JPH09147863A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH09147863A JPH09147863A JP7329511A JP32951195A JPH09147863A JP H09147863 A JPH09147863 A JP H09147863A JP 7329511 A JP7329511 A JP 7329511A JP 32951195 A JP32951195 A JP 32951195A JP H09147863 A JPH09147863 A JP H09147863A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous electrolyte
- electrolyte battery
- positive electrode
- lithium
- transition metal
- 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
【０００２】[0002]
【発明の属する技術分野】この発明は、負極に金属リチ
ウム又はリチウムイオンの吸蔵，放出が可能な材料を用
いると共に、正極にリチウムイオンの吸蔵，放出が可能
なリチウム遷移金属複合酸化物を用いた非水電解質電池
に係り、特に、その正極材料が改良されて充放電サイク
ル特性等が向上した非水電解質電池に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a material capable of occluding and releasing metallic lithium or lithium ions for the negative electrode and a lithium transition metal composite oxide capable of occluding and releasing lithium ions for the positive electrode. The present invention relates to a non-aqueous electrolyte battery, and more particularly to a non-aqueous electrolyte battery in which the positive electrode material is improved and the charge / discharge cycle characteristics and the like are improved.
【０００３】[0003]
【従来の技術】近年、高出力，高エネルギー密度の新型
二次電池の１つとして、電解質に非水電解液等の非水電
解質を用い、リチウム等の酸化，還元を利用して放電及
び充電を行なうようにした非水電解質電池が利用される
ようになった。2. Description of the Related Art In recent years, as one of new high-output and high-energy-density secondary batteries, a non-aqueous electrolyte such as a non-aqueous electrolyte is used as an electrolyte for discharging and charging by utilizing oxidation and reduction of lithium. The non-aqueous electrolyte battery adapted to do so has come to be used.
【０００４】そして、このような非水電解質電池におけ
る正極や負極の材料としては、従来より様々な材料が使
用されており、その正極の材料としては、例えば、リチ
ウムイオンの吸蔵，放出が可能なＬｉＴｉＯ2 ，ＬｉＦ
ｅＯ2 ，ＬｉＣｏＯ2 ，ＬｉＮｉＯ2 等の各種のリチウ
ム遷移金属複合酸化物が一般に使用されていた。Various materials have been conventionally used as materials for the positive electrode and the negative electrode in such a non-aqueous electrolyte battery. As the material for the positive electrode, for example, lithium ions can be occluded and released. LiTiO 2 , LiF
Various lithium-transition metal composite oxides such as eO 2 , LiCoO 2 and LiNiO 2 have been commonly used.
【０００５】しかし、上記のようなリチウム遷移金属複
合酸化物は一般に触媒作用が強く、これを正極材料に用
いた場合、上記のリチウム遷移金属複合酸化物が非水電
解質電池における非水電解液等と反応してこの非水電解
液等が分解され、ガス等が発生して、この非水電解質電
池における保存性や充放電サイクル特性が低下するとい
う問題があった。However, the above lithium-transition metal composite oxide generally has a strong catalytic action, and when it is used as a positive electrode material, the above-mentioned lithium-transition metal composite oxide becomes a non-aqueous electrolytic solution in a non-aqueous electrolyte battery. There is a problem in that the non-aqueous electrolyte solution is decomposed to generate gas and the like, which deteriorates the storage stability and charge / discharge cycle characteristics of the non-aqueous electrolyte battery.
【０００６】[0006]
【発明が解決しようとする課題】この発明は、負極に金
属リチウム又はリチウムイオンの吸蔵，放出が可能な材
料を用いると共に、正極にリチウムイオンの吸蔵，放出
が可能なリチウム遷移金属複合酸化物を用いた非水電解
質電池における上記のような問題を解決することを課題
とするものであり、上記のように正極材料にリチウム遷
移金属複合酸化物を用いた場合においても、この正極材
料と非水電解液等とが反応し、この非水電解液等が分解
されてガス等が発生するということがなく、保存性や充
放電サイクル特性に優れた非水電解質電池が得られるよ
うにすることを課題とするものである。SUMMARY OF THE INVENTION The present invention uses a material capable of occluding and releasing lithium metal or lithium ions for the negative electrode and a lithium transition metal composite oxide capable of occluding and releasing lithium ions for the positive electrode. It is intended to solve the above problems in the non-aqueous electrolyte battery used, even when using a lithium transition metal composite oxide in the positive electrode material as described above, this positive electrode material and non-aqueous electrolyte It is necessary to obtain a non-aqueous electrolyte battery that has excellent storage stability and charge / discharge cycle characteristics without reacting with the electrolytic solution or the like and decomposing the non-aqueous electrolytic solution or the like to generate gas or the like. This is an issue.
