.4d
eg. And the peak intensity ratio I (101) / I (001)
The present invention provides nickel hydroxide characterized by being <0.5.
【００１１】また、本発明は、本発明の水酸化ニッケル
の好ましい製造方法として、硝酸ニッケル水溶液、硝酸
コバルト又は硝酸マンガン水溶液、及びアンモニア水溶
液からなる混合水溶液を６０〜９０℃、３時間以上の条
件で撹拌下に混合し、次いでアルカリ水溶液を滴下しつ
つ煮沸して該混合水溶液をｐＨ６．６〜７．５に維持
し、その後、アルカリ水溶液中で８時間以上熟成するこ
とを特徴とする水酸化ニッケルの製造方法を提供するも
のである。The present invention also relates to a preferred method for producing the nickel hydroxide of the present invention, wherein a mixed aqueous solution comprising an aqueous solution of nickel nitrate, an aqueous solution of cobalt nitrate or manganese nitrate, and an aqueous solution of ammonia is used at 60 to 90 ° C. for 3 hours or more. The mixture is stirred under stirring, and then the mixture is boiled while dropping an aqueous alkaline solution to maintain the mixed aqueous solution at a pH of 6.6 to 7.5, and then aged in an aqueous alkaline solution for at least 8 hours. A method for producing nickel is provided.
【００１２】更に、本発明は、下記組成式（２） ＬｉＮｉ1-x Ａx Ｏ2 （２） （Ａはコバルト又はマンガン、０．１０＜ｘ＜０．５）
で示され、その一次粒子径が０．５〜５μｍ、最も配向
しやすいサンプリングをして得られたＸ線回折によるピ
ーク強度比Ｉ（１０１）／Ｉ（００１）＜０．４である
ことを特徴とするニッケル酸リチウムを提供するもので
ある。Further, the present invention provides a composition of the following formula (2): LiNi 1-x A x O 2 (2) (A is cobalt or manganese, 0.10 <x <0.5)
Where the primary particle diameter is 0.5 to 5 μm, and the peak intensity ratio I (101) / I (001) <0.4 by X-ray diffraction obtained by sampling which is most easily oriented. A feature of the present invention is to provide lithium nickelate.
【００１３】また、本発明は、上記水酸化ニッケルをリ
チウム化合物と混合し、これを焼成して得られた上記ニ
ッケル酸リチウムを正極活物質に用いたことを特徴とす
るリチウムイオン二次電池を提供するものである。Further, the present invention provides a lithium ion secondary battery characterized in that the above-mentioned nickel hydroxide is mixed with a lithium compound, and the above-mentioned lithium nickel oxide obtained by calcining the mixture is used as a positive electrode active material. To provide.
【００１４】[0014]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明の水酸化ニッケルは、下記組成式（１） Ｎｉ1-x Ａx （ＯＨ)2 （１） で示される。上記組成式において、Ａはコバルト又はマ
ンガンであり、好ましくはコバルトである。また、ｘは
０．１０超、かつ０．５未満である。ｘが０．１以下で
は、添加元素の効果が十分得られず、また０．５以上で
は容量低下が著しくなるため、いずれも好ましくない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The nickel hydroxide of the present invention is represented by the following composition formula (1): Ni 1-x A x (OH) 2 (1) In the above composition formula, A is cobalt or manganese, preferably cobalt. X is more than 0.10 and less than 0.5. When x is 0.1 or less, the effect of the added element is not sufficiently obtained, and when x is 0.5 or more, the capacity is remarkably reduced.
【００１５】この水酸化ニッケルは、結晶方位の揃った
積層体または単結晶からなり、その一次粒子径が０．５
〜５μｍである。一次粒子径が０．５μｍ未満では、比
表面積が大き過ぎ、十分な熱安定性に欠け、また５μｍ
を超えると焼成の際に粒子内部まで完全に反応させるこ
とが難しくなるため、いずれも好ましくない。The nickel hydroxide is composed of a laminate or a single crystal having a uniform crystal orientation, and has a primary particle diameter of 0.5.
５5 μm. If the primary particle size is less than 0.5 μm, the specific surface area is too large, lacks sufficient thermal stability, and
If the ratio exceeds, it is difficult to completely react the inside of the particles at the time of firing.
