JP3141858B2 - Lithium transition metal halide oxide, method for producing the same and use thereof - Google Patents
Lithium transition metal halide oxide, method for producing the same and use thereofInfo
- Publication number
- JP3141858B2 JP3141858B2 JP10296266A JP29626698A JP3141858B2 JP 3141858 B2 JP3141858 B2 JP 3141858B2 JP 10296266 A JP10296266 A JP 10296266A JP 29626698 A JP29626698 A JP 29626698A JP 3141858 B2 JP3141858 B2 JP 3141858B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- metal halide
- transition metal
- oxide
- halogen
- 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
-
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明はリチウム二次電池に適し
た正極材料およびその製造方法並びにその用途に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cathode material suitable for a lithium secondary battery, a method for producing the same, and a use thereof.
【０００２】[0002]
【従来の技術】近年、ノート型パーソナルコンピュータ
ー、携帯電話等ポータブル機器の性能の進歩は著しく、
小型軽量化、高性能化が促進され、それに伴い、これら
機器の電源として搭載される電池についても、小型軽量
で高性能の充放電サイクル劣化の少ない二次電池が必要
とされ、リチウムイオン二次電池が実用化された。ま
た、環境問題が深刻化する中、電気自動車用の二次電池
や夜間の余剰電力の平均化使用のための電力貯蔵用の二
次電池としてリチウムイオン二次電池を使用する研究が
行われている。正極材料に関しては、現在市販のリチウ
ムイオン二次電池の正極材料として用いられているＬｉ
ＣｏＯ2は高価なコバルトを原料に用いるため、製造コ
ストを下げるため安価なニッケルやマンガンを原料とす
るリチウム含有遷移金属酸化物であるＬｉＮｉＯ2やＬ
ｉＭｎ2Ｏ4が注目され、その研究が活発に進められてい
る。2. Description of the Related Art In recent years, the performance of portable devices such as notebook personal computers and mobile phones has been remarkably advanced.
With the promotion of miniaturization, lightening and high performance, batteries used as power supplies for these devices also need to be small, lightweight, and high performance secondary batteries with little deterioration in charge / discharge cycles. The battery has been put to practical use. In addition, as environmental problems become more serious, research is being conducted on the use of lithium-ion secondary batteries as secondary batteries for electric vehicles and as secondary batteries for storing power for averaging excess power at night. I have. Regarding the positive electrode material, Li which is currently used as a positive electrode material of a commercially available lithium ion secondary battery
Since CoO 2 uses expensive cobalt as a raw material, LiNiO 2 or L, which is a lithium-containing transition metal oxide made from inexpensive nickel or manganese as a raw material in order to reduce manufacturing costs, is used.
Attention has been paid to iMn 2 O 4 , and its research is being actively promoted.
【０００３】しかしながら、従来のリチウム含有遷移金
属酸化物を正極材料として用いるリチウム二次電池は、
充放電の繰り返しによる容量減少や保存特性が５０℃程
度以上の高温で顕著に悪くなるという問題がある。この
原因としては、正極と負極と電解液の界面における電解
液の分解と被膜の形成、正極材料からの金属元素の溶出
などが考えられている（特にスピネル型構造を有するマ
ンガン酸リチウムにおいてはこの現象が顕著である）。
正極から金属元素が溶出すると正極材料内の構造が変化
したり、正極材料と導電剤との接触が損なわれたりして
容量が低下すると考えられている。この様な高温での二
次電池としての諸特性の低下は、高熱を発するノート型
パーソナルコンピューターや炎天下にさらされる自動車
で使用する場合に改善が必須であるといえる。However, a conventional lithium secondary battery using a lithium-containing transition metal oxide as a positive electrode material is:
There is a problem that the capacity is reduced due to repetition of charge and discharge and the storage characteristics are significantly deteriorated at a high temperature of about 50 ° C. or higher. This is considered to be caused by decomposition of the electrolytic solution and formation of a coating film at the interface between the positive electrode, the negative electrode and the electrolytic solution, and elution of a metal element from the positive electrode material (especially in lithium manganate having a spinel structure). The phenomenon is remarkable).
It is considered that when the metal element elutes from the positive electrode, the structure in the positive electrode material changes, or the contact between the positive electrode material and the conductive agent is damaged, and the capacity decreases. It can be said that such a decrease in the characteristics of the secondary battery at a high temperature must be improved when the battery is used in a notebook personal computer that emits high heat or in an automobile exposed to the sun.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、リチ
ウム二次電池用の正極材料として、高温下でもサイクル
特性や保存安定性が良好で且つ高容量が得られるリチウ
ム−遷移金属系ハロゲン化酸化物およびその製造方法を
提供することにあり、このリチウム−遷移金属系ハロゲ
ン化酸化物を正極に用いて高温下でもサイクル特性や保
存安定性が良好で且つ高容量、高出力が得られるリチウ
ム二次電池を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a lithium-transition metal halide as a cathode material for a lithium secondary battery, which has good cycle characteristics and storage stability even at high temperatures and has a high capacity. An object of the present invention is to provide an oxide and a method for producing the same, wherein the lithium-transition metal halide oxide is used as a positive electrode to obtain lithium having good cycle characteristics and storage stability even at a high temperature and high capacity and high output. An object of the present invention is to provide a secondary battery.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記課題を
解決するために鋭意検討を行った結果、本発明に至っ
た。 本発明は、一般式 ＬｉaＭbＯcＸd （式中、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏから選ばれた少な
くとも１種類以上の金属元素であり、Ｘは少なくとも１
種類以上のハロゲン元素である。ａは０．２≦ａ≦１．
２、ｂは０．８≦ｂ≦１．２、ｃは１．７≦ｃ≦２．
１、ｄは０≦ｄ≦０．３である。）で表されるリチウム
含有遷移金属酸化物またはリチウム含有遷移金属ハロゲ
ン化酸化物を主成分とし、その粒子表面が結晶性の金属
ハロゲン化物ＮＸe（ここで、Ｎは、Ｌｉ、Ｍｇ、Ａ
ｌ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏから選ば
れた少なくとも１種類以上の金属元素であり、Ｘは少な
くとも１種類以上のハロゲン元素であり、ｅは金属元素
Ｎの価数と等しい。）で被覆されているリチウム−遷移
金属系ハロゲン化酸化物であって、粒子表面に結晶性の
金属ハロゲン化物の状態で存在するハロゲンの量が、Ｘ
／Ｍ原子比で０．０１〜０．５であり、粒子内部の酸素
原子を置換した固溶体の状態で存在するハロゲンの量
が、Ｘ／Ｍ原子比で０．００２以上であり、かつ粒子表
面に結晶性の金属ハロゲン化物の状態で存在するハロゲ
ンと粒子内部の酸素原子を置換した固溶体の状態で存在
するハロゲンとの合計量が、Ｘ／Ｍ原子比で０．０２〜
０．５であることを特徴とするリチウム−遷移金属系ハ
ロゲン化酸化物に関する。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. The present invention, in the general formula Li a M b O c X d ( wherein, M represents Cr, Mn, Fe, at least one or more metal elements selected from Co, X is at least 1
More than one kind of halogen element. a is 0.2 ≦ a ≦ 1.
2, b is 0.8 ≦ b ≦ 1.2, c is 1.7 ≦ c ≦ 2.
1, d is 0 ≦ d ≦ 0.3. ) Represented by the formula (1), wherein the main component is a lithium-containing transition metal oxide or a lithium-containing transition metal halide oxide, and the particle surface of which is crystalline NX e (where N is Li, Mg, A
1, at least one metal element selected from Ca, Ti, V, Cr, Mn, Fe, and Co , X is at least one halogen element, and e is the valence of the metal element N. equal. ), Wherein the amount of halogen present in the form of crystalline metal halide on the particle surface is X
/ M atomic ratio is 0.01 to 0.5, and the amount of halogen present in the form of a solid solution in which oxygen atoms inside the particles are substituted is 0.002 or more in X / M atomic ratio, and the particle surface The total amount of halogen present in the form of a crystalline metal halide and halogen present in the form of a solid solution in which oxygen atoms inside the grains have been substituted is 0.02
0.5, which relates to a lithium-transition metal halide oxide.
【０００６】また、本発明は、リチウム化合物、金属ハ
ロゲン化物、およびＣｒ、Ｍｎ、Ｆｅ、Ｃｏから選ばれ
た少なくとも１種類以上の金属元素を含有する化合物か
らなる混合物を５００℃〜８００℃で加熱することを特
徴とするリチウム−遷移金属系ハロゲン化酸化物の製造
方法に関する。また、本発明は、リチウム化合物、マン
ガン化合物および金属ハロゲン化物からなる混合物を５
００℃〜８００℃で加熱することを特徴とするリチウム
−遷移金属系ハロゲン化酸化物の製造方法に関する。ま
た、本発明は、リチウム化合物、マンガン化合物、金属
ハロゲン化物、およびＢ、Ｍｇ、Ａｌ、Ｐ、Ｃａ、Ｔ
ｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｂａ、Ｇａ、
Ｔａから選ばれる少なくとも１種類以上の金属元素を含
有する化合物からなる混合物を５００℃〜８００℃で加
熱することを特徴とするリチウム−遷移金属系ハロゲン
化酸化物の製造方法に関する。さらに、本発明は、正極
活物質として、前記リチウム−遷移金属系ハロゲン化酸
化物を使用することを特徴とするリチウム二次電池に関
する。Further, the present invention provides a method for heating a mixture comprising a lithium compound, a metal halide, and a compound containing at least one or more metal elements selected from Cr, Mn, Fe, and Co at 500 ° C. to 800 ° C. And a method for producing a lithium-transition metal halide oxide. The present invention also relates to a mixture comprising a lithium compound, a manganese compound and a metal halide.
The present invention relates to a method for producing a lithium-transition metal-based halogenated oxide, wherein the method is heated at a temperature of 00 ° C to 800 ° C. Further, the present invention relates to a lithium compound, a manganese compound, a metal halide, and B, Mg, Al, P, Ca, T
i, V, Cr, Fe, Co, Cu , Zn, Ba, Ga,
The present invention relates to a method for producing a lithium-transition metal halide oxide, comprising heating a mixture comprising a compound containing at least one metal element selected from Ta at 500 ° C. to 800 ° C. Furthermore, the present invention relates to a lithium secondary battery using the lithium-transition metal halide oxide as a positive electrode active material.
【０００７】[0007]
【発明の実施の形態】本発明における一般式ＬｉaＭbＯ
cＸdにおける前記ａ，ｂ，ｃの範囲限定の理由は以下の
通りである。本発明で用いる正極活物質は、層状構造の
ＬｉＭＯ2もしくはスピネル型構造のＬｉＭ2Ｏ4（ただ
し、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏから選ばれた少なくと
も１種類以上の金属元素である。）を基本組成とし、構
成元素であるＬｉ、ＭおよびＯの含有量が基本組成から
特定の範囲にまで拡張されると共に、ハロゲン元素を含
有していることを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The general formula Li a M b O according to the present invention
The reason for the a, b, limiting the range of c in c X d are as follows. The positive electrode active material used in the present invention is LiMO 2 having a layered structure or LiM 2 O 4 having a spinel structure (where M is at least one metal element selected from Cr, Mn, Fe, and Co ). , The content of the constituent elements Li, M, and O is expanded from the basic composition to a specific range, and a halogen element is contained.