【０００７】[0007]
【課題を解決するための手段】この発明においては、上
記のような課題を解決するため、負極に金属リチウム又
はリチウムイオンの吸蔵，放出が可能な材料を用いると
共に、正極にリチウムイオンの吸蔵，放出が可能なリチ
ウム遷移金属複合酸化物を用いた非水電解質電池におい
て、上記の正極に使用するリチウム遷移金属複合酸化物
に対してＬｉ6ＣｏＯ4 を添加させるようにしたのであ
る。In order to solve the above-mentioned problems, the present invention uses a material capable of absorbing and desorbing metallic lithium or lithium ions for the negative electrode, and a positive electrode for absorbing and desorbing lithium ions. In a non-aqueous electrolyte battery using a desorbable lithium transition metal composite oxide, Li 6 CoO 4 was added to the lithium transition metal composite oxide used for the positive electrode.
【０００８】そして、この発明における非水電解質電池
のように、正極材料に使用するリチウム遷移金属複合酸
化物にＬｉ6 ＣｏＯ4 を添加させて、このＬｉ6 ＣｏＯ
4 を上記のリチウム遷移金属複合酸化物の表面に付着さ
せると、４．２Ｖ程度の充電ではこのＬｉ6 ＣｏＯ4 が
Ｌｉ5 ＣｏＯ4 まで充電されるだけで、Ｃｏの酸価数が
３を超えないため、このＬｉ6 ＣｏＯ4 が付着した部分
において、上記のリチウム遷移金属複合酸化物における
触媒作用が弱くなり、非水電解液等との接触による反応
が抑制され、非水電解質電池における保存性やサイクル
特性が向上されると共に、このＬｉ6 ＣｏＯ4 がリチウ
ムイオンの吸蔵，放出を行なうため、正極における特性
が低下して放電特性等が低下するということも少ない。Then, as in the non-aqueous electrolyte battery according to the present invention, Li 6 CoO 4 is added to the lithium transition metal composite oxide used for the positive electrode material, and this Li 6 CoO is added.
When 4 is attached to the surface of the above lithium-transition metal composite oxide, the Li 6 CoO 4 is only charged to Li 5 CoO 4 at a charge of about 4.2 V, and the acid value of Co exceeds 3. Therefore, the catalytic action of the above-mentioned lithium-transition metal composite oxide is weakened in the portion to which the Li 6 CoO 4 is attached, the reaction due to contact with the non-aqueous electrolyte solution is suppressed, and the storage stability in the non-aqueous electrolyte battery is reduced. The cycle characteristics are improved and the Li 6 CoO 4 absorbs and desorbs lithium ions, so that the characteristics of the positive electrode and the discharge characteristics are less likely to deteriorate.
【０００９】ここで、上記のようにＬｉ6 ＣｏＯ4 を添
加させるリチウム遷移金属複合酸化物としては、従来よ
りリチウムイオンの吸蔵，放出が可能な正極材料として
一般に使用されているものであれば良く、例えば、下記
の構造式（１）〜（３）で表わされるリチウム遷移金属
複合酸化物を用いることができ、特に、下記の構造式
（１）で示されるリチウム遷移金属複合酸化物に対して
Ｌｉ6 ＣｏＯ4 を添加させると、サイクル特性が非常に
優れた非水電解質電池が得られるようになる。 Ｌｉx Ｎｉy Ｃｏz Ｍ1-y-z Ｏa （１） ［この構造式（１）中において、ＭはＢ，Ｎａ，Ｍｇ，
Ａｌ，Ｓｉ，Ｋ，Ｃａ，Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，
Ｆｅ，Ｃｕ，Ｚｎ，Ｇａ，Ｇｅ，Ｚｒ，Ｎｂ，Ｒｕ，Ａ
ｇ，Ｔａ，Ｂｉ，Ｉｎ，Ｍｏ，Ｗの中から選ばれる少な
くとも１種の元素であり、ｘ，ｙ，ｚ及びａは、０＜ｘ
＜１．３、０．５≦ｙ＋ｚ≦１、１．８≦ａ≦２．２で
あり、ｘは充放電によって変化する。］ Ｌｉx Ｆｅy Ｍ1-y Ｏa （２） ［この構造式（２）中において、ＭはＢ，Ｎａ，Ｍｇ，
Ａｌ，Ｓｉ，Ｋ，Ｃａ，Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，
Ｃｕ，Ｚｎ，Ｇａ，Ｇｅ，Ｚｒ，Ｎｂ，Ｒｕ，Ａｇ，Ｔ
ａ，Ｂｉ，Ｉｎ，Ｍｏ，Ｗ，Ｃｏ，Ｎｉの中から選ばれ
る少なくとも１種の元素であり、ｘ，ｙ及びａは、０＜
ｘ＜２．６、１≦ｙ≦２、３．６≦ａ≦４．４であり、
ｘは充放電によって変化する。］ Ｌｉx Ｍｎy Ｍ2-y Ｏa （３） ［この構造式（３）中において、ＭはＢ，Ｎａ，Ｍｇ，
Ａｌ，Ｓｉ，Ｋ，Ｃａ，Ｓｃ，Ｖ，Ｃｒ，Ｆｅ，Ｔｉ，
Ｃｕ，Ｚｎ，Ｇａ，Ｇｅ，Ｚｒ，Ｎｂ，Ｒｕ，Ａｇ，Ｔ
ａ，Ｂｉ，Ｉｎ，Ｍｏ，Ｗ，Ｃｏ，Ｎｉの中から選ばれ
る少なくとも１種の元素であり、ｘ，ｙ及びａは、０＜