【００１６】また、本発明の水酸化ニッケルの最も配向
しやすいサンプリングをして得られたＸ線回折による半
値全幅が（００１）＜０．３ｄｅｇ．、（１０１）＜
０．４ｄｅｇ．、かつピーク強度比 Ｉ（１０１）／Ｉ
（００１）＜０．５であることが必要であり、この範囲
を逸脱した場合には結晶方位の揃い方又は単結晶と見な
せる粒界の大きさが不十分となり、好ましくない。Further, the full width at half maximum by X-ray diffraction obtained by sampling the most easily oriented nickel hydroxide of the present invention is (001) <0.3 deg. , (101) <
0.4 deg. And peak intensity ratio I (101) / I
It is necessary that (001) <0.5, and if it is out of this range, the orientation of the crystallographic orientation or the size of the grain boundary regarded as a single crystal becomes insufficient, which is not preferable.
【００１７】本発明の水酸化ニッケルの走査型電子顕微
鏡（ＳＥＭ）写真（×５０００）を図１に示す。また、
比較として従来の微粉状水酸化ニッケルの走査型電子顕
微鏡写真（×１００００）を図２に、また球状水酸化ニ
ッケルの走査型電子顕微鏡写真（×１００００）を図３
にそれぞれ示す。また、本発明の水酸化ニッケルのＸ線
回折図を図４に示す。FIG. 1 shows a scanning electron microscope (SEM) photograph (× 5000) of the nickel hydroxide of the present invention. Also,
For comparison, FIG. 2 shows a scanning electron micrograph (× 10000) of a conventional powdery nickel hydroxide, and FIG. 3 shows a scanning electron micrograph (× 10000) of a spherical nickel hydroxide.
Are shown below. FIG. 4 shows an X-ray diffraction diagram of the nickel hydroxide of the present invention.
【００１８】図１から明らかなように、本発明の水酸化
ニッケルは、結晶方位の揃った積層体または単結晶であ
ることが判る。また、図１と図２〜３との比較から明ら
かなように、本発明の水酸化ニッケルは、微粉状又は球
状の水酸化ニッケルに比較して一次粒子径が大きいこと
が判る。As is clear from FIG. 1, the nickel hydroxide of the present invention is a laminate or a single crystal having a uniform crystal orientation. In addition, as is clear from the comparison between FIG. 1 and FIGS. 2 to 3, it is understood that the nickel hydroxide of the present invention has a larger primary particle diameter than the fine powder or spherical nickel hydroxide.
【００１９】上述した本発明の水酸化ニッケルは、以下
の方法によって製造される。先ず、硝酸ニッケル水溶
液、硝酸コバルト又は硝酸マンガン水溶液、及びアンモ
ニア含有水溶液を用い、この混合水溶液を６０〜９０
℃、好ましくは７５〜８５℃、３時間以上撹拌下に混合
する。この際のアンモニア／（ニッケル＋コバルト又は
マンガン）のモル比は、３〜４である。また、硝酸ニッ
ケル＋硝酸コバルト又は硝酸マンガン水溶液の濃度は、
０．５〜２．０モル／ｌである。また、アンモニア含有
水溶液とは、アンモニウムイオンを供給できる水溶液で
あり、アンモニア水溶液や硝酸アンモニウム、炭酸アン
モニウム、塩化アンモニウム、尿素等が例示される。The above-described nickel hydroxide of the present invention is produced by the following method. First, using an aqueous solution of nickel nitrate, an aqueous solution of cobalt nitrate or manganese nitrate, and an aqueous solution containing ammonia, the mixed aqueous solution
C., preferably at 75-85.degree. C., with stirring for 3 hours or more. In this case, the molar ratio of ammonia / (nickel + cobalt or manganese) is 3 to 4. The concentration of nickel nitrate + cobalt nitrate or manganese nitrate aqueous solution is
It is 0.5 to 2.0 mol / l. The ammonia-containing aqueous solution is an aqueous solution that can supply ammonium ions, and examples thereof include an aqueous ammonia solution, ammonium nitrate, ammonium carbonate, ammonium chloride, and urea.