【０００８】基本組成がＬｉＭＯ2の場合における０．
２≦ａ≦１．２という範囲は、正極活物質からリチウム
が脱離された状態と脱離される前の初期状態との両方を
想定して設定した範囲である。ａが０．２よりも過度に
小さくなるか、１．２よりも過度に大きくなると充放電
の可逆性が著しく悪化して二次電池としての使用が困難
になる。０．８≦ｂ≦１．２という範囲は、ＬｉＭＯ2
が固有の結晶構造を維持できる範囲を想定している。ｂ
が０．８よりも過度に小さくなるか、１．２よりも過度
に大きくなると格子の安定性が著しく低下し、相転移を
起こして崩壊する。１．７≦ｃ≦２．１という範囲は、
ＬｉＭＯ2の結晶構造の安定性と充放電サイクル特性の
両方から設定した。ｃが１．７よりも過度に小さくなる
と、陰イオン欠損が大きくなり、格子が膨張して、充放
電サイクル特性が著しく悪化する。また、逆にｃが２．
１よりも過度に大きくなると、ＬｉＭＯ2が固有の結晶
構造を維持できなくなり、正極活物質として使用できな
くなる。ｄ≦０．３という範囲は、ＬｉＭＯ2の電気特
性から設定した。ｄが０．３よりも過度に大きくなる
と、Ｌｉイオンの拡散が妨げられ、電気抵抗が上がっ
て、正極活物質として使用できなくなる。In the case where the basic composition is LiMO 2 .
The range of 2 ≦ a ≦ 1.2 is a range set assuming both a state where lithium is desorbed from the positive electrode active material and an initial state before lithium is desorbed. If a is excessively smaller than 0.2 or excessively larger than 1.2, the reversibility of charge and discharge remarkably deteriorates, and it becomes difficult to use the secondary battery. The range 0.8 ≦ b ≦ 1.2 corresponds to LiMO 2
Assumes a range in which a unique crystal structure can be maintained. b
Is too small below 0.8 or too large, the stability of the lattice is remarkably reduced, causing a phase transition and collapse. The range of 1.7 ≦ c ≦ 2.1 is
It was set from both the stability of the crystal structure of LiMO 2 and the charge / discharge cycle characteristics. When c is excessively smaller than 1.7, anion deficiency increases, the lattice expands, and the charge / discharge cycle characteristics deteriorate significantly. On the other hand, when c is 2.
If it is excessively larger than 1, LiMO 2 cannot maintain its intrinsic crystal structure and cannot be used as a positive electrode active material. The range of d ≦ 0.3 was set from the electrical characteristics of LiMO 2 . If d is excessively larger than 0.3, the diffusion of Li ions is hindered, the electrical resistance increases, and the lithium ion cannot be used as a positive electrode active material.
【０００９】基本組成がＬｉＭ2Ｏ4の、すなわち、Ｌｉ
0.5ＭＯ2の場合における０．２≦ａ≦１．２という範囲
は、スピネル型構造の安定性から設定した。通常の製造
方法においては、ａが０．２よりも過度に小さくなる
と、スピネル型ＬｉＭ2Ｏ4単相の結晶を得ることができ
ない。前もってスピネル型ＬｉＭ2Ｏ4を製造した後、化
学処理または電気化学処理によりリチウムを脱離させ
て、スピネル型構造を有するａが０．２よりも小さい物
質を合成することは可能であるが、正極活物質としてリ
チウム二次電池に組み込むのは実用的ではない。また、
立方晶スピネル型の結晶構造を維持したままａが１．２
よりも過度に大きくになるまでリチウムを吸蔵すること
は困難である。０．８≦ｂ≦１．２という範囲は、Ｌｉ
Ｍ2Ｏ4がスピネル型結晶構造を維持できる範囲を想定し
ている。ｂが０．８よりも過度に小さくなるか、１．２
よりも過度に大きくなると格子の安定性が著しく低下
し、相転移を起こして崩壊する。１．７≦ｃ≦２．１と
いう範囲は、ＬｉＭ2Ｏ4のスピネル型結晶構造の安定性
と充放電サイクル特性の両方から設定した。ｃが１．７
よりも過度に小さくなると、陰イオン欠損が大きくな
り、格子が膨張して、充放電サイクル特性が著しく悪化
する。また、逆にｃが２．１よりも過度に大きくなる
と、ＬｉＭ2Ｏ4がスピネル型結晶構造を維持できなくな
り、正極活物質として使用できなくなる。ｄ≦０．３と
いう範囲は、ＬｉＭ2Ｏ4の電気特性から設定した。ｄが
０．３よりも過度に大きくなるとＬｉイオンの拡散が妨
げられ、電気抵抗が上がって、正極活物質として使用で
きなくなる。The basic composition is LiM 2 O 4 , that is, Li
The range of 0.2 ≦ a ≦ 1.2 in the case of 0.5 MO 2 was set from the stability of the spinel structure. In a normal production method, if a is excessively smaller than 0.2, a single-phase spinel-type LiM 2 O 4 crystal cannot be obtained. After manufacturing spinel type LiM 2 O 4 in advance, it is possible to desorb lithium by chemical treatment or electrochemical treatment to synthesize a substance having a spinel type structure with a smaller than 0.2. It is not practical to incorporate it into a lithium secondary battery as a positive electrode active material. Also,
A is 1.2 while maintaining the cubic spinel crystal structure
It is difficult to occlude lithium until it becomes too large. The range of 0.8 ≦ b ≦ 1.2 is expressed as Li
It is assumed that M 2 O 4 can maintain a spinel-type crystal structure. b is too small below 0.8 or 1.2
If it is excessively large, the stability of the lattice is remarkably reduced, and a phase transition occurs to cause collapse. The range of 1.7 ≦ c ≦ 2.1 was set from both the stability of the spinel crystal structure of LiM 2 O 4 and the charge / discharge cycle characteristics. c is 1.7
If it is too small, the anion deficiency becomes large, the lattice expands, and the charge / discharge cycle characteristics deteriorate significantly. On the other hand, if c is excessively larger than 2.1, LiM 2 O 4 cannot maintain a spinel-type crystal structure and cannot be used as a positive electrode active material. The range of d ≦ 0.3 was set from the electrical characteristics of LiM 2 O 4 . If d is excessively larger than 0.3, diffusion of Li ions is hindered, electric resistance increases, and the electrode cannot be used as a positive electrode active material.
【００１０】本発明のリチウム−遷移金属系ハロゲン化
酸化物は、一般式ＬｉaＭbＯcＸd（式中、ＭはＣｒ、Ｍ
ｎ、Ｆｅ、Ｃｏから選ばれた少なくとも１種類以上の金
属元素であり、Ｘは少なくとも１種類以上のハロゲン元
素である。ａは０．２≦ａ≦１．２、ｂは０．８≦ｂ≦
１．２、ｃは１．７≦ｃ≦２．１、ｄは０≦ｄ≦０．３
である。）で表されるリチウム含有遷移金属酸化物また
はリチウム含有遷移金属ハロゲン化酸化物を主成分と
し、その粒子表面が結晶性の金属ハロゲン化物ＮＸ
e（ここで、Ｎは、Ｌｉ、Ｍｇ、Ａｌ、Ｃａ、Ｔｉ、
Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏから選ばれた少なくとも１
種類以上の金属元素であり、Ｘは少なくとも１種類以上
のハロゲン元素であり、ｅは金属元素Ｎの価数と等し
い。）で被覆されているリチウム−遷移金属系ハロゲン
化酸化物であって、粒子表面に結晶性の金属ハロゲン化
物の状態で存在するハロゲンの量が、Ｘ／Ｍ原子比で
０．０１〜０．５であり、粒子内部の酸素原子を置換し
た固溶体の状態で存在するハロゲンの量が、Ｘ／Ｍ原子
比で０．００２以上であり、かつ粒子表面に結晶性の金
属ハロゲン化物の状態で存在するハロゲンと粒子内部の
酸素原子を置換した固溶体の状態で存在するハロゲンと
の合計量が、Ｘ／Ｍ原子比で０．０２〜０．５であるこ
とを特徴としている。このような特徴を有するリチウム
−遷移金属系ハロゲン化酸化物は、リチウム二次電池の
正極材料として使用した場合に、正極表面での電解液の
分解や電解液中への遷移金属イオンの溶出などを著しく
抑制することができる。このため、本発明のリチウム−
遷移金属系ハロゲン化酸化物を正極に使用したリチウム
二次電池は、高温下でも優れた充放電サイクル特性と保
存安定性を示す。[0010] lithium present invention - transition metal system halogenated oxides of the general formula Li a M b O c X d ( wherein, M represents Cr, M
At least one kind of metal element selected from n, Fe, and Co , and X is at least one kind of halogen element. a is 0.2 ≦ a ≦ 1.2, b is 0.8 ≦ b ≦
1.2, c is 1.7 ≦ c ≦ 2.1, d is 0 ≦ d ≦ 0.3
It is. A) a metal halide NX comprising a lithium-containing transition metal oxide or a lithium-containing transition metal halide represented by the formula
e (where N is Li, Mg, Al, Ca, Ti,
At least one selected from V, Cr, Mn, Fe, and Co
X is at least one kind of halogen element, and e is equal to the valence of the metal element N. ), Wherein the amount of halogen present in the form of a crystalline metal halide on the surface of the particles is from 0.01 to 0.1 at an X / M atomic ratio. 5, wherein the amount of halogen present in the form of a solid solution in which oxygen atoms have been substituted in the grains is 0.002 or more in an X / M atomic ratio, and is present in the form of a crystalline metal halide on the surface of the grains. The total amount of the halogens present and the halogens present in the form of a solid solution in which the oxygen atoms inside the grains have been substituted is 0.02 to 0.5 in terms of the X / M atomic ratio. Lithium-transition metal halide oxides having such characteristics, when used as a positive electrode material of a lithium secondary battery, decompose the electrolytic solution on the positive electrode surface or elute transition metal ions into the electrolytic solution. Can be significantly suppressed. For this reason, the lithium-
Lithium secondary batteries using transition metal halide oxides for the positive electrode exhibit excellent charge / discharge cycle characteristics and storage stability even at high temperatures.
【００１１】本発明において、金属ハロゲン化物ＮＸe
のＬｉイオン伝導性はそれ程大きくはないので、粒子表
面に結晶性の金属ハロゲン化物の状態で存在するハロゲ
ンの量はＸ／Ｍ原子比で０．５以下が好ましく、一方、
結晶性の金属ハロゲン化物の状態で存在するハロゲンの
量がＸ／Ｍ原子比で０．０１よりも過度に小さくなると
単位表面積当たりの金属ハロゲン化物の層の厚さが薄く
なりすぎ上記の効果が期待できないので好ましくない。In the present invention, the metal halide NX e
Is not so large, the amount of halogen present in the form of crystalline metal halide on the particle surface is preferably 0.5 or less in X / M atomic ratio, while
If the amount of halogen present in the crystalline metal halide state is excessively smaller than 0.01 in the X / M atomic ratio, the thickness of the metal halide layer per unit surface area becomes too small, and the above-mentioned effect is not obtained. It is not desirable because it cannot be expected.