ｘ＜１．３、０．５≦ｙ≦１、１．８≦ａ≦２．２であ
り、ｘは充放電によって変化する。］The lithium-transition metal composite oxide to which Li 6 CoO 4 is added as described above may be any one that has been conventionally used as a positive electrode material capable of absorbing and desorbing lithium ions. For example, a lithium transition metal composite oxide represented by the following structural formulas (1) to (3) can be used, and particularly for a lithium transition metal composite oxide represented by the following structural formula (1): Addition of Li 6 CoO 4 makes it possible to obtain a non-aqueous electrolyte battery having very excellent cycle characteristics. Lix Niy Coz M1-yz Oa (1) [In the structural formula (1), M is B, Na, Mg,
Al, Si, K, Ca, Sc, Ti, V, Cr, Mn,
Fe, Cu, Zn, Ga, Ge, Zr, Nb, Ru, A
At least one element selected from g, Ta, Bi, In, Mo and W, and x, y, z and a are 0 <x.
<1.3, 0.5 ≦ y + z ≦ 1, 1.8 ≦ a ≦ 2.2, and x changes depending on charge and discharge. ] Lix Fey M1-y Oa (2) [In this structural formula (2), M is B, Na, Mg,
Al, Si, K, Ca, Sc, Ti, V, Cr, Mn,
Cu, Zn, Ga, Ge, Zr, Nb, Ru, Ag, T
at least one element selected from a, Bi, In, Mo, W, Co and Ni, and x, y and a are 0 <
x <2.6, 1 ≦ y ≦ 2, 3.6 ≦ a ≦ 4.4,
x changes with charge and discharge. Lix Mny M2-y Oa (3) [In the structural formula (3), M is B, Na, Mg,
Al, Si, K, Ca, Sc, V, Cr, Fe, Ti,
Cu, Zn, Ga, Ge, Zr, Nb, Ru, Ag, T
at least one element selected from a, Bi, In, Mo, W, Co and Ni, and x, y and a are 0 <
x <1.3, 0.5 ≦ y ≦ 1, 1.8 ≦ a ≦ 2.2, and x changes due to charge / discharge. ]
【００１０】そして、上記のようなリチウム遷移金属複
合酸化物に対してＬｉ6 ＣｏＯ4 を添加させるにあた
り、その添加量が少なすぎると、Ｌｉ6 ＣｏＯ4 が上記
のリチウム遷移金属複合酸化物に付着する部分が少な
く、上記のリチウム遷移金属複合酸化物と非水電解液等
が接触して反応するのを十分に抑制することができず、
保存性やサイクル特性を改善することができなくなる一
方、このＬｉ6 ＣｏＯ4 の添加量が多くなりすぎると、
このＬｉ6 ＣｏＯ4 における負荷特性が上記のリチウム
遷移金属複合酸化物に比べて悪く、大電流での放電特性
が悪くなるため、好ましくは、リチウム遷移金属複合酸
化物に対してＬｉ6 ＣｏＯ4 を０．１〜２０ｍｏｌ％の
範囲で、より好ましくは、０．５〜１０ｍｏｌ％の範囲
で添加させるようにする。When Li 6 CoO 4 is added to the above-mentioned lithium-transition metal composite oxide in an excessively small amount, Li 6 CoO 4 adheres to the above-mentioned lithium-transition metal composite oxide. There are few parts to do, it is not possible to sufficiently suppress the reaction of the lithium transition metal composite oxide and the nonaqueous electrolytic solution in contact with each other,
While it becomes impossible to improve the storability and cycle characteristics, if the amount of addition of Li 6 CoO 4 becomes too large,
Since the load characteristics of this Li 6 CoO 4 are worse than that of the above lithium transition metal composite oxide and the discharge characteristics at large current are poor, it is preferable to add Li 6 CoO 4 to the lithium transition metal composite oxide. It is added in the range of 0.1 to 20 mol%, and more preferably in the range of 0.5 to 10 mol%.