【００２０】混合温度が６０℃未満又は９０℃超では、
目的の粒子径が得られなくなり、また混合時間が３時間
未満では、粒径０．５μｍ以下の微粉が発生し、いずれ
も好ましくない。When the mixing temperature is lower than 60 ° C. or higher than 90 ° C.,
If the desired particle size cannot be obtained, and if the mixing time is less than 3 hours, fine powder having a particle size of 0.5 μm or less is generated, which is not preferable.
【００２１】次いで、この混合水溶液中に、アルカリ水
溶液、例えば水酸化ナトリウムを滴下しながら煮沸し、
アンモニアを除去する。この際には、混合水溶液は、ｐ
Ｈを６．６〜７．５に維持することが必要であり、ｐＨ
がこの範囲を外れると粒径０．５μｍ以下の微粉が発生
し、望ましくない。Next, an aqueous alkaline solution, for example, sodium hydroxide is dropped into the aqueous mixed solution while boiling,
Remove the ammonia. At this time, the mixed aqueous solution is p
It is necessary to maintain H between 6.6 and 7.5,
Is out of this range, a fine powder having a particle size of 0.5 μm or less is generated, which is not desirable.
【００２２】その後、アルカリ水溶液中で６０〜９０℃
で８時間以上熟成し、不純物を除去する。熟成温度が上
記範囲を超えると溶液量の保持が難しく、上記範囲未満
では不純物除去に多大の時間を要する。熟成時間が８時
間未満では、不純物除去が不十分となる。アルカリ水溶
液の濃度は１．０モル／ｌ近傍であることが望ましい。Then, in an alkaline aqueous solution at 60 to 90 ° C.
For at least 8 hours to remove impurities. If the aging temperature exceeds the above range, it is difficult to maintain the amount of the solution, and if the aging temperature is below the above range, it takes a long time to remove impurities. If the aging time is less than 8 hours, the removal of impurities will be insufficient. It is desirable that the concentration of the alkaline aqueous solution is around 1.0 mol / l.
【００２３】最後に、通常の条件、方法によって純水洗
浄、濾過、乾燥して上記物性及び性状を有する水酸化ニ
ッケルを得る。純水洗浄、濾過、乾燥の条件は、例えば
５倍量の純水で洗浄し、吸引濾過後、６０〜１００℃で
８時間以上真空乾燥する。Finally, washing with pure water, filtration and drying are carried out under ordinary conditions and methods to obtain nickel hydroxide having the above-mentioned properties and properties. The conditions of washing with pure water, filtration, and drying are, for example, washing with pure water in an amount of 5 times, suction filtration, and vacuum drying at 60 to 100 ° C for 8 hours or more.
【００２４】本発明の水酸化ニッケルは、炭酸リチウ
ム、水酸化リチウム、酸化リチウム等のリチウム源とな
るリチウム化合物と混合し、焼成してニッケル酸リチウ
ムとされる。このリチウム源となるリチウム化合物とし
ては水酸化リチウム一水和物が好適に用いられる。この
際の水酸化ニッケルと例えば水酸化リチウムの混合比
（モル比）は１：１．０〜１：１．１であることが必要
である。また、焼成条件は、大気中又は酸素雰囲気下、
７００〜８５０℃、１２〜４０時間である。The nickel hydroxide of the present invention is mixed with a lithium compound serving as a lithium source such as lithium carbonate, lithium hydroxide and lithium oxide, and calcined to form lithium nickel oxide. As the lithium compound serving as the lithium source, lithium hydroxide monohydrate is suitably used. At this time, the mixing ratio (molar ratio) between nickel hydroxide and, for example, lithium hydroxide needs to be 1: 1.0 to 1: 1.1. The firing conditions are as follows:
700-850 ° C, 12-40 hours.