【００１２】本発明において、粒子内部のリチウム含有
遷移金属酸化物またはリチウム含有遷移金属ハロゲン化
酸化物中の酸素原子を置換した固溶体の状態で存在する
ハロゲンの量がＸ／Ｍ原子比で０．００２よりも過度に
小さいと上記の効果が期待できないので好ましくない。In the present invention, the amount of halogen present as a solid solution in which oxygen atoms have been substituted in the lithium-containing transition metal oxide or the lithium-containing transition metal halide oxide inside the particles is 0.1% by X / M atomic ratio. If the value is excessively smaller than 002, the above-described effects cannot be expected, which is not preferable.
【００１３】粒子表面に結晶性の金属ハロゲン化物の状
態で存在するハロゲンと粒子内部の酸素原子を置換した
固溶体の状態で存在するハロゲンとの合計量は、Ｘ／Ｍ
原子比で０．０２〜０．５であることが好ましい。Ｘ／
Ｍ原子比が０．０２よりも過度に小さいと、電解液中へ
の遷移金属イオンの溶出量が増大し、充放電サイクル特
性が悪化するので好ましくない。また、Ｘ／Ｍ原子比が
０．５よりも過度に大きいと、正極表面および正極内部
におけるＬｉイオンの拡散が妨げられ、電気抵抗が上が
って、正極活物質として使用できなくなる。The total amount of halogen present in the form of a crystalline metal halide on the surface of the particle and halogen present in the form of a solid solution in which oxygen atoms inside the particle are substituted is X / M
The atomic ratio is preferably 0.02 to 0.5. X /
If the M atomic ratio is excessively smaller than 0.02, the amount of transition metal ions eluted into the electrolytic solution increases, and the charge / discharge cycle characteristics are undesirably deteriorated. On the other hand, if the X / M atomic ratio is excessively larger than 0.5, diffusion of Li ions on the surface of the positive electrode and inside the positive electrode is hindered, the electrical resistance increases, and the positive electrode cannot be used as a positive electrode active material.
【００１４】また、ハロゲン元素としては、フッ素、塩
素、臭素などが挙げられるが、リチウムイオン伝導性か
らフッ素が好ましい。また、金属ハロゲン化物ＮＸeと
しては、Ｌｉ、Ｍｇ、Ａｌ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｍ
ｎ、Ｆｅ、Ｃｏから選ばれた少なくとも１種類以上の金
属元素と前記フッ素、塩素、臭素などのハロゲン元素と
のそれぞれの組み合せが可能であるが、リチウムイオン
伝導性を考慮するとＬｉＦが最も好ましい。本発明にお
いて、粒子の最表面に存在する結晶性の金属ハロゲン化
物層と粒子内部のリチウム含有遷移金属酸化物またはリ
チウム含有遷移金属ハロゲン化酸化物との間に表層側か
ら内部に向かって酸素原子を置換したハロゲンの濃度が
減少してゆく濃度傾斜層が存在し、表層側界面のハロゲ
ン濃度の１０％に減衰するまでの深さが、表層側界面か
ら０．５〜８０ｎｍであるような傾斜構造を有すること
が好ましい。Examples of the halogen element include fluorine, chlorine, and bromine, and fluorine is preferred from the viewpoint of lithium ion conductivity. Further, as the metal halide NX e , Li, Mg, Al, Ca, Ti, V, Cr, M
Each combination of at least one or more metal elements selected from n, Fe, and Co with the above-described halogen elements such as fluorine, chlorine, and bromine is possible, but LiF is most preferable in consideration of lithium ion conductivity. In the present invention, between the crystalline metal halide layer present on the outermost surface of the particle and the lithium-containing transition metal oxide or the lithium-containing transition metal halide oxide inside the particle, an oxygen atom is introduced from the surface side toward the inside. Concentration gradient layer in which the concentration of the halogen substituted for the compound is reduced, and the depth from the surface side interface to the attenuation of 10% of the halogen concentration is 0.5 to 80 nm from the surface side interface. It preferably has a structure.
【００１５】本発明において、リチウム含有遷移金属酸
化物またはリチウム含有遷移金属ハロゲン化酸化物粒子
内の表面近傍に存在するハロゲン元素の濃度傾斜層は金
属ハロゲン化物がリチウム含有遷移金属酸化物またはリ
チウム含有遷移金属ハロゲン化酸化物中に固溶すること
により形成されるが、ハロゲン濃度が高い領域ではイオ
ン伝導性があまり高くないので、その厚さ（粒子の表層
側から内部に向かってハロゲン濃度が減少し、表層側界
面のハロゲン濃度の１０％に減少するまでの深さ）は８
０ｎｍ以下が好ましく、傾斜層の厚さが０．５ｎｍ未満
になると傾斜層の厚さが薄すぎ、上記の効果が期待でき
ないので好ましくない。In the present invention, the concentration gradient layer of the halogen element present in the vicinity of the surface in the lithium-containing transition metal oxide or lithium-containing transition metal halide oxide particles is such that the metal halide has a lithium-containing transition metal oxide or lithium-containing transition metal oxide. It is formed by solid solution in the transition metal halide oxide. However, since ion conductivity is not so high in the region where the halogen concentration is high, the thickness (the halogen concentration decreases from the surface side to the inside of the particle) And the depth at which the halogen concentration at the surface side interface decreases to 10%) is 8
The thickness is preferably 0 nm or less. If the thickness of the gradient layer is less than 0.5 nm, the thickness of the gradient layer is too thin, and the above-mentioned effects cannot be expected.
【００１６】上記の効果が発現されるためには、リチウ
ム含有遷移金属酸化物またはリチウム含有遷移金属ハロ
ゲン化酸化物の粒子の表面の７０％以上が金属ハロゲン
化物及びハロゲン元素濃度傾斜層により覆われているこ
とが好ましい。また、本発明において、一般式 ＬｉaＭbＯcＸd （式中、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏから選ばれた少な
くとも１種類以上の金属元素であり、Ｘは少なくとも１
種類以上のハロゲン元素である。ａは０．２≦ａ≦１．
２、ｂは０．８≦ｂ≦１．２、ｃは１．７≦ｃ≦２．
１、ｄは０≦ｄ≦０．３である。）で表されるリチウム
含有遷移金属酸化物またはリチウム含有遷移金属ハロゲ
ン化酸化物が、立方晶のスピネル型構造を有するマンガ
ン酸リチウムであり、且つ、その格子定数が０．８２４
０５ｎｍ以下であるリチウム−遷移金属系ハロゲン化酸
化物であることが好ましい。格子定数が０．８２４０５
ｎｍを超えて大きくなると、スピネル型結晶内部におけ
るマンガン−酸素間またはマンガン−ハロゲン間の結合
距離が長くなるために、これらの原子間の結合強度が低
下して、格子の安定性が低下する。このため、充放電サ
イクルによって膨張−収縮を繰り返すと結晶構造が崩壊
して、サイクル特性が悪化し、充放電の繰り返しに耐え
ることができなくなる。In order to exhibit the above-mentioned effects, 70% or more of the surface of the particles of the lithium-containing transition metal oxide or the lithium-containing transition metal halide oxide is covered with the metal halide and halogen element concentration gradient layer. Is preferred. Further, in the present invention, in the general formula Li a M b O c X d ( wherein, M represents Cr, Mn, Fe, at least one or more metal elements selected from Co, X is at least 1
More than one kind of halogen element. a is 0.2 ≦ a ≦ 1.
2, b is 0.8 ≦ b ≦ 1.2, c is 1.7 ≦ c ≦ 2.
1, d is 0 ≦ d ≦ 0.3. The lithium-containing transition metal oxide or the lithium-containing transition metal halide represented by the formula (1) is lithium manganate having a cubic spinel structure, and has a lattice constant of 0.824.
It is preferably a lithium-transition metal halide oxide having a thickness of not more than 05 nm. Lattice constant is 0.82405
If the diameter exceeds nm, the bonding distance between manganese and oxygen or between manganese and halogen in the spinel-type crystal becomes longer, so that the bonding strength between these atoms decreases and the stability of the lattice decreases. For this reason, when expansion and contraction are repeated by the charge / discharge cycle, the crystal structure collapses, the cycle characteristics deteriorate, and it becomes impossible to withstand repeated charge / discharge.
【００１７】また、本発明において、立方晶のスピネル
型構造を有するマンガン酸リチウムの結晶中におけるリ
チウムまたはマンガンの占有する格子サイトの一部が
Ｂ、Ｍｇ、Ａｌ、Ｐ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｂａ、Ｇａ、Ｔａから選ばれる
少なくとも１種類以上の元素で置換されたリチウム−遷
移金属系ハロゲン化酸化物が好ましい。上記の置換元素
の中では、特にマグネシウムの置換効果が顕著であり、
リチウムまたはマンガンの占有する格子サイトの一部が
マグネシウムで置換されたスピネル型マンガン酸リチウ
ムは、高温での充放電サイクルにおいても、電解液中で
のマンガンの溶出量が少なく、優れた充放電サイクル特
性を示す。Further, in the present invention, in the crystal of lithium manganate having a cubic spinel structure, part of lattice sites occupied by lithium or manganese is B, Mg, Al, P, Ca, Ti, V, Cr, Fe, C
Lithium-transition metal halide oxides substituted with at least one or more elements selected from o, Ni, Cu, Zn, Ba, Ga, and Ta are preferred. Among the above substitution elements, the substitution effect of magnesium is particularly remarkable,
Lithium or manganese occupies a part of the lattice sites replaced by magnesium. Show characteristics.
【００１８】また、本発明において、粒子表面に結晶性
の金属ハロゲン化物の状態で存在するハロゲンの量が、
Ｘ／Ｍ原子比で０．１１５〜０．５であり、粒子内部の
酸素原子を置換した固溶体の状態で存在するハロゲンの
量が、Ｘ／Ｍ原子比で０．００４以上であり、かつ粒子
表面に結晶性の金属ハロゲン化物の状態で存在するハロ
ゲンと粒子内部の酸素原子を置換した固溶体の状態で存
在するハロゲンとの合計量が、Ｘ／Ｍ原子比で０．１２
〜０．５であるリチウム−遷移金属系ハロゲン化酸化物
が好ましい。Further, in the present invention, the amount of halogen present in the form of a crystalline metal halide on the particle surface is
An X / M atomic ratio of 0.115 to 0.5, the amount of halogen present in the form of a solid solution in which oxygen atoms have been substituted in the particles is 0.004 or more in an X / M atomic ratio, and The total amount of the halogen present in the form of a crystalline metal halide on the surface and the halogen present in the form of a solid solution in which oxygen atoms inside the grains have been substituted is 0.12 in X / M atomic ratio.
Lithium-transition metal-based halogenated oxides of 0.5 to 0.5 are preferred.
【００１９】スピネル型構造のマンガン酸リチウムにお
いては、特に充放電サイクルに伴う正極表面での電解液
の分解とマンガンイオンの溶出が大きな問題となってい
る。電解液の分解は、正極表面のマンガンイオンが電解
液を構成する有機溶媒の分解を加速する触媒作用を有す
るためと考えられている。また、マンガンイオンの溶出
は、電解液中の酸（Ｈ+）の攻撃により正極表面の酸素
イオンが水素イオンと結合する際の電荷補償のために進
行すると考えられている。電解液の分解およびマンガン
イオンの溶出は、共に５０℃以上の高温で著しく顕著に
なるため、高温で使用されるマンガン酸リチウム正極に
対しては、より多くの量の金属ハロゲン化物および固溶
ハロゲンを存在させて、電池特性の安定化を図る必要が
ある。In the case of lithium manganate having a spinel structure, decomposition of an electrolytic solution and elution of manganese ions on the surface of the positive electrode, particularly during charge / discharge cycles, are serious problems. The decomposition of the electrolytic solution is considered to be because manganese ions on the positive electrode surface have a catalytic action to accelerate the decomposition of the organic solvent constituting the electrolytic solution. It is also believed that manganese ion elution proceeds for charge compensation when oxygen ions on the positive electrode surface combine with hydrogen ions due to the attack of acid (H + ) in the electrolytic solution. Since the decomposition of the electrolytic solution and the elution of manganese ions are both remarkable at a high temperature of 50 ° C. or higher, a larger amount of a metal halide and a solid solution halogen are required for a lithium manganate cathode used at a high temperature. To stabilize the battery characteristics.