【００１１】また、この発明における非水電解質電池に
おいて、負極に使用する負極材料としては、上記のよう
に金属リチウムの他に、リチウムイオンの吸蔵，放出が
可能な材料を用いることができ、例えば、黒鉛，コーク
ス，有機物焼成体等の炭素材料や、Ｌｉ−Ａｌ，Ｌｉ−
Ｉｎ，Ｌｉ−Ｓｎ，Ｌｉ−Ｐｂ，Ｌｉ−Ｂｉ，Ｌｉ−Ｇ
ａ，Ｌｉ−Ｓｒ，Ｌｉ−Ｓｉ，Ｌｉ−Ｚｎ，Ｌｉ−Ｃ
ｄ，Ｌｉ−Ｃａ，Ｌｉ−Ｂａ等のリチウム合金を使用す
ることができる。Further, in the non-aqueous electrolyte battery according to the present invention, as the negative electrode material used for the negative electrode, in addition to metallic lithium as described above, a material capable of inserting and extracting lithium ions can be used. , Carbon materials such as graphite, coke, and calcined organic matter, Li-Al, Li-
In, Li-Sn, Li-Pb, Li-Bi, Li-G
a, Li-Sr, Li-Si, Li-Zn, Li-C
Lithium alloys such as d, Li-Ca and Li-Ba can be used.
【００１２】また、この発明における非水電解質電池に
おいて、その非水電解質としては、公知の非水電解液や
高分子固体電解質を使用することでき、非水電解液にお
ける溶媒としても公知のものを使用することができ、例
えば、プロピレンカーボネート、エチレンカーボネー
ト、γ−ブチロラクトン、ジメチルカーボネート、ジメ
チルスルホキシド、アセトニトリル、ブチレンカーボネ
ート、１，２−ジメトキシエタン、ジエチルカーボネー
ト等の有機溶媒を１種又は２種以上組み合わせて使用す
ることができ、またこの溶媒に溶解させる溶質として
も、公知のものを使用することができ、例えば、トリフ
ルオロメタンスルホン酸リチウムＬｉＣＦ3ＳＯ3 ，ヘ
キサフルオロリン酸リチウムＬｉＰＦ6 ，過塩素酸リチ
ウムＬｉＣｌＯ4 ，テトラフルオロホウ酸リチウムＬｉ
ＢＦ4 ，トリフルオロメタンスルホン酸イミドリチウム
ＬｉＮ（ＣＦ3 ＳＯ2 ）2 等のリチウム化合物を使用す
ることができる。Further, in the non-aqueous electrolyte battery of the present invention, a known non-aqueous electrolyte or polymer solid electrolyte can be used as the non-aqueous electrolyte, and a known solvent as the solvent in the non-aqueous electrolyte can be used. It is possible to use, for example, propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl carbonate, dimethylsulfoxide, acetonitrile, butylene carbonate, 1,2-dimethoxyethane, diethyl carbonate and the like organic solvent in combination of one kind or two or more kinds. Known solutes can be used as the solute to be dissolved in this solvent, and examples thereof include lithium trifluoromethanesulfonate LiCF 3 SO 3 , lithium hexafluorophosphate LiPF 6 , and perchloric acid. lithium LiClO 4, Te Rafuruorohou acid lithium (Li)
Lithium compounds such as BF 4 and trifluoromethanesulfonic acid imide lithium LiN (CF 3 SO 2 ) 2 can be used.
【００１３】また、高分子固体電解質を使用する場合に
も、この高分子固体電解質を構成する高分子に公知のも
のを用いることができ、特に、リチウムイオンに対する
イオン導電性の高い高分子を使用することが好ましく、
例えば、ポリエチレンオキサイド，ポリプロピレンオキ
サイド，ポリエチレンイミン等が好適に使用され、また
この高分子に対して上記の溶質と共に、上記の溶媒を加
えてゲル状にして使用することも可能である。Also, when a polymer solid electrolyte is used, a known polymer can be used as the polymer constituting the polymer solid electrolyte, and in particular, a polymer having a high ionic conductivity for lithium ions is used. Preferably
For example, polyethylene oxide, polypropylene oxide, polyethyleneimine and the like are preferably used, and it is also possible to add the above solvent to the polymer together with the above solvent to form a gel.
【００１４】[0014]
【実施例】以下、この発明に係る非水電解質電池につい
て実験例を挙げて具体的に説明すると共に、この発明の
実施例に係る非水電解質電池が充放電サイクル特性等の
点で優れていることを明らかにする。なお、この発明に
おける非水電解質電池は、下記に示したものに限定され
るものではなく、その要旨を変更しない範囲において適
宜変更して実施することができるものである。EXAMPLES The non-aqueous electrolyte battery according to the present invention will be specifically described below with reference to experimental examples, and the non-aqueous electrolyte battery according to the examples of the present invention is excellent in terms of charge / discharge cycle characteristics and the like. Make it clear. The non-aqueous electrolyte battery according to the present invention is not limited to the ones shown below, and can be implemented with appropriate modifications without departing from the scope of the invention.