【００２５】本発明のリチウム酸ニッケルは、下記組成
式（２） ＬｉＮｉ1-x Ａx Ｏ2 （２） （Ａはコバルト又はマンガン、０．１０＜ｘ＜０．５）
で示され、その一次粒子径が０．５〜５μｍ、最も配向
しやすいサンプリングをして得られたＸ線回折によるピ
ーク強度比Ｉ（１０１）／Ｉ（００１）＜０．４である
ことを特徴とする。The nickel lithium oxide of the present invention has the following composition formula (2) LiNi 1-x A x O 2 (2) (A is cobalt or manganese, 0.10 <x <0.5)
Where the primary particle diameter is 0.5 to 5 μm, and the peak intensity ratio I (101) / I (001) <0.4 by X-ray diffraction obtained by sampling which is most easily oriented. Features.
【００２６】本発明のニッケル酸リチウムは、その一次
粒子径が０．５〜５μｍである。一次粒子径が０．５μ
ｍ未満では、粒子同士の凝集が無視できない位大きくな
り粉体特性が低下し、また５μｍを超えると粒子内部に
充放電に使用されない領域を生じやすくなるため、いず
れも好ましくない。The lithium nickelate of the present invention has a primary particle size of 0.5 to 5 μm. 0.5μ primary particle size
When the particle size is less than m, the aggregation of the particles becomes too large to be neglected and the powder characteristics are deteriorated.
【００２７】また、このニッケル酸リチウムは最も配向
しやすいサンプリングをして得られたＸ線回析図による
ピーク強度比Ｉ（１０１）／Ｉ（００１）＜０．４であ
る。この範囲を逸脱した場合には積層体の結晶方位の揃
い方、又は単結晶と見なせる粒界の大きさが不十分とな
り、好ましくない。The lithium nickelate has a peak intensity ratio I (101) / I (001) <0.4 according to an X-ray diffraction diagram obtained by sampling which is most easily oriented. If the ratio is out of this range, the orientation of the crystal orientation of the stacked body or the size of the grain boundary regarded as a single crystal becomes insufficient, which is not preferable.
【００２８】本発明のニッケル酸リチウム（ＬｉＮｉ
1-x Ｃｏx Ｏ2 （ｘ＞０））の走査型電子顕微鏡（ＳＥ
Ｍ）写真（×５０００）を図５に示す。また、比較とし
て従来の微粉状水酸化ニッケルを用いて得られたニッケ
ル酸リチウム（ＬｉＮｉ1-x Ｃｏx Ｏ2 （ｘ＞０））の
走査型電子顕微鏡写真（×１００００）を図６に、また
球状水酸化ニッケルを用いて得られたニッケル酸リチウ
ム（ＬｉＮｉ1-x ＣｏxＯ2 （ｘ＞０））の走査型電子
顕微鏡写真（×１００００）を図７にそれぞれ示す。ま
た、本発明のニッケル酸リチウムのＸ線回折図を図８に
示す。The lithium nickelate of the present invention (LiNi
1-x Co x O 2 (x> 0)) scanning electron microscope (SE
M) A photograph (× 5000) is shown in FIG. For comparison, FIG. 6 shows a scanning electron micrograph (× 10000) of lithium nickelate (LiNi 1-x Co x O 2 (x> 0)) obtained by using conventional finely powdered nickel hydroxide. FIG. 7 shows scanning electron micrographs (× 10000) of lithium nickelate (LiNi 1-x Co x O 2 (x> 0)) obtained using spherical nickel hydroxide. FIG. 8 shows an X-ray diffraction diagram of the lithium nickelate of the present invention.
【００２９】本発明では、このニッケル酸リチウムをリ
チウムイオン二次電池の正極活物質として用いる。この
ようにして得られたリチウムイオン二次電池は、電池特
性を低下させることなく、充電時の熱特性を改善するこ
とができる。In the present invention, this lithium nickelate is used as a positive electrode active material of a lithium ion secondary battery. The thus obtained lithium ion secondary battery can improve the thermal characteristics during charging without deteriorating the battery characteristics.
【００３０】[0030]
【実施例】以下、実施例等に基づき本発明を具体的に説
明する。EXAMPLES Hereinafter, the present invention will be specifically described based on examples and the like.
【００３１】（実施例１）硝酸ニッケル８５％、硝酸コ
バルト１５％水溶液、及びアンモニア水溶液を用い、こ
の混合水溶液を８０℃、３時間以上撹拌下に混合した。
この際のアンモニア／（ニッケル＋コバルト）のモル比
は、３である。また、硝酸ニッケル水溶液＋硝酸コバル
ト水溶液の濃度は、１．７モル／ｌとした。Example 1 An aqueous solution of 85% nickel nitrate, 15% cobalt nitrate and an aqueous ammonia solution were mixed with stirring at 80 ° C. for 3 hours or more.