【００２０】マンガン酸リチウムと電解液との間に結晶
性の金属ハロゲン化物ＮＸeの層を介在させることによ
り正極表面での電解液の分解が抑制されて、充放電サイ
クル特性が向上する。結晶性の金属ハロゲン化物の状態
で存在するハロゲンの量が、Ｘ／Ｍ原子比で０．１１５
よりも過度に小さくなると、単位面積当たりの金属ハロ
ゲン化物層の厚さが薄くなるために、電解液の分解抑制
効果が小さくなる。このため、充放電サイクルに伴うク
ーロン効率の低下を防止する作用が小さくなり、サイク
ル特性を向上させる効果もあまり見られなくなって、高
温で使用されるリチウム二次電池の正極活物質として使
用することが難しくなるので好ましくない。The decomposition of the electrolyte solution positive electrode surface by interposing a layer of crystalline metal halide NX e between the lithium manganate and the electrolyte solution is suppressed, thereby improving the charge-discharge cycle characteristics. The amount of halogen present in the crystalline metal halide state is 0.115 by X / M atomic ratio.
If it is too small, the thickness of the metal halide layer per unit area becomes small, and the effect of suppressing the decomposition of the electrolytic solution becomes small. For this reason, the effect of preventing a decrease in Coulomb efficiency due to a charge / discharge cycle is reduced, and the effect of improving the cycle characteristics is hardly seen, so that it is used as a positive electrode active material of a lithium secondary battery used at a high temperature. Is not preferable because it becomes difficult.
【００２１】一方、金属ハロゲン化物ＮＸeのリチウム
イオン伝導性はそれ程大きくはないので、粒子表面に結
晶性の金属ハロゲン化物の状態で存在するハロゲンの量
はＸ／Ｍ原子比で０．５以下が好ましい。ハロゲンの量
がＸ／Ｍ原子比で０．５よりも過度に大きくなると、リ
チウムイオンの伝導度が低いことに起因して、電池の内
部抵抗が増大し、大電流を取り出すことができなくなる
ので好ましくない。On the other hand, since the lithium ion conductivity of the metal halide NX e is not so large, the amount of halogen existing in the form of a crystalline metal halide on the particle surface is 0.5 or less in X / M atomic ratio. Is preferred. If the amount of halogen is excessively larger than 0.5 in the X / M atomic ratio, the internal resistance of the battery increases due to the low conductivity of lithium ions, and a large current cannot be taken out. Not preferred.
【００２２】本発明において、マンガン酸リチウム結晶
内部の酸素原子をハロゲン原子で置換すると、スピネル
型構造が安定化され、格子が強化される。すなわち、ス
ピネル型結晶内部におけるマンガン原子−酸素原子間お
よびマンガン原子−ハロゲン原子間の結合強度が増大
し、電解液中へのマンガンの溶出が抑制される。粒子内
部の酸素原子を置換した固溶体の状態で存在するハロゲ
ンの量が、Ｘ／Ｍ原子比で０．００４よりも過度に小さ
くなると、スピネル型構造の安定化作用が小さくなり、
高温におけるマンガンの溶出量が増大して、充放電サイ
クル特性が悪化するので好ましくない。逆に、酸素原子
を置換した固溶体の状態で存在するハロゲンの量が、過
度に増大すると、スピネル型結晶内部の陰イオンの価数
が小さくなりすぎ、充放電に際して、リチウムの吸蔵−
放出が難しくなる恐れがある。マンガン酸リチウムの結
晶内部の酸素原子を置換固溶したハロゲン原子は、粒子
内部の表面近傍に厚さ０．５〜８０ｎｍ程度のハロゲン
元素の濃度傾斜層として存在させることが好ましい。こ
のような濃度傾斜層の存在により、粒子表面の金属ハロ
ゲン化物層とスピネル型マンガン酸リチウム粒子が強固
に結合され、充放電に伴う結晶の膨張収縮の際にも、金
属ハロゲン化物層がスピネル型マンガン酸リチウム粒子
から剥離することがなく、長期にわたって安定した充放
電サイクル特性を持続することができる。粒子表面に結
晶性の金属ハロゲン化物の状態で存在するハロゲンと粒
子内部の酸素原子を置換した固溶体の状態で存在するハ
ロゲンとの合計量は、Ｘ／Ｍ原子比で０．１２〜０．５
であることが好ましい。結晶性の金属ハロゲン化物の状
態で存在するハロゲンと酸素原子を置換した固溶体の状
態で存在するハロゲンとの合計量がＸ／Ｍ原子比で０．
１２よりも過度に小さくなると、特に高温での充放電サ
イクルに伴う正極表面での電解液の分解とマンガンイオ
ンの溶出が進行して、サイクル特性が悪化するので好ま
しくない。結晶性の金属ハロゲン化物の状態で存在する
ハロゲンと酸素原子を置換した固溶体の状態で存在する
ハロゲンとの合計量がＸ／Ｍ原子比で０．５よりも過度
に大きくなると、金属ハロゲン化物層およびスピネル型
マンガン酸リチウム内部におけるリチウムイオンの伝導
度低下に起因して、リチウムの拡散が悪くなり、充放電
のクーロン効率、サイクル特性が悪化するので好ましく
ない。また、電池の内部抵抗が増大して、大電流を取り
出すことができなくなるので好ましくない。In the present invention, when the oxygen atom in the lithium manganate crystal is replaced with a halogen atom, the spinel structure is stabilized and the lattice is strengthened. That is, the bond strength between the manganese atom and the oxygen atom and between the manganese atom and the halogen atom in the spinel crystal is increased, and the elution of manganese into the electrolytic solution is suppressed. When the amount of the halogen present in the state of the solid solution in which the oxygen atoms in the grains are substituted becomes excessively smaller than 0.004 in the X / M atomic ratio, the stabilizing effect of the spinel structure decreases.
It is not preferable because the amount of manganese eluted at a high temperature increases and the charge / discharge cycle characteristics deteriorate. Conversely, if the amount of halogen present in the state of a solid solution in which oxygen atoms have been substituted is excessively increased, the valence of anions inside the spinel-type crystal becomes too small, and the charge and discharge of lithium during charging and discharging takes place.
Release may be difficult. It is preferable that the halogen atoms obtained by substituting the oxygen atoms inside the crystal of lithium manganate and forming a solid solution exist in the vicinity of the surface inside the grains as a halogen element concentration gradient layer having a thickness of about 0.5 to 80 nm. Due to the presence of such a concentration gradient layer, the metal halide layer on the particle surface and the spinel-type lithium manganate particles are firmly bonded, and even when the crystal expands and contracts due to charge / discharge, the metal halide layer remains in the spinel-type. It is possible to maintain stable charge / discharge cycle characteristics for a long time without peeling off from the lithium manganate particles. The total amount of the halogen present in the form of a crystalline metal halide on the surface of the particle and the halogen present in the form of a solid solution in which oxygen atoms inside the particle are substituted is 0.12 to 0.5 in terms of X / M atomic ratio.
It is preferred that The total amount of halogen present in the form of a crystalline metal halide and halogen present in the form of a solid solution in which oxygen atoms have been substituted is 0.
An excessively smaller value than 12 is not preferable because the decomposition of the electrolytic solution and the elution of manganese ions on the positive electrode surface accompanying the charge / discharge cycle at a high temperature in particular progress, thereby deteriorating the cycle characteristics. If the total amount of halogen present in the form of crystalline metal halide and halogen present in the form of a solid solution in which oxygen atoms have been substituted becomes excessively larger than 0.5 in the X / M atomic ratio, the metal halide layer In addition, the decrease in the conductivity of lithium ions inside the spinel-type lithium manganate is not preferable because the diffusion of lithium deteriorates, and the Coulomb efficiency and cycle characteristics of charging and discharging deteriorate. Further, the internal resistance of the battery is increased, so that a large current cannot be taken out, which is not preferable.
【００２３】また、本発明において、マンガン酸リチウ
ムの結晶中におけるリチウムまたはマンガンの占有する
格子サイトの一部がＢ、Ｍｇ、Ａｌ、Ｐ、Ｃａ、Ｔｉ、
Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｂａ、Ｇ
ａ、Ｔａから選ばれる少なくとも１種類以上の元素で置
換された立方晶スピネル型構造のマンガン酸リチウムの
格子定数は０．８２４０５ｎｍ以下であることが好まし
い。格子定数が０．８２４０５ｎｍよりも過度に大きい
と、スピネル型結晶内部におけるマンガン−酸素間また
はマンガン−ハロゲン間の結合距離が長くなるために、
これらの原子間の結合強度が低下して、格子の安定性が
低下する。このため、充放電サイクルによって膨張−収
縮を繰り返すと結晶構造が崩壊して、サイクル特性が悪
化し、充放電の繰り返しに耐えることができなくなる。In the present invention, lithium or manganese occupies a part of the lattice sites occupied by B, Mg, Al, P, Ca, Ti, in the lithium manganate crystal.
V, Cr, Fe, Co, Ni, Cu, Zn, Ba, G
The lattice constant of the cubic spinel-type lithium manganate substituted with at least one element selected from a and Ta is preferably 0.82405 nm or less. If the lattice constant is excessively larger than 0.82405 nm, the manganese-oxygen or manganese-halogen bond distance inside the spinel crystal becomes long,
The bond strength between these atoms decreases, and the stability of the lattice decreases. For this reason, when expansion and contraction are repeated by the charge / discharge cycle, the crystal structure collapses, the cycle characteristics deteriorate, and it becomes impossible to withstand repeated charge / discharge.