【００１５】（実験例１〜１０）これらの実施例１〜１
０においては、下記のようにして作製した正極と負極を
用いると共に、下記のようにして調製した非水電解液を
用いて、図１に示すような直径が２４．０ｍｍ，厚さが
３．０ｍｍのコイン型になった非水電解質電池を得るよ
うにした。Experimental Examples 1 to 10 These Examples 1 to 1
No. 0, the positive electrode and the negative electrode produced as described below were used, and the nonaqueous electrolytic solution prepared as described below was used to obtain a diameter of 24.0 mm and a thickness of 3. A 0 mm coin type non-aqueous electrolyte battery was obtained.
【００１６】［正極の作製］正極を作製するにあたって
は、Ｌｉ2 ＣＯ3 とＭｎＯ2 とをモル比１：４の割合に
なるようにして乳鉢内で混合させた後、この混合物を乾
燥空気雰囲気下において７５０℃で２０時間熱処理し、
その後、これを石川式らいかい乳鉢中において粉砕し
て、ＬｉＭｎ2 Ｏ4 の粉末を作製した。一方、Ｌｉ2 Ｏ
とＣｏＯとをモル比６：１の割合で混合した後、これを
６００℃で熱処理してＬｉ6 ＣｏＯ4 を作製した。[Preparation of Positive Electrode] To prepare a positive electrode, Li 2 CO 3 and MnO 2 were mixed in a mortar at a molar ratio of 1: 4, and this mixture was dried in an atmosphere of dry air. Heat treated at 750 ° C for 20 hours under
Then, this was crushed in an Ishikawa type raid mortar to prepare a LiMn 2 O 4 powder. On the other hand, Li 2 O
And CoO were mixed at a molar ratio of 6: 1 and then heat-treated at 600 ° C. to prepare Li 6 CoO 4 .
【００１７】ここで、実験例１においては、正極材料と
して上記のＬｉＭｎ2 Ｏ4 の粉末だけを用いる一方、実
施例２〜１０においては、正極材料としてＬｉＭｎ2 Ｏ
4 の粉末に対して上記のＬｉ6 ＣｏＯ4 を下記の表１に
示す割合（ｍｏｌ％）で添加して混合させたものを使用
した。[0017] Here, in the experimental example 1, while using only the powder of the above LiMn 2 O 4 as a cathode material, in Examples 2 to 10 are, LiMn 2 O as a positive electrode material
The above-mentioned Li 6 CoO 4 was added to the powder of 4 at the ratio (mol%) shown in Table 1 below and mixed.
【００１８】そして、これらの正極材料と、導電剤であ
るアセチレンブラックと、結着剤であるポリフッ化ビニ
リデンとを重量比９０：６：４の割合で混合して各正極
合剤を調製し、各正極合剤を２トン／ｃｍ2 の圧力で加
圧して直径２０ｍｍの円板状に成型した後、これを２５
０℃で２時間熱処理して各正極を作製した。Then, these positive electrode materials, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder are mixed at a weight ratio of 90: 6: 4 to prepare each positive electrode mixture, After pressurizing each positive electrode mixture with a pressure of 2 ton / cm 2 to form a disk having a diameter of 20 mm,
Each positive electrode was manufactured by heat treatment at 0 ° C. for 2 hours.
【００１９】［負極の作製］負極を作製するにあたって
は、所定厚みの金属リチウムの圧延板を直径２０ｍｍの
円板状に打ち抜いて負極を作製した。[Production of Negative Electrode] In producing the negative electrode, a negative electrode was produced by punching out a rolled metal lithium plate having a predetermined thickness into a disk shape having a diameter of 20 mm.
【００２０】［非水電解液の調製］非水電解液を調製す
るにあたっては、プロピレンカーボネートと１，２−ジ
メトキシエタンとを１：１の体積比で混合させた混合溶
媒を用い、この混合溶媒に過塩素酸リチウムＬｉＣｌＯ
4 を１ｍｏｌ／ｌの割合で溶解させて非水電解液を調製
した。[Preparation of Non-Aqueous Electrolyte] In preparing the non-aqueous electrolyte, a mixed solvent prepared by mixing propylene carbonate and 1,2-dimethoxyethane at a volume ratio of 1: 1 was used. Lithium perchlorate LiClO
4 was dissolved at a ratio of 1 mol / l to prepare a non-aqueous electrolytic solution.