At this time, the molar ratio of ammonia / (nickel + cobalt) is 3. The concentration of the aqueous solution of nickel nitrate + the aqueous solution of cobalt nitrate was 1.7 mol / l.
【００３２】次いで、この混合水溶液中に、１．０モル
／ｌの水酸化ナトリウムを滴下しながら煮沸し、アンモ
ニアを除去した。この際には、混合水溶液のｐＨは６．
９〜７．２の範囲に維持された。その後、濃度１モル／
ｌの水酸化ナトリウム水溶液中で、８０℃、８時間以上
熟成し、不純物を除去した。Next, 1.0 mol / l sodium hydroxide was added dropwise to the mixed aqueous solution and the mixture was boiled to remove ammonia. In this case, the pH of the mixed aqueous solution is 6.
It was maintained in the range of 9-7.2. Then, a concentration of 1 mol /
The solution was aged at 80 ° C. for 8 hours or more in 1 l of an aqueous sodium hydroxide solution to remove impurities.
【００３３】最後に、純水洗浄、濾過、乾燥してＮｉ
0.85Ｃｏ0.15（ＯＨ）2 の組成を有する水酸化ニッケル
を得た。純水洗浄、濾過、乾燥の条件は、５倍量の純水
で洗浄し、吸引濾過後、７０℃で１２時間真空乾燥し
た。このようにして得られた水酸化ニッケルは、図１に
示されるような粒子構造をしていた。また、一次粒子径
は２μｍ、半値全幅（００１）＝０．１８ｄｅｇ．、
（１０１）＝０．３２ｄｅｇ．、ピーク強度比Ｉ（１０
１）／Ｉ（００１）＝０．３９であった。Finally, washing with pure water, filtration, and drying
A nickel hydroxide having a composition of 0.85 Co 0.15 (OH) 2 was obtained. The conditions of washing with pure water, filtration, and drying were as follows: washing with 5 times the amount of pure water, suction filtration, and vacuum drying at 70 ° C. for 12 hours. The nickel hydroxide thus obtained had a particle structure as shown in FIG. The primary particle diameter was 2 μm, full width at half maximum (001) = 0.18 deg. ,
(101) = 0.32 deg. , Peak intensity ratio I (10
1) / I (001) = 0.39.
【００３４】この組成を有する水酸化ニッケルと、水酸
化リチウム一水和物とを混合し、酸素雰囲気中、７５０
℃で２０時間焼成し、Ｌｉ（Ｎｉ0.85Ｃｏ0.15）Ｏ2 の
組成を有するニッケル酸リチウムを得た。この時の水酸
化ニッケルと、水酸化リチウム一水和物の混合比（モル
比）は１：１．０５ であった。このようにして得られ
たニッケル酸リチウムは、図５に示されるような粒子構
造をしていた。また、一次粒子径は２μｍ、ピーク強度
比Ｉ（１０１）／Ｉ（００１）＝０．１９８であった。A mixture of nickel hydroxide having the above composition and lithium hydroxide monohydrate was mixed in an oxygen atmosphere at 750.
C. for 20 hours to obtain lithium nickelate having a composition of Li (Ni 0.85 Co 0.15 ) O 2 . At this time, the mixing ratio (molar ratio) of nickel hydroxide and lithium hydroxide monohydrate was 1: 1.05. The thus obtained lithium nickelate had a particle structure as shown in FIG. The primary particle diameter was 2 μm, and the peak intensity ratio I (101) / I (001) = 0.198.