【００２４】前記リチウム−遷移金属系ハロゲン化酸化
物を正極材料として使用することにより、高温下でのリ
チウム二次電池のサイクル特性や保存安定性を向上させ
ることができる。これは、正極活物質と電解液との界面
において金属ハロゲン化物ＮＸeの層とリチウム含有遷
移金属酸化物またはリチウム含有遷移金属ハロゲン化酸
化物粒子がこの粒子内の表面近傍に存在する０．５〜８
０ｎｍ程度の厚さのハロゲン元素の濃度傾斜層を介して
強固に結びつけられているため、リチウム含有遷移金属
酸化物またはリチウム含有遷移金属ハロゲン化酸化物表
面における触媒的な電解液の分解が抑制されたこと、こ
の様な層で覆われていない場合、電解液中の酸（Ｈ+）
の正極へのアタックにより正極材料中の酸素が水として
電解液中へ溶け出すと同時に電荷補償の為に遷移金属イ
オンが電解液中に溶け出すが、金属ハロゲン化物ＮＸe
の層が介在することにより、Ｌｉイオンの出入りは妨げ
ず、遷移金属イオンの伝導は抑制するので遷移金属イオ
ンの溶出が抑制されたことによると考えられる。また、
ハロゲン元素の濃度傾斜層が存在することにより、充放
電に伴う結晶の膨張収縮の際にも金属ハロゲン化物の層
をリチウム含有遷移金属酸化物またはリチウム含有遷移
金属ハロゲン化酸化物粒子から剥離させることがないの
で長期のサイクルに亘って上記の効果を持続することが
できる。また、本発明のリチウム二次電池の作動電圧は
３〜４．５Ｖである。By using the lithium-transition metal halide oxide as a positive electrode material, the cycle characteristics and storage stability of a lithium secondary battery at high temperatures can be improved. This is because at the interface between the positive electrode active material and the electrolyte, the layer of the metal halide NX e and the lithium-containing transition metal oxide or lithium-containing transition metal halide oxide particles are present in the vicinity of the surface in the particles. ~ 8
Since it is firmly bound through the concentration gradient layer of the halogen element having a thickness of about 0 nm, catalytic decomposition of the electrolytic solution on the surface of the lithium-containing transition metal oxide or the lithium-containing transition metal halide oxide is suppressed. That, if not covered with such a layer, the acid (H + )
Oxygen in the positive electrode material dissolves into the electrolyte as water due to the attack on the positive electrode, and at the same time, transition metal ions dissolve in the electrolyte for charge compensation, but the metal halide NX e
It is considered that the interposition of the layer does not hinder the entrance and exit of Li ions and suppresses the conduction of transition metal ions, so that the elution of transition metal ions is suppressed. Also,
The presence of the concentration gradient layer of the halogen element allows the metal halide layer to be exfoliated from the lithium-containing transition metal oxide or the lithium-containing transition metal halide oxide particles even when the crystal expands and contracts due to charge and discharge. The above effect can be maintained over a long cycle because of the absence of the above. The operating voltage of the lithium secondary battery of the present invention is 3 to 4.5V.
【００２５】本発明のリチウム二次電池用正極材料の製
造方法について説明する。原料としては、リチウム含有
遷移金属酸化物またはリチウム含有遷移金属ハロゲン化
酸化物のリチウム源となるリチウム化合物、リチウム含
有遷移金属酸化物またはリチウム含有遷移金属ハロゲン
化酸化物の遷移金属源となる遷移金属化合物、リチウム
含有遷移金属酸化物またはリチウム含有遷移金属ハロゲ
ン化酸化物が立方晶のスピネル型構造を有するマンガン
酸リチウムの場合には、結晶中におけるリチウムまたは
マンガンの占有する格子サイトの一部をＭｎ以外の元素
で置換する際に必要な置換元素源となる置換元素を含む
化合物、そして金属ハロゲン化物である。The method for producing the positive electrode material for a lithium secondary battery according to the present invention will be described. As a raw material, a lithium compound serving as a lithium source of a lithium-containing transition metal oxide or a lithium-containing transition metal halide oxide, a transition metal serving as a transition metal source of a lithium-containing transition metal oxide or a lithium-containing transition metal halide oxide In the case where the compound, the lithium-containing transition metal oxide or the lithium-containing transition metal halide is lithium manganate having a cubic spinel structure, a part of lattice sites occupied by lithium or manganese in the crystal is Mn. A compound containing a substitution element that is a source of a substitution element necessary for substitution with an element other than the above, and a metal halide.
【００２６】リチウム源となるリチウム化合物としては
熱処理時に酸化物となるものであれば特に限定されない
が、酸化リチウム、炭酸リチウム、水酸化リチウム、硝
酸リチウム、塩化リチウム、酢酸リチウム、蓚酸リチウ
ム等が挙げられる。遷移金属源としては遷移金属元素の
Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏを含む化合物で熱処理時に酸化
物となるものであれば特に限定されないが、これらの遷
移金属元素を含む酸化物、炭酸塩、水酸化物、硝酸塩、
酢酸塩、蓚酸塩等が挙げられる。特に、スピネル型マン
ガン酸リチウム製造の場合には、マンガン源として、平
均酸化数が２．７５〜３．４価であるマンガン酸化物ま
たはオキシ水酸化マンガンを用いることが好ましい。平
均酸化数が２．７５〜３．４価であるマンガン酸化物ま
たはオキシ水酸化マンガンの使用により、本発明におけ
る粒子表面に結晶性の金属ハロゲン化物の状態で存在す
るハロゲンと粒子内部の酸素原子を置換した固溶体の状
態で存在するハロゲンの存在量を制御しやすくなるばか
りでなく、より均質で結晶性の良好なスピネル型マンガ
ン酸リチウムが得られ、充放電サイクル特性が向上す
る。置換元素源としては置換元素であるＢ、Ｍｇ、Ａ
ｌ、Ｐ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚ
ｎ、Ｂａ、Ｇａ、Ｔａを含む化合物で熱処理時に酸化物
となるものであれば特に限定されないが、置換元素を含
む酸化物、炭酸塩、水酸化物、硝酸塩、酢酸塩、蓚酸塩
等が挙げられる。The lithium compound serving as a lithium source is not particularly limited as long as it becomes an oxide during heat treatment, and examples thereof include lithium oxide, lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride, lithium acetate, and lithium oxalate. Can be The transition metal source is not particularly limited as long as it is a compound containing the transition metal elements Cr, Mn, Fe, and Co and becomes an oxide during heat treatment. Object, nitrate,
Acetate, oxalate and the like can be mentioned. In particular, in the case of spinel-type lithium manganate production, it is preferable to use manganese oxide or manganese oxyhydroxide having an average oxidation number of 2.75 to 3.4 as a manganese source. By using manganese oxide or manganese oxyhydroxide having an average oxidation number of 2.75 to 3.4, halogens present in the form of crystalline metal halides on the surface of the particles and oxygen atoms inside the particles are used in the present invention. Not only is it easier to control the amount of halogen present in the state of a solid solution in which is substituted, but also spinel-type lithium manganate having more uniform and excellent crystallinity is obtained, and the charge-discharge cycle characteristics are improved. B, Mg, A which are the substitution elements
1, P, Ca, Ti, V, Cr, Fe, Co, Cu , Z
The compound containing n, Ba, Ga, and Ta is not particularly limited as long as it becomes an oxide during heat treatment, and examples thereof include an oxide containing a substitution element, a carbonate, a hydroxide, a nitrate, an acetate, and an oxalate. Can be
【００２７】まず、これらの原料を混合するが、混合方
法としては特に限定されず、乳鉢、ミキサー、ボールミ
ル等を用いて混合する乾式法、水やエタノールなどを用
いる湿式混合法など均一に混合できる方法であればよ
い。First, these raw materials are mixed, but the mixing method is not particularly limited, and a uniform mixing method such as a dry method using a mortar, a mixer, a ball mill or the like, or a wet mixing method using water or ethanol is used. Any method is acceptable.
【００２８】本発明のリチウム二次電池用正極材料の製
造においては、前記の混合物を５００℃〜８００℃、好
ましくは６７０℃〜７７０℃で１時間以上熱処理を行
う。８００℃よりも高い温度では金属ハロゲン化物とリ
チウム含有遷移金属酸化物またはリチウム含有遷移金属
ハロゲン化酸化物の反応が進行し、金属ハロゲン化物が
リチウム含有遷移金属酸化物またはリチウム含有遷移金
属ハロゲン化酸化物の結晶粒子の内部まで固溶してしま
い、ハロゲン濃度が平均化され傾斜層の厚さが厚くなり
すぎるので好ましくない。また、５００℃より低い温度
ではリチウム含有遷移金属酸化物またはリチウム含有遷
移金属ハロゲン化酸化物の結晶粒子の成長が著しく遅く
て、正極材料の比表面積が大きくなるので単位面積当た
りの金属ハロゲン化物の量が少なくなりすぎることとリ
チウム含有遷移金属酸化物またはリチウム含有遷移金属
ハロゲン化酸化物粒子表面においてハロゲン元素の濃度
傾斜層が形成されないため好ましくない。また、金属ハ
ロゲン化物の種類にもよるが例えば金属ハロゲン化物が
ＬｉＦの場合、リチウム源となるリチウム化合物とＬｉ
Ｆの二成分状態図において共晶温度（硝酸リチウム；２
５１℃、水酸化リチウム；４３１℃、炭酸リチウム；６
０９℃、塩化リチウム；５０１℃）より低い温度域では
ＬｉＦが溶融状態を経ることがないためＬｉＦが表面の
大部分を覆うのが困難になるとともに、反応性が低下
し、ＬｉＦが粒子表面から内部に固溶していくことが困
難になるので好ましくない。従って、リチウム源として
ＬｉＦとの共晶温度が５００℃より高いリチウム化合物
を使用する場合は共晶温度より高い温度で熱処理するこ
とが好ましい。In the production of the positive electrode material for a lithium secondary battery according to the present invention, the above mixture is heat-treated at 500 ° C. to 800 ° C., preferably 670 ° C. to 770 ° C., for 1 hour or more. At a temperature higher than 800 ° C., the reaction between the metal halide and the lithium-containing transition metal oxide or the lithium-containing transition metal halide proceeds, and the metal halide is converted to the lithium-containing transition metal oxide or the lithium-containing transition metal halide oxide. This is not preferable because the solid solution forms a solid solution inside the crystal grains of the product, the halogen concentration is averaged, and the thickness of the inclined layer becomes too large. At a temperature lower than 500 ° C., the growth of crystal grains of a lithium-containing transition metal oxide or a lithium-containing transition metal halide is extremely slow, and the specific surface area of the positive electrode material is increased. It is not preferable that the amount is too small and that the concentration gradient layer of the halogen element is not formed on the surface of the lithium-containing transition metal oxide or lithium-containing transition metal halide oxide particles. Further, depending on the type of the metal halide, for example, when the metal halide is LiF, a lithium compound serving as a lithium source and Li
In the binary phase diagram of F, the eutectic temperature (lithium nitrate; 2
51 ° C, lithium hydroxide; 431 ° C, lithium carbonate; 6
(09 ° C., lithium chloride; 501 ° C.). In a temperature range lower than (Li), LiF does not go through a molten state, so that it is difficult for LiF to cover most of the surface, and the reactivity decreases, and LiF is removed from the particle surface. It is not preferable because solid solution inside becomes difficult. Therefore, when a lithium compound having a eutectic temperature with LiF higher than 500 ° C. is used as the lithium source, it is preferable to perform the heat treatment at a temperature higher than the eutectic temperature.
【００２９】次に、本発明のリチウム二次電池について
詳細に説明する。本発明のリチウム二次電池の正極は、
前述した本発明のリチウム二次電池用正極材料を活物質
として含むものである。該正極は、具体的には、該リチ
ウム−遷移金属ハロゲン化酸化物粉末、導電剤、バイン
ダーからなり、導電材としては、天然黒鉛、人造黒鉛、
コークス類などの炭素質材料が挙げられ、バインダーと
しては、ポリフッ化ビニリデン、ポリテトラフルオロエ
チレン、ポリエチレン、ポリプロピレンなどの熱可塑性
樹脂が挙げられる。Next, the lithium secondary battery of the present invention will be described in detail. The positive electrode of the lithium secondary battery of the present invention,
The positive electrode material for a lithium secondary battery of the present invention described above is included as an active material. The positive electrode is specifically composed of the lithium-transition metal halide oxide powder, a conductive agent, and a binder. As the conductive material, natural graphite, artificial graphite,
Carbonaceous materials such as cokes are exemplified, and binders include thermoplastic resins such as polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, and polypropylene.