【００２１】［電池の作製］実験例１〜１０の各非水電
解質電池を作製するにあたっては、図１に示すように、
上記のようにして作製した各正極１と負極２との間にそ
れぞれポリプロピレン製の微多孔膜（ヘキストセラニー
ズ社製，セルガード）で構成されたセパレータ３を挟み
込み、このセパレータ３に上記の非水電解液を含浸させ
て、これらを正極缶４ａと負極缶４ｂとによって形成さ
れる電池ケース４内に収容させ、正極集電体５を介して
正極１を正極缶４ａに接続させる一方、負極集電体６を
介して負極２を負極缶４ｂに接続させ、この正極缶４ａ
と負極缶４ｂとをポリプロピレン製の絶縁性パッキン７
により電気的に絶縁させて、各非水電解質電池を作製し
た。そして、各非水電解質電池の内部で生じた化学エネ
ルギーを正極缶４ａと負極缶４ｂの両端子から電気エネ
ルギーとして外部へ取り出すようにした。[Production of Battery] In producing each of the nonaqueous electrolyte batteries of Experimental Examples 1 to 10, as shown in FIG.
A separator 3 composed of a polypropylene microporous film (Hoechst Celanese Co., Ltd., Celgard) is sandwiched between each of the positive electrode 1 and the negative electrode 2 produced as described above. The electrolytic solution is impregnated and housed in a battery case 4 formed by a positive electrode can 4a and a negative electrode can 4b, and the positive electrode 1 is connected to the positive electrode can 4a through a positive electrode current collector 5, while the negative electrode collector 4a is connected. The negative electrode 2 is connected to the negative electrode can 4b through the electric body 6, and the positive electrode can 4a
Insulating packing 7 made of polypropylene for the negative electrode can 4b
To electrically insulate each nonaqueous electrolyte battery. Then, the chemical energy generated inside each non-aqueous electrolyte battery was taken out as electric energy from both terminals of the positive electrode can 4a and the negative electrode can 4b.
【００２２】次に、上記の実験例１〜１０の各非水電解
質電池について、それぞれ充電電流密度３ｍＡで４．２
Ｖまで充電させた後、放電電流密度１０ｍＡで２．７５
Ｖまで放電させる工程を１サイクルとする充放電サイク
ル試験を行ない、１サイクル目における各非水電解質電
池の放電容量を測定すると共に、１５０サイクル目にお
ける各非水電解質電池の放電容量を測定し、１サイクル
目の放電容量に対する１５０サイクル目の放電容量の劣
化率を求め、その結果を下記の表１に合わせて示した。 劣化率＝100 ×(1サイクル目の放電容量−150サイクル 目の放電
容量）／1サイクル 目の放電容量Next, with respect to each of the non-aqueous electrolyte batteries of Experimental Examples 1 to 10 described above, 4.2 at a charging current density of 3 mA.
After charging to V, 2.75 at a discharge current density of 10 mA
A charging / discharging cycle test in which the step of discharging to V is one cycle is performed, and the discharge capacity of each non-aqueous electrolyte battery in the first cycle is measured, and the discharge capacity of each non-aqueous electrolyte battery in the 150th cycle is measured, The deterioration rate of the discharge capacity at the 150th cycle with respect to the discharge capacity at the first cycle was determined, and the results are also shown in Table 1 below. Deterioration rate = 100 x (Discharge capacity at 1st cycle-Discharge capacity at 150th cycle) / Discharge capacity at 1st cycle
【００２３】[0023]
【表１】 [Table 1]
【００２４】この結果から明らかなように、正極活物質
であるＬｉＭｎ2 Ｏ4 に対して、Ｌｉ6 ＣｏＯ4 を０．
１〜２０ｍｏｌ％の範囲で添加させた実験例３〜９の各
非水電解質電池は、その劣化率が２４％以下で、Ｌｉ6
ＣｏＯ4 を添加しなかった実験例１の非水電解質電池
や、Ｌｉ6 ＣｏＯ4 の添加量が０．０５ｍｏｌ％と非常
に少ない実験例２の非水電解質電池に比べて劣化率が低
くなって、サイクル特性が向上しており、また１サイク
ル目の放電容量も１３０ｍＡｈ以上であり、Ｌｉ6 Ｃｏ
Ｏ4 を２０ｍｏｌ％より多く添加した実験例１０の非水
電解質電池に比べて１サイクル目の放電容量が高く、放
電容量の低下が少なくなっており、特に、Ｌｉ6 ＣｏＯ
4 を０．５〜１０ｍｏｌ％の範囲で添加させた実験例５
〜７の各非水電解質電池においては、その劣化率が１５
％でかつ１サイクル目の放電容量が１５０ｍＡｈ以上に
なっており、放電容量の低下を少なくしてサイクル特性
を十分に向上させることができた。As is clear from this result, Li 6 CoO 4 was added to LiMn 2 O 4 as a positive electrode active material in an amount of 0.