【００３５】このニッケル酸リチウムを正極材料（正極
活物質）として用い、正極材料：アセチレンブラック：
テフロンバインダー＝０．８５：０．１：０．０３の重
量比率になるように混合し、１２０℃で２時間、予備乾
燥した。これから０．０５ｇを秤量し直径１ｃｍの円盤
状に３ｔの一軸圧力をかけて成型した後、２００℃で２
時間乾燥して正極用ペレットとした。Using this lithium nickelate as a positive electrode material (positive electrode active material), a positive electrode material: acetylene black:
The mixture was mixed so as to have a weight ratio of Teflon binder = 0.85: 0.1: 0.03, and preliminarily dried at 120 ° C. for 2 hours. From this, 0.05 g was weighed and molded into a disk having a diameter of 1 cm by applying a uniaxial pressure of 3 t.
After drying for a time, pellets for the positive electrode were obtained.
【００３６】このペレットを図９に示すようなモデルセ
ルに組み込んだ。負極には直径１ｃｍの金属リチウム、
電解液にはプロピレンカーボネートとジメチルエーテル
の１：１混合液を溶媒とした四フッ化ホウ素リチウム
（ＬｉＢＦ4)１ｍｏｌ／ｌ溶液を使用した。なお、同図
において、１は負極端子、２は絶縁物（テフロン材）、
３は負極集電板、４は負極材料、５はセパレーター、６
は正極ペレット、７は正極端子をそれぞれ示す。電池試
験は０．４４１ｍＡで４．３Ｖまで充電し、０．８８２
ｍＡで３．０Ｖまで放電した。開放時間は１０分とし
た。The pellet was assembled in a model cell as shown in FIG. For the negative electrode, metallic lithium with a diameter of 1 cm,
As the electrolytic solution, a 1 mol / l solution of lithium boron tetrafluoride (LiBF 4 ) using a 1: 1 mixture of propylene carbonate and dimethyl ether as a solvent was used. In the figure, 1 is a negative electrode terminal, 2 is an insulator (Teflon material),
3 is a negative electrode current collector plate, 4 is a negative electrode material, 5 is a separator, 6
Denotes a positive electrode pellet, and 7 denotes a positive electrode terminal. The battery test was charged at 0.441 mA to 4.3 V and 0.882
Discharged to 3.0 V at mA. The opening time was 10 minutes.
【００３７】このテストセルについて充電状態での正極
の示差熱分析を行い、結果を図１０に示した。この示差
熱分析は、正電圧４．３Ｖまで充電後、ジメチルエーテ
ルで洗浄したものをサンプルとして行った。また、この
セルの充放電特性を図１１に示した。Differential thermal analysis of the positive electrode in the charged state was performed on this test cell, and the results are shown in FIG. This differential thermal analysis was performed using a sample which was charged to a positive voltage of 4.3 V and washed with dimethyl ether. FIG. 11 shows the charge / discharge characteristics of this cell.
【００３８】（比較例１）水酸化ニッケルとして図２に
示されるような微粉状水酸化ニッケルを用いた以外は、
実施例１と同様にして、図６に示されるようなＬｉ（Ｎ
ｉ0.85Ｃｏ0.15）Ｏ2 の組成を有するニッケル酸リチウ
ムを得た。このニッケル酸リチウムを正極材料（正極活
物質）として用い、実施例１と同様にセストテセルに組
み込んだ。このテストセルについて、実施例１と同様に
充電状態での正極の示差熱分析を行い、結果を図１０に
示した。また、このセルの充放電特性を図１２に示し
た。(Comparative Example 1) Except that a fine powdered nickel hydroxide as shown in FIG. 2 was used as the nickel hydroxide,
In the same manner as in Example 1, Li (N
A lithium nickelate having a composition of i 0.85 Co 0.15 ) O 2 was obtained. This lithium nickelate was used as a positive electrode material (positive electrode active material), and was incorporated in a Sest Tecell in the same manner as in Example 1. This test cell was subjected to differential thermal analysis of the positive electrode in the charged state in the same manner as in Example 1, and the results are shown in FIG. FIG. 12 shows the charge / discharge characteristics of this cell.
【００３９】図１０に示されるように、実施例１のほう
が比較例１よりも示差熱分析のピーク値が高温側にあ
り、熱特性に優れていることが判る。また、図１１と図
１２の比較から、実施例１のほうが比較例１よりも充放
電特性が良好であり、電池性能に優れることが判る。As shown in FIG. 10, the peak value of the differential thermal analysis of Example 1 is higher than that of Comparative Example 1, indicating that the thermal characteristics are superior. Also, from a comparison between FIG. 11 and FIG. 12, it can be seen that Example 1 has better charge / discharge characteristics than Comparative Example 1 and is superior in battery performance.