【００３０】本発明のリチウム二次電池の負極として
は、リチウム金属、リチウム合金、またはリチウムイオ
ンを吸蔵、放出可能な材料が用いられる。リチウムイオ
ンを吸蔵、放出可能な材料としては、天然黒鉛、人造黒
鉛、コークス類、カーボンブラック、熱分解炭素類、炭
素繊維などの炭素質材料が挙げられる。As the negative electrode of the lithium secondary battery of the present invention, a lithium metal, a lithium alloy, or a material capable of inserting and extracting lithium ions is used. Materials capable of occluding and releasing lithium ions include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, and carbon fibers.
【００３１】本発明のリチウム二次電池の電解質として
は、リチウム塩を有機溶媒に溶解させた非水電解質溶
液、または、固体電解質のいずれかから選ばれる公知の
ものが用いられる。リチウム塩としては、ＬｉＣｌ
Ｏ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＢＦ4、ＬｉＣＦ3
ＳＯ3などのうち一種あるいは二種以上の混合物が挙げ
られる。As the electrolyte of the lithium secondary battery of the present invention, a known electrolyte selected from a non-aqueous electrolyte solution obtained by dissolving a lithium salt in an organic solvent and a solid electrolyte is used. As the lithium salt, LiCl
O 4 , LiPF 6 , LiAsF 6 , LiBF 4 , LiCF 3
One or a mixture of two or more of SO 3 and the like can be mentioned.
【００３２】有機溶媒としてはプロピレンカーボネー
ト、エチレンカーボネート、ジメチルカーボネート、ジ
エチルカーボネートなどのカーボネート類、１，２−ジ
メトキシエタン、１，３−ジメトキシプロパン、テトラ
ヒドロフランなどのエーテル類、ギ酸メチル、酢酸メチ
ル、γ−ブチルラクトンなどのエステル類、アセトニト
リル、ブチロニトリルなどのニトリル類、Ｎ，Ｎ−ジメ
チルホルムアミドなどのアミド類、スルホラン、ジメチ
ルスルホキシド、１，３−プロパンサルトンなどの含硫
黄化合物が挙げられるが、通常はこれらのうち二種以上
を混合して用いる。Examples of the organic solvent include carbonates such as propylene carbonate, ethylene carbonate, dimethyl carbonate and diethyl carbonate, ethers such as 1,2-dimethoxyethane, 1,3-dimethoxypropane and tetrahydrofuran, methyl formate, methyl acetate, γ Esters such as -butyllactone; nitriles such as acetonitrile and butyronitrile; amides such as N, N-dimethylformamide; and sulfur-containing compounds such as sulfolane, dimethylsulfoxide and 1,3-propanesultone. Are used by mixing two or more of them.
【００３３】固体電解質としてはポリエチレンオキサイ
ド誘導体か該誘導体を含むポリマー、ポリプロピレンオ
キサイド誘導体か該誘導体を含むポリマーなどの有機固
体電解質や、Ｌｉ3Ｎ、ＬｉＩ、Ｌｉ3Ｎ−ＬｉＩ−Ｌｉ
ＯＨ、Ｌｉ4ＳｉＯ4、Ｌｉ4ＳｉＯ4−Ｌｉ3ＰＯ4などの
無機固体電解質が挙げられる。また、高分子に非水電解
質溶液を保持させたゲル状のものを用いることもでき
る。本発明のリチウム二次電池の形状は特に限定され
ず、ペーパー型、コイン型、円筒型、角型などのいずれ
であってもよい。As the solid electrolyte, an organic solid electrolyte such as a polyethylene oxide derivative or a polymer containing the derivative, a polypropylene oxide derivative or a polymer containing the derivative, Li 3 N, LiI, Li 3 N—LiI—Li
Inorganic solid electrolytes such as OH, Li 4 SiO 4 and Li 4 SiO 4 —Li 3 PO 4 are exemplified. Further, a gel in which a non-aqueous electrolyte solution is held in a polymer can also be used. The shape of the lithium secondary battery of the present invention is not particularly limited, and may be any of a paper type, a coin type, a cylindrical type, a square type, and the like.
【００３４】[0034]
【実施例】以下、本発明を実施例によりさらに詳細に説
明するが、本発明はこれらによって何ら限定されるもの
ではない。実施例１〜１６及び比較例１〜５ 表１に示す割合［ＬｉＯＨ／（Ｍ＋Ｔ）；Ｔ／（Ｍ＋
Ｔ）；Ｘ／Ｍ（表中、比は全て原子比）］でＬｉＯＨ・
Ｈ2Ｏと遷移金属Ｍ源と置換元素Ｔ源及びＬｉＦを乳鉢
で擂潰混合し更に乾式振動ミルでよく混合した後、空気
中、表１に示す焼成温度で焼成して正極活物質粉末を得
た。図１に比較例１（図中、上段に示す。）および実施
例１（図中、下段に示す。）の正極材料のＸ線回折測定
の結果を示す。図１より、得られた正極材料はＪＣＰＤ
Ｓ：Ｎｏ．３５−７８２のＬｉＭｎ2Ｏ4と同様のパター
ンを示す立方晶のスピネル型結晶構造であることが分か
り、図２に拡大図を示すように、実施例１の正極材料に
はその他にＬｉＦのピーク（図中、矢印で示す。）が検
出された。比較例２および３は比較例１と同様のパター
ンで、実施例２〜１５および比較例４は実施例１と同様
のパターンであった。比較例５と実施例１６の正極材料
は何れもＪＣＰＤＳ：Ｎｏ．１６−４２７のＬｉＣｏＯ
2と同様のパターンを示す層状岩塩型構造であることが
分かり、実施例１６についてはその他にＬｉＦのピーク
が検出された。また、実施例１〜１６及び比較例１〜５
の粉末の立方晶のスピネル型結晶構造または層状岩塩型
構造の格子定数を表２に示す。The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. Examples 1 to 16 and Comparative Examples 1 to 5 [LiOH / (M + T); T / (M +
T); X / M (all ratios in the table are atomic ratios)]
H 2 O, the transition metal M source, the substitution element T source, and LiF were ground and mixed in a mortar, mixed well with a dry vibrating mill, and then fired in air at the firing temperature shown in Table 1 to obtain a positive electrode active material powder. Obtained. FIG. 1 shows the results of X-ray diffraction measurement of the positive electrode materials of Comparative Example 1 (shown in the upper part of the figure) and Example 1 (shown in the lower part of the figure). From FIG. 1, the obtained cathode material is JCPD
S: No. It was found that the positive electrode material of Example 1 had a LiF peak in addition to the cubic spinel-type crystal structure showing a pattern similar to that of LiMn 2 O 4 of No. 35-782. (Indicated by an arrow in the figure). Comparative Examples 2 and 3 had the same pattern as Comparative Example 1, and Examples 2 to 15 and Comparative Example 4 had the same pattern as Example 1. The positive electrode materials of Comparative Example 5 and Example 16 were all JCPDS: No. 16-427 LiCoO
2 shows that a layered rock-salt structure exhibiting similar pattern with a peak of Other LiF for Example 16 were detected. Examples 1 to 16 and Comparative Examples 1 to 5
Table 2 shows the lattice constant of the cubic spinel-type crystal structure or the layered rock-salt-type structure of the powder of Table 1.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】『リチウム含有遷移金属酸化物またはリチ
ウム含有遷移金属ハロゲン化酸化物粒子表面におけるハ
ロゲン元素濃度傾斜層の厚さの評価および金属ハロゲン
化物として存在するハロゲンの量とリチウム含有遷移金
属酸化物またはリチウム含有遷移金属ハロゲン化酸化物
粒子中に固溶体の状態で存在するハロゲンの量の評価』
実施例１〜１６及び比較例１〜５で得られた正極材料粉
末をＬｉＦの水に対する溶解度が０．１３３ｗｔ％（２
５℃）であり、リチウム含有遷移金属化合物が水に不溶
であることを利用し、十分に水洗を行い濾過乾燥して表
面を覆うＬｉＦを完全に除去した粉末を得た。この粒子
表面について、フッ素イオンの深さ方向の分布を粒子の
表面の任意の位置をイオンビームによりスパッタしなが
らＴＯＦ−ＳＩＭＳによりＦ濃度の深さ方向の分布を調
べＦイオン強度が表層部分での強度の１０％になる深さ
（傾斜層の厚さ）を求めた。その結果を表３に示す。
尚、厚さは単結晶Ｓｉ換算の厚さである。"Evaluation of the thickness of the gradient layer of the halogen element concentration on the surface of the lithium-containing transition metal oxide or lithium-containing transition metal halide oxide particles and the amount of the halogen present as the metal halide and the lithium-containing transition metal oxide or Evaluation of the amount of halogens present in solid solution in lithium-containing transition metal halide oxide particles "
The solubility of LiF in water was 0.133 wt% (2%) for the positive electrode material powders obtained in Examples 1 to 16 and Comparative Examples 1 to 5.
Taking advantage of the fact that the lithium-containing transition metal compound is insoluble in water, a powder was obtained by thoroughly washing with water and filtering and drying to completely remove LiF covering the surface. With respect to the particle surface, the distribution of fluorine concentration in the depth direction was examined by TOF-SIMS while sputtering an arbitrary position on the surface of the particle with an ion beam. The depth at which the strength becomes 10% (thickness of the inclined layer) was determined. Table 3 shows the results.
The thickness is a thickness in terms of single crystal Si.
【００３８】[0038]
【表３】 [Table 3]
【００３９】また、水洗を行う前の粉末と水洗を行った
後の粉末をそれぞれ湿式分解した後、遷移金属Ｍの含有
量をＩＣＰにより、Ｆの含有量をイオンクロマトグラフ
により測定し、ＬｉＦとして存在するＦ量［Ｆ（Ｌｉ
Ｆ）］、リチウム含有遷移金属酸化物またはリチウム含
有遷移金属ハロゲン化酸化物粒子中に固溶体の状態で存
在するＦ量［Ｆ（ＬｉＭＯ）］、これらの合計量をそれ
ぞれＭの原子数に対する比で求めた結果を表３に示す。After the powder before and after the water washing was wet-decomposed, the content of the transition metal M was measured by ICP, and the content of F was measured by ion chromatography. The amount of F present [F (Li
F)], the amount of F present as a solid solution in the lithium-containing transition metal oxide or lithium-containing transition metal halide oxide particles [F (LiMO)], and the total amount thereof in a ratio to the number of M atoms. Table 3 shows the obtained results.