Each of the nonaqueous electrolyte batteries of Experimental Examples 3 to 9 added in the range of 1 to 20 mol% had a deterioration rate of 24% or less, and Li 6
The deterioration rate was lower than that of the non-aqueous electrolyte battery of Experimental Example 1 in which CoO 4 was not added and the non-aqueous electrolyte battery of Experimental Example 2 in which the amount of Li 6 CoO 4 added was very small at 0.05 mol%. , has improved cycle characteristics and it is also 130mAh or more discharge capacity at the first cycle, Li 6 Co
Compared with the non-aqueous electrolyte battery of Experimental Example 10 in which O 4 was added in an amount of more than 20 mol%, the discharge capacity at the first cycle was high and the decrease in discharge capacity was small, and in particular Li 6 CoO
Experimental Example 5 in which 4 was added in the range of 0.5 to 10 mol%
In each of the nonaqueous electrolyte batteries No. 7 to No. 7, the deterioration rate is 15
%, And the discharge capacity in the first cycle was 150 mAh or more, and the decrease in discharge capacity was reduced and the cycle characteristics could be sufficiently improved.
【００２５】（実験例１１〜２０）これらの実験例１１
〜２０の各非水電解質電池においては、正極を作製する
にあたり、Ｌｉ2 ＣＯ3 とＦｅ2 Ｏ3 とをモル比１：１
の割合になるようにして乳鉢内で混合させた後、この混
合物を乾燥空気雰囲気下において８５０℃で２０時間熱
処理し、その後、これを石川式らいかい乳鉢中において
粉砕して、ＬｉＦｅＯ2 の粉末を作製した。(Experimental Examples 11 to 20) These Experimental Examples 11
In each of the non-aqueous electrolyte batteries No. 20 to No. 20, Li 2 CO 3 and Fe 2 O 3 were used in a molar ratio of 1: 1 when producing the positive electrode.
The mixture was heat-treated at 850 ° C. for 20 hours in a dry air atmosphere, and then crushed in an Ishikawa-type Raikai mortar to obtain LiFeO 2 powder. Was produced.
【００２６】そして、実験例１１においては、正極材料
として上記のＬｉＦｅＯ2 粉末だけを用いる一方、実験
例１２〜２０においては、正極材料としてこのＬｉＦｅ
Ｏ2粉末に対して前記のＬｉ6 ＣｏＯ4 を下記の表２に
示す割合（ｍｏｌ％）で添加して混合させたものを使用
し、それ以外については、上記の実験例１〜１０の場合
と同様にして各非水電解質電池を作製した。Then, in Experimental Example 11, only the above-mentioned LiFeO 2 powder was used as the positive electrode material, while in Experimental Examples 12 to 20, this LiFe was used as the positive electrode material.
The above-mentioned Li 6 CoO 4 was added to and mixed with O 2 powder at the ratio (mol%) shown in Table 2 below. Each non-aqueous electrolyte battery was produced in the same manner as in.
【００２７】次に、上記のようにして作製した実験例１
１〜２０の各非水電解質電池についても、前記の場合と
同様にして、１サイクル目における各非水電解質電池の
放電容量を測定すると共に、１５０サイクル目における
各非水電解質電池の放電容量を測定し、１サイクル目の
放電容量に対する１５０サイクル目の放電容量の劣化率
を求め、その結果を下記の表２に合わせて示した。Next, Experimental Example 1 produced as described above
For each of the nonaqueous electrolyte batteries 1 to 20, the discharge capacity of each nonaqueous electrolyte battery in the first cycle was measured and the discharge capacity of each nonaqueous electrolyte battery in the 150th cycle was measured in the same manner as described above. The deterioration rate of the discharge capacity at the 150th cycle relative to the discharge capacity at the first cycle was measured, and the results are shown in Table 2 below.
【００２８】[0028]
【表２】 [Table 2]
【００２９】この結果から明らかなように、正極活物質
にＬｉＦｅＯ2 を使用した場合においても、上記の実験
例１〜１０の場合と同様に、前記のＬｉ6 ＣｏＯ4 を
０．１〜２０ｍｏｌ％の範囲で添加させた実験例１３〜
１９の各非水電解質電池は、その劣化率が２４％以下
で、Ｌｉ6 ＣｏＯ4 を添加しなかった実験例１１の非水
電解質電池や、Ｌｉ6 ＣｏＯ4 の添加量が０．０５ｍｏ
ｌ％と非常に少ない実験例１２の非水電解質電池に比べ
て劣化率が低くなって、サイクル特性が向上しており、
また１サイクル目の放電容量も１３０ｍＡｈ以上で、Ｌ
ｉ6 ＣｏＯ4 を２０ｍｏｌ％より多く添加した実験例２
０の非水電解質電池に比べて１サイクル目の放電容量が
高く、放電容量の低下が少なくなっており、特にＬｉ6
ＣｏＯ4 を０．５〜１０ｍｏｌ％の範囲で添加させた実
験例１５〜１７の各非水電解質電池においては、その劣
化率が１５％でかつ１サイクル目の放電容量が１４０ｍ
Ａｈ以上になっており、放電容量の低下を少なくしてサ
イクル特性を十分に向上させることができた。As is clear from these results, even when LiFeO 2 was used as the positive electrode active material, the Li 6 CoO 4 content was 0.1 to 20 mol% as in Experimental Examples 1 to 10 above. Experimental example 13 added in the range of
Each of the non-aqueous electrolyte batteries of 19 had a deterioration rate of 24% or less, and the non-aqueous electrolyte battery of Experimental Example 11 in which Li 6 CoO 4 was not added or the addition amount of Li 6 CoO 4 was 0.05 mo.