【００４０】以上説明したように、本発明の水酸化ニッ
ケルを正極活物質の原料とすることによって、電池特性
を低下させることなく、充電時の熱特性を改善したリチ
ウムイオン二次電池が得られる。また、本発明の製造方
法によって、上記水酸化ニッケルが簡便かつ高収率で得
られる。As described above, by using the nickel hydroxide of the present invention as a raw material for the positive electrode active material, a lithium ion secondary battery having improved thermal characteristics during charging without lowering battery characteristics can be obtained. . In addition, the production method of the present invention allows the above-mentioned nickel hydroxide to be obtained simply and in high yield.
【図１】本発明の水酸化ニッケルの粒子構造を示す走査
型電子顕微鏡写真（×５０００）。FIG. 1 is a scanning electron micrograph (× 5000) showing the particle structure of nickel hydroxide of the present invention.
【図２】微粉状の水酸化ニッケルの粒子構造を示す走査
型電子顕微鏡写真（×１００００）。FIG. 2 is a scanning electron micrograph (× 10000) showing the particle structure of finely divided nickel hydroxide.
【図３】球状の水酸化ニッケルの粒子構造を示す走査型
電子顕微鏡写真（×１００００）。FIG. 3 is a scanning electron micrograph (× 10000) showing the particle structure of spherical nickel hydroxide.
【図４】本発明の水酸化ニッケル（Ｎｉ1-x Ｃｏx （Ｏ
Ｈ）2 ）のＸ線回折図。FIG. 4 shows the nickel hydroxide (Ni 1-x Co x (O
H) X-ray diffraction diagram of 2 ).
【図５】本発明のニッケル酸リチウム（ＬｉＮｉ1-x Ｃ
ｏx Ｏ2 （ｘ＞０））の粒子構造を示す走査型電子顕微
鏡写真（×５０００）。FIG. 5 shows a lithium nickelate (LiNi 1-x C) of the present invention.
o x O 2 (x> 0 )) scanning electron microscope photograph showing the particle structure of the (× 5000).
【図６】微粉状の水酸化ニッケルを用いて得られたニッ
ケル酸リチウム（ＬｉＮｉ1-xＣｏx Ｏ2 （ｘ＞０））
の粒子構造を示す走査型電子顕微鏡写真（×１０００
０）。FIG. 6 Lithium nickelate (LiNi 1 -x Co x O 2 (x> 0)) obtained using finely divided nickel hydroxide
Scanning electron micrograph (× 1000) showing the particle structure of
0).
【図７】球状の水酸化ニッケルを用いて得られたニッケ
ル酸リチウム（ＬｉＮｉ1-x Ｃｏx Ｏ2 （ｘ＞０））の
粒子構造を示す走査型電子顕微鏡写真（×１０００
０）。FIG. 7 is a scanning electron micrograph (× 1000) showing the particle structure of lithium nickelate (LiNi 1-x Co x O 2 (x> 0)) obtained using spherical nickel hydroxide.
0).
【図８】本発明のニッケル酸リチウム（ＬｉＮｉ1-x Ｃ
ｏx Ｏ2 （ｘ＞０））のＸ線回折図。FIG. 8 shows a lithium nickelate (LiNi 1-x C) of the present invention.
o x O 2 X-ray diffraction pattern of the (x> 0)).
【図９】実施例及び比較例で用いたテストセルの概略断
面図。FIG. 9 is a schematic sectional view of a test cell used in Examples and Comparative Examples.
【図１０】実施例１及び比較例１の充電状態での正極の
示差熱分析図。FIG. 10 is a differential thermal analysis diagram of a positive electrode in a charged state of Example 1 and Comparative Example 1.
【図１１】実施例１のセルの充放電グラフ。FIG. 11 is a charge / discharge graph of the cell of Example 1.
【図１２】比較例１のセルの充放電グラフ。FIG. 12 is a charge / discharge graph of the cell of Comparative Example 1.