【００４０】『充放電特性の評価』 実施例１〜１５及び比較例１〜５で得られた正極材料を
使用し、以下のようにコイン型テストセルを構成し、高
温（６０℃）における充放電特性を測定した。正極活物
質粉末８０重量部と導電剤のアセチレンブラックとグラ
ファイトをそれぞれ５重量部ずつとフッ素系高分子バイ
ンダーのポリフッ化ビニリデン１０重量部とを１−メチ
ル−２−ピロリドン溶媒を加えて混合したものをアルミ
ニウム箔の集電体上に塗布し、１−メチル−２−ピロリ
ドンを充分に乾燥して加圧成型、加熱処理して約２ｃｍ
2の円盤状の正極を作製した。この際、正極中に最終的
に含まれる活物質量は約２０ｍｇとなるように調整し
た。負極活物質の天然黒鉛９０重量部とフッ素系高分子
バインダーのポリフッ化ビニリデン１０重量部とを１−
メチル−２−ピロリドン溶媒を加えて均一に混合したも
のを銅箔の集電体上に塗布し、１−メチル−２−ピロリ
ドンを充分に乾燥して加圧成型、加熱処理して約２ｃｍ
2の円盤状の負極を作製した。この際、負極中に最終的
に含まれる活物質量は約１０ｍｇとなるように調整し
た。この様にして得られた正極と負極とを用い、更に、
非水電解液にＬｉＰＦ6をエチレンカーボネートとジメ
チルカーボネートを体積比で１：２の割合で混合した溶
媒中に１Ｍの濃度で溶解させたものを用い、コイン型の
電池を作製した。この電池を用い高温（６０℃）での充
放電サイクル試験を行った。充放電を行う期間は１週間
とし、１週間経過後充放電を止め、速やかに次の項で説
明するＭｎ溶出量の評価の実験を行った。充放電の条件
は以下のように設定した。充電は定電流−定電圧モード
で、定電流時の電流密度を０．４ｍＡ／ｃｍ2、定電圧
設定値を４．２Ｖ、充電開始からの全充電時間を５時間
とした。即ち、充放電のスタート時は定電流で充電を行
い、電池の電圧が４．２Ｖに達した時点（理論容量から
５時間より必ず短い）で定電圧モードに切り替え、充電
開始から５時間経過後充電は終了する。放電は０．４ｍ
Ａ／ｃｍ2定電流モードで電池の電圧が２．７Ｖに達し
た時点で放電が終了するように設定した。１サイクル目
の放電容量を１００とした場合の２５サイクル目の放電
容量維持率（％）を表４に示す。[Evaluation of Charge / Discharge Characteristics] Using the positive electrode materials obtained in Examples 1 to 15 and Comparative Examples 1 to 5 , a coin-type test cell was constructed as follows, and charged at a high temperature (60 ° C.). The discharge characteristics were measured. A mixture obtained by adding 1-methyl-2-pyrrolidone solvent to 80 parts by weight of a positive electrode active material powder, 5 parts by weight of each of acetylene black and graphite as conductive agents, and 10 parts by weight of polyvinylidene fluoride as a fluorine-based polymer binder. Is applied on a current collector of aluminum foil, 1-methyl-2-pyrrolidone is sufficiently dried, molded under pressure, and heat-treated for about 2 cm.
A disk-shaped positive electrode of No. 2 was produced. At this time, the amount of the active material finally contained in the positive electrode was adjusted to be about 20 mg. 90 parts by weight of natural graphite as a negative electrode active material and 10 parts by weight of polyvinylidene fluoride as a fluoropolymer binder were added to 1-
A mixture obtained by adding a methyl-2-pyrrolidone solvent and uniformly mixing the mixture was applied on a copper foil current collector, and 1-methyl-2-pyrrolidone was sufficiently dried, molded under pressure, and heat-treated to about 2 cm.
A disk-shaped negative electrode of No. 2 was produced. At this time, the amount of the active material finally contained in the negative electrode was adjusted to be about 10 mg. Using the positive electrode and the negative electrode thus obtained,
A coin-type battery was manufactured using a non-aqueous electrolyte in which LiPF 6 was dissolved at a concentration of 1M in a solvent in which ethylene carbonate and dimethyl carbonate were mixed at a volume ratio of 1: 2. A charge / discharge cycle test at a high temperature (60 ° C.) was performed using this battery. The charging / discharging period was set to one week, and after one week, the charging / discharging was stopped, and an experiment for evaluating the amount of Mn elution described in the next section was immediately performed. Charge and discharge conditions were set as follows. The charging was performed in a constant current-constant voltage mode, the current density at the time of constant current was 0.4 mA / cm 2 , the constant voltage set value was 4.2 V, and the total charging time from the start of charging was 5 hours. That is, at the start of charging / discharging, charging is performed with a constant current, and when the battery voltage reaches 4.2 V (it is always shorter than 5 hours from the theoretical capacity), the mode is switched to the constant voltage mode. Charging ends. Discharge is 0.4m
The discharge was set to end when the battery voltage reached 2.7 V in the A / cm 2 constant current mode. Table 4 shows the discharge capacity retention rate (%) at the 25th cycle when the discharge capacity at the first cycle is 100.
【００４１】[0041]
【表４】 [Table 4]
【００４２】表５より、実施例１〜１６の電池は正極活
物質表面にＬｉＦ層とＦ濃度傾斜層を有しない比較例
１、２、５に比べて高温（６０℃）サイクル特性が向上
していることが分かる。一方、比較例３の電池の放電容
量維持率は比較例１よりは高いが比較例２よりやや小さ
い値となった。これは、ＬｉＦ層やＦ濃度傾斜層の厚さ
が薄すぎるためこれらの層による高温での充放電特性改
善の効果が十分に現れなかったためと考えられる。ま
た、比較例４の電池は比較例２と同程度であった。これ
は、ＬｉＦ層やＦ濃度傾斜層の厚さが厚すぎるためＬｉ
イオンの拡散が妨げられ、過負荷状態になったためと考
えられる。[0042] Table 5 from comparison no LiF layer and F concentration gradient layer on the surface of the cathode active material cell of Examples 1-16 Example
It can be seen that the high-temperature (60 ° C.) cycle characteristics are improved as compared with 1 , 2, and 5 . On the other hand, the discharge capacity retention ratio of the battery of Comparative Example 3 was higher than that of Comparative Example 1, but slightly smaller than that of Comparative Example 2. This is considered to be because the LiF layer and the F-concentration gradient layer were too thin, and the effect of improving the charge / discharge characteristics at high temperatures by these layers did not appear sufficiently. Further, the battery of Comparative Example 4 was comparable to that of Comparative Example 2. This is because the thickness of the LiF layer or the F concentration gradient layer is too large,
It is considered that the diffusion of ions was hindered, resulting in an overload condition.
【００４３】『電解液中へのＭｎ溶出量の評価』 実施例１〜１５と比較例１〜４について上記の充放電特
性の評価（１週間の充放電）終了後の電池を分解し、電
解液中に存在するＭｎと負極上に析出したＭｎの全量
（即ち、Ｍｎ溶出量）を、電解液と負極を酸中で加熱分
解して検液を作製しこれをＩＣＰによりＭｎ濃度分析を
行うことにより求めた。この様にして求めた正極活物質
２０ｍｇ当たりの全Ｍｎ溶出量（μｇ）を表５に示す。[Evaluation of Mn Elution Amount in Electrolyte Solution] The batteries after Examples 1 to 15 and Comparative Examples 1 to 4 after the above-described evaluation of charge / discharge characteristics (one-week charge / discharge) were disassembled. The total amount of Mn present in the solution and Mn deposited on the negative electrode (that is, the amount of Mn eluted) is thermally decomposed in an electrolytic solution and a negative electrode in an acid to prepare a test solution, which is subjected to Mn concentration analysis by ICP. I asked for it. Table 5 shows the total elution amount of Mn (μg) per 20 mg of the positive electrode active material thus determined.
【００４４】[0044]
【表５】 [Table 5]
【００４５】表５より、実施例１〜１５の電池は正極活
物質表面にＬｉＦ層とＦ濃度傾斜層を有しない比較例
１、２に比べて一週間の高温（６０℃）サイクルにより
Ｍｎ溶出量が減少していることが分かる。一方、比較例
３の電池のＭｎ溶出量は比較例１よりは少ないが比較例
２よりやや多い値となった。これは、ＬｉＦ層やＦ濃度
傾斜層厚さが薄すぎるためこれらの層によるＭｎ溶出抑
制の効果が十分に現れなかったためと考えられる。As shown in Table 5, the batteries of Examples 1 to 15 eluted Mn by one-week high-temperature (60 ° C.) cycle compared to Comparative Examples 1 and 2 having no LiF layer and F-gradient layer on the surface of the positive electrode active material. It can be seen that the amount has decreased. On the other hand, the amount of Mn eluted in the battery of Comparative Example 3 was smaller than that of Comparative Example 1, but slightly larger than that of Comparative Example 2. This is presumably because the LiF layer and the F-concentration gradient layer were too thin, and the effect of these layers to suppress Mn elution was not sufficiently exhibited.
【００４６】[0046]
【発明の効果】以上の説明から明らかなように、本発明
のリチウム−遷移金属系ハロゲン化酸化物は、リチウム
含有遷移金属酸化物またはリチウム含有遷移金属ハロゲ
ン化酸化物粒子表面が金属ハロゲン化物で覆われ且つリ
チウム含有遷移金属酸化物またはリチウム含有遷移金属
ハロゲン化酸化物粒子内の表面近傍にハロゲン元素濃度
傾斜層を有することにより、リチウム二次電池用の正極
材料として、高出力、高エネルギー密度が得られ、高温
下でもサイクル特性や保存特性が良好なリチウム含有遷
移金属酸化物系の正極材料およびその製造方法を提供す
ることができ、この材料を正極に用いて高温下でもサイ
クル特性や保存特性が良好なリチウム二次電池を提供す
ることができる。As is clear from the above description, the lithium-transition metal halide oxide of the present invention is characterized in that the surface of the lithium-containing transition metal oxide or the surface of the lithium-containing transition metal halide oxide is a metal halide. By having a halogen element concentration gradient layer in the vicinity of the surface of the covered transition metal oxide or lithium-containing transition metal halide oxide particles covered with the lithium-containing transition metal oxide or lithium-containing transition metal halide, it has high output and high energy density as a cathode material for a lithium secondary battery. It is possible to provide a lithium-containing transition metal oxide-based positive electrode material having good cycle characteristics and storage characteristics even at high temperatures and a method for producing the same. A lithium secondary battery having favorable characteristics can be provided.
【図１】実施例１（図中、下段）および比較例１（図
中、上段）で得られた正極材料のＸ線回折図である。FIG. 1 is an X-ray diffraction diagram of a positive electrode material obtained in Example 1 (lower part in the figure) and Comparative Example 1 (upper part in the figure).
【図２】図１における実施例１のＸ線回折図の拡大図で
ある。FIG. 2 is an enlarged view of an X-ray diffraction diagram of Example 1 in FIG.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０１Ｇ 53/09 Ｃ０１Ｇ 53/09 Ｈ０１Ｍ 4/58 Ｈ０１Ｍ 4/58 10/40 10/40 Ｚ // Ｈ０１Ｍ 4/02 4/02 Ｃ 4/04 4/04 Ａ (56)参考文献 特開 平７−33443（ＪＰ，Ａ) 特開 平10−334918（ＪＰ，Ａ) 特開 平６−44971（ＪＰ，Ａ) 特開 平10−294100（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 37/06 C01G 45/06 C01G 49/10 C01G 51/08 C01G 53/09 H01M 4/02 ＢＥＩＬＳＴＥＩＮ（ＳＴＮ)Continued on the front page (51) Int.Cl. 7 Identification code FI C01G 53/09 C01G 53/09 H01M 4/58 H01M 4/58 10/40 10/40 Z // H01M 4/02 4/02 C 4 / 04 4/04 A (56) References JP-A-7-33443 (JP, A) JP-A-10-334918 (JP, A) JP-A-6-44971 (JP, A) JP-A-10-294100 ( JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01G 37/06 C01G 45/06 C01G 49/10 C01G 51/08 C01G 53/09 H01M 4/02 BEILSTEIN (STN)
Claims (16)
くとも１種類以上の金属元素であり、Ｘは少なくとも１
種類以上のハロゲン元素である。ａは０．２≦ａ≦１．
２、ｂは０．８≦ｂ≦１．２、ｃは１．７≦ｃ≦２．
１、ｄは０≦ｄ≦０．３である。）で表されるリチウム
含有遷移金属酸化物またはリチウム含有遷移金属ハロゲ
ン化酸化物を主成分とし、その粒子表面が結晶性の金属
ハロゲン化物ＮＸe（ここで、Ｎは、Ｌｉ、Ｍｇ、Ａ
ｌ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏから選ば
れた少なくとも１種類以上の金属元素であり、Ｘは少な
くとも１種類以上のハロゲン元素であり、ｅは金属元素
Ｎの価数と等しい。）で被覆されているリチウム−遷移
金属系ハロゲン化酸化物であって、粒子表面に結晶性の
金属ハロゲン化物の状態で存在するハロゲンの量が、Ｘ
／Ｍ原子比で０．０１〜０．５であり、粒子内部の酸素
原子を置換した固溶体の状態で存在するハロゲンの量
が、Ｘ／Ｍ原子比で０．００２以上であり、かつ粒子表
面に結晶性の金属ハロゲン化物の状態で存在するハロゲ
ンと粒子内部の酸素原子を置換した固溶体の状態で存在
するハロゲンとの合計量が、Ｘ／Ｍ原子比で０．０２〜
０．５であることを特徴とするリチウム−遷移金属系ハ
ロゲン化酸化物。1. A in the general formula Li a M b O c X d ( wherein, M represents Cr, Mn, Fe, at least one or more metal elements selected from Co, X is at least 1
More than one kind of halogen element. a is 0.2 ≦ a ≦ 1.
2, b is 0.8 ≦ b ≦ 1.2, c is 1.7 ≦ c ≦ 2.
1, d is 0 ≦ d ≦ 0.3. ) Represented by the formula (1), wherein the main component is a lithium-containing transition metal oxide or a lithium-containing transition metal halide oxide, and the particle surface of which is crystalline NX e (where N is Li, Mg, A
1, at least one metal element selected from Ca, Ti, V, Cr, Mn, Fe, and Co , X is at least one halogen element, and e is the valence of the metal element N. equal. ), Wherein the amount of halogen present in the form of crystalline metal halide on the particle surface is X
/ M atomic ratio is 0.01 to 0.5, and the amount of halogen present in the form of a solid solution in which oxygen atoms inside the particles are substituted is 0.002 or more in X / M atomic ratio, and the particle surface The total amount of halogen present in the form of a crystalline metal halide and halogen present in the form of a solid solution in which oxygen atoms inside the grains have been substituted is 0.02
0.5, a lithium-transition metal halide oxide.
ハロゲン化物層と粒子内部のリチウム含有遷移金属酸化
物またはリチウム含有遷移金属ハロゲン化酸化物との間
に表層側から内部に向かって酸素原子を置換したハロゲ
ンの濃度が減少してゆく濃度傾斜層が存在し、表層側界
面のハロゲン濃度の１０％に減衰するまでの深さが、表
層側界面から０．５〜８０ｎｍであるような傾斜構造を
有することを特徴とする請求項１に記載のリチウム−遷
移金属系ハロゲン化酸化物。2. A method according to claim 1, wherein oxygen is present between the crystalline metal halide layer present on the outermost surface of the grains and the lithium-containing transition metal oxide or the lithium-containing transition metal halide oxide inside the grains from the surface side toward the inside. There is a concentration gradient layer in which the concentration of halogen substituted for atoms is reduced, and the depth until the concentration is reduced to 10% of the halogen concentration at the surface side interface is 0.5 to 80 nm from the surface side interface. The lithium-transition metal-based halogenated oxide according to claim 1, having a tilted structure.
くとも１種類以上の金属元素であり、Ｘは少なくとも１
種類以上のハロゲン元素である。ａは０．２≦ａ≦１．
２、ｂは０．８≦ｂ≦１．２、ｃは１．７≦ｃ≦２．
１、ｄは０≦ｄ≦０．３である。）で表されるリチウム
含有遷移金属酸化物またはリチウム含有遷移金属ハロゲ
ン化酸化物が、立方晶のスピネル型構造を有するマンガ
ン酸リチウムであり、且つ、その格子定数が０．８２４
０５ｎｍ以下であることを特徴とする請求項１または２
に記載のリチウム−遷移金属系ハロゲン化酸化物。3. In the general formula Li a M b O c X d ( wherein, M represents Cr, Mn, Fe, at least one or more metal elements selected from Co, X is at least 1
More than one kind of halogen element. a is 0.2 ≦ a ≦ 1.
2, b is 0.8 ≦ b ≦ 1.2, c is 1.7 ≦ c ≦ 2.
1, d is 0 ≦ d ≦ 0.3. The lithium-containing transition metal oxide or the lithium-containing transition metal halide represented by the formula (1) is lithium manganate having a cubic spinel structure, and has a lattice constant of 0.824.
3. The structure according to claim 1, wherein the thickness is equal to or less than 0.05 nm.
4. The lithium-transition metal halide oxide described in 1. above.
ガン酸リチウムの結晶中におけるリチウムまたはマンガ
ンの占有する格子サイトの一部がＢ、Ｍｇ、Ａｌ、Ｐ、
Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｂ
ａ、Ｇａ、Ｔａから選ばれる少なくとも１種類以上の元
素で置換されたものであることを特徴とする請求項３に
記載のリチウム−遷移金属系ハロゲン化酸化物。4. In a lithium manganate crystal having a cubic spinel structure, part of lattice sites occupied by lithium or manganese is B, Mg, Al, P,
Ca, Ti, V, Cr, Fe, Co, Cu , Zn, B
4. The lithium-transition metal halide oxide according to claim 3, wherein the lithium-transition metal halide oxide is substituted with at least one element selected from a, Ga, and Ta. 5.
子サイトの一部がＭｇで置換されたものであることを特
徴とする請求項４に記載のリチウム−遷移金属系ハロゲ
ン化酸化物。5. The lithium-transition metal halide oxide according to claim 4, wherein a part of lattice sites occupied by lithium or manganese is substituted by Mg.
の状態で存在するハロゲンの量が、Ｘ／Ｍ原子比で０．
１１５〜０．５であり、粒子内部の酸素原子を置換した
固溶体の状態で存在するハロゲンの量が、Ｘ／Ｍ原子比
で０．００４以上であり、かつ粒子表面に結晶性の金属
ハロゲン化物の状態で存在するハロゲンと粒子内部の酸
素原子を置換した固溶体の状態で存在するハロゲンとの
合計量が、Ｘ／Ｍ原子比で０．１２〜０．５であること
を特徴とする請求項３〜５に記載のリチウム−遷移金属
系ハロゲン化酸化物。6. The amount of halogen present in the form of a crystalline metal halide on the surface of a grain is 0.1% by X / M atomic ratio.
The amount of halogen present in the form of a solid solution in which oxygen atoms in the grains have been substituted is 115 to 0.5, and the X / M atomic ratio is 0.004 or more, and a crystalline metal halide is present on the grain surface. The total amount of the halogen existing in the state of (1) and the halogen existing in the state of a solid solution in which oxygen atoms inside the grains are substituted is 0.12 to 0.5 in X / M atomic ratio. 6. The lithium-transition metal halide oxide according to 3 to 5.
およびＣｒ、Ｍｎ、Ｆｅ、Ｃｏから選ばれた少なくとも
１種類以上の金属元素を含有する化合物からなる混合物
を５００℃〜８００℃で加熱することを特徴とする請求
項１または２に記載のリチウム−遷移金属系ハロゲン化
酸化物の製造方法。7. A lithium compound, a metal halide,
The mixture according to claim 1 or 2, wherein a mixture comprising a compound containing at least one metal element selected from the group consisting of Cr, Mn, Fe, and Co is heated at 500 ° C to 800 ° C. A method for producing a transition metal halide oxide.
び金属ハロゲン化物からなる混合物を５００℃〜８００
℃で加熱することを特徴とする請求項３または６に記載
のリチウム−遷移金属系ハロゲン化酸化物の製造方法。8. A mixture comprising a lithium compound, a manganese compound, and a metal halide is heated at 500 ° C. to 800 ° C.
The method for producing a lithium-transition metal-based halogenated oxide according to claim 3 or 6, wherein the method is heated at a temperature of ° C.
属ハロゲン化物、およびＢ、Ｍｇ、Ａｌ、Ｐ、Ｃａ、Ｔ
ｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｂａ、
Ｇａ、Ｔａから選ばれる少なくとも１種類以上の金属元
素を含有する化合物からなる混合物を５００℃〜８００
℃で加熱することを特徴とする請求項４〜６に記載のリ
チウム−遷移金属系ハロゲン化酸化物の製造方法。9. A lithium compound, a manganese compound, a metal halide, and B, Mg, Al, P, Ca, T
i, V, Cr, Fe, Co, Ni, Cu, Zn, Ba,
A mixture comprising a compound containing at least one or more metal elements selected from Ga and Ta at 500 ° C. to 800 ° C.
The method for producing a lithium-transition metal-based halogenated oxide according to any one of claims 4 to 6, wherein the method is heated at ℃.
が２．７５〜３．４価であるマンガン酸化物またはオキ
シ水酸化マンガンを用いることを特徴とする請求項７〜
９に記載のリチウム−遷移金属系ハロゲン化酸化物の製
造方法。10. The method according to claim 7, wherein the manganese compound is manganese oxide or manganese oxyhydroxide having an average oxidation number of 2.75 to 3.4.
10. The method for producing a lithium-transition metal halide oxide according to item 9.
特徴とする請求項１〜６に記載のリチウム−遷移金属系
ハロゲン化酸化物。11. The lithium-transition metal halide oxide according to claim 1, wherein the halogen element is fluorine.
ＬｉＦであることを特徴とする請求項１〜６または請求
項１１に記載のリチウム−遷移金属系ハロゲン化酸化
物。12. The lithium-transition metal halide oxide according to claim 1, wherein the crystalline metal halide NX e is LiF.
請求項１１または請求項１２に記載のリチウム−遷移金
属系ハロゲン化酸化物を使用することを特徴とするリチ
ウム二次電池。13. The positive electrode active material according to claim 1, wherein
A lithium secondary battery comprising the lithium-transition metal halide oxide according to claim 11.
が３〜４．５Ｖであることを特徴とする請求項１３に記
載のリチウム二次電池。14. The lithium secondary battery according to claim 13, wherein the operating voltage of the lithium secondary battery is 3 to 4.5 V.
特徴とする請求項７〜１０に記載のリチウム−遷移金属
系ハロゲン化酸化物の製造方法。15. The method for producing a lithium-transition metal-based halogenated oxide according to claim 7, wherein the halogen element is fluorine.
ＬｉＦであることを特徴とする請求項７〜１０に記載の
リチウム−遷移金属系ハロゲン化酸化物の製造方法。16. The method for producing a lithium-transition metal halide oxide according to claim 7, wherein the crystalline metal halide NX e is LiF.
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| JP10296266A JP3141858B2 (en) | 1998-10-19 | 1998-10-19 | Lithium transition metal halide oxide, method for producing the same and use thereof |
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