１：負極端子、２：絶縁物（テフロン材）、３：負極集
電板、４：負極材料、５：セパレーター、６：正極ペレ
ット、７：正極端子。1: negative electrode terminal, 2: insulator (Teflon material), 3: negative electrode current collector plate, 4: negative electrode material, 5: separator, 6: positive electrode pellet, 7: positive electrode terminal.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｚ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI H01M 10/40 H01M 10/40 Z
Claims (5)
で示され、結晶方位の揃った積層体または単結晶からな
り、その一次粒子径が０．５〜５μｍ、最も配向しやす
いサンプリングをして得られたＸ線回折による半値全幅
が（００１）＜０．３ｄｅｇ．、（１０１）＜０．４ｄ
ｅｇ．、かつピーク強度比Ｉ（１０１）／Ｉ（００１）
＜０．５であることを特徴とする水酸化ニッケル。1. The following composition formula (1): Ni 1-x A x (OH) 2 (1) (A is cobalt or manganese, 0.10 <x <0.5)
And has a primary particle size of 0.5 to 5 μm and a full width at half maximum by X-ray diffraction obtained by sampling which is most easily oriented (001) < 0.3 deg. , (101) <0.4d
eg. And the peak intensity ratio I (101) / I (001)
Nickel hydroxide characterized by being <0.5.
硝酸マンガン水溶液、及びアンモニア水溶液からなる混
合水溶液を６０〜９０℃、３時間以上の条件で撹拌下に
混合し、次いでアルカリ水溶液を滴下しつつ煮沸して該
混合水溶液をｐＨ６．６〜７．５に維持し、その後、ア
ルカリ水溶液中で８時間以上熟成することを特徴とする
水酸化ニッケルの製造方法。2. A mixed aqueous solution composed of an aqueous solution of nickel nitrate, an aqueous solution of cobalt nitrate or manganese nitrate, and an aqueous solution of ammonia are mixed under stirring at 60 to 90 ° C. for 3 hours or more, and then the aqueous solution is boiled while adding an aqueous alkaline solution dropwise. A method for producing nickel hydroxide, comprising maintaining the mixed aqueous solution at a pH of 6.6 to 7.5 and then aging the aqueous solution in an alkaline aqueous solution for 8 hours or more.
で示され、その一次粒子径が０．５〜５μｍ、最も配向
しやすいサンプリングをして得られたＸ線回折によるピ
ーク強度比Ｉ（１０１）／Ｉ（００１）＜０．４である
ことを特徴とするニッケル酸リチウム。3. The following composition formula (2): LiNi 1-x A x O 2 (2) (A is cobalt or manganese, 0.10 <x <0.5)
Where the primary particle diameter is 0.5 to 5 μm, and the peak intensity ratio I (101) / I (001) <0.4 by X-ray diffraction obtained by sampling which is most easily oriented. Features lithium nickelate.
チウム化合物との混合体を焼成することを特徴とするニ
ッケル酸リチウムの製造方法。4. A method for producing lithium nickel oxide, comprising firing a mixture of the nickel hydroxide according to claim 1 and a lithium compound.
正極活物質として用いたリチウムイオン二次電池。5. A lithium ion secondary battery using the lithium nickelate according to claim 3 as a positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9218792A JPH1160243A (en) | 1997-08-13 | 1997-08-13 | Nickel hydroxide, lithium nickelate, their production and lithium ion secondary battery using the lithium nickelate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9218792A JPH1160243A (en) | 1997-08-13 | 1997-08-13 | Nickel hydroxide, lithium nickelate, their production and lithium ion secondary battery using the lithium nickelate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1160243A true JPH1160243A (en) | 1999-03-02 |
Family
ID=16725448
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9218792A Pending JPH1160243A (en) | 1997-08-13 | 1997-08-13 | Nickel hydroxide, lithium nickelate, their production and lithium ion secondary battery using the lithium nickelate |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000285918A (en) * | 1999-03-31 | 2000-10-13 | Kawatetsu Mining Co Ltd | Material for positive electrode of lithium secondary battery |
| KR100307163B1 (en) * | 1999-06-12 | 2001-11-01 | 김순택 | Method of preparing positive active material of lithium secondary battery |
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