The deterioration rate is lower than that of the non-aqueous electrolyte battery of Experimental Example 12 which is very small as 1%, and cycle characteristics are improved.
In addition, the discharge capacity of the first cycle is 130 mAh or more,
Experimental Example 2 in which i 6 CoO 4 was added in an amount of more than 20 mol%
High discharge capacity in the first cycle as compared to the non-aqueous electrolyte battery of 0, a decrease in the discharge capacity has become less, especially Li 6
In each of the non-aqueous electrolyte batteries of Experimental Examples 15 to 17 to which CoO 4 was added in the range of 0.5 to 10 mol%, the deterioration rate was 15% and the discharge capacity at the first cycle was 140 m.
Since it was Ah or more, the decrease in discharge capacity was reduced and the cycle characteristics could be sufficiently improved.
【００３０】（実験例２１〜３０）これらの実験例２１
〜３０の各非水電解質電池においては、正極を作製する
にあたり、ＬｉＯＨとＮｉ（ＯＨ）2 とＣｏ（ＯＨ）2
とをモル比２：１：１の割合で乳鉢内で混合させた後、
この混合物を乾燥空気雰囲気下において７５０℃で２０
時間熱処理し、その後、これを石川式らいかい乳鉢中に
おいて粉砕して、ＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 の粉末を作
製した。(Experimental Examples 21 to 30) These Experimental Examples 21
In each of the nonaqueous electrolyte batteries No. 30 to No. 30, LiOH, Ni (OH) 2 and Co (OH) 2 were used to prepare the positive electrode.
After mixing and in a mortar in a molar ratio of 2: 1: 1,
This mixture was heated at 750 ° C. under a dry air atmosphere for 20 minutes.
And time heat treatment, after which it was triturated in Ishikawa automated mortar mortar to prepare a LiNi 0. Of 5 Co 0. 5 O 2 powder.
【００３１】そして、実験例２１においては、正極材料
として上記のＬｉＮｉ0.5 Ｃｏ0.5Ｏ2 粉末だけを用い
る一方、実験例２２〜３０においては、正極材料として
このＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 粉末に対して前記のＬｉ
6 ＣｏＯ4 を下記の表３に示す割合（ｍｏｌ％）で添加
して混合させたものを使用し、それ以外については、上
記の各実験例の場合と同様にして各非水電解質電池を作
製した。[0031] In Experimental Example 21, while using only LiNi 0. 5 Co 0. 5 O 2 powder above as a positive electrode material, in the experimental examples 22 to 30, the LiNi 0 as a positive electrode material. 5 Co 0 . the relative 5 O 2 powder Li
6 CoO 4 was added and mixed at the ratio (mol%) shown in Table 3 below, and other than that, each non-aqueous electrolyte battery was prepared in the same manner as in the above-mentioned experimental examples. did.
【００３２】次に、上記のようにして作製した実験例２
１〜３０の各非水電解質電池についても、前記の場合と
同様にして、１サイクル目における各非水電解質電池の
放電容量を測定すると共に、１５０サイクル目における
各非水電解質電池の放電容量を測定し、１サイクル目の
放電容量に対する１５０サイクル目の放電容量の劣化率
を求め、その結果を下記の表３に合わせて示した。Next, Experimental Example 2 produced as described above
For each of the nonaqueous electrolyte batteries 1 to 30, the discharge capacity of each nonaqueous electrolyte battery in the first cycle was measured and the discharge capacity of each nonaqueous electrolyte battery in the 150th cycle was measured in the same manner as described above. The deterioration rate of the discharge capacity at the 150th cycle relative to the discharge capacity at the first cycle was measured, and the results are shown in Table 3 below.
【００３３】[0033]
【表３】 [Table 3]
【００３４】この結果から明らかなように、正極活物質
にＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 を使用した場合において
も、前記の各実験例の場合と同様に、上記のＬｉ6 Ｃｏ
Ｏ4 を０．１〜２０ｍｏｌ％の範囲で添加させた実験例
２３〜２９の各非水電解質電池は、その劣化率が１０％
以下で、Ｌｉ6 ＣｏＯ4 を添加しなかった実験例２１の
非水電解質電池や、Ｌｉ6 ＣｏＯ4 の添加量が０．０５
ｍｏｌ％と非常に少ない実験例２２の非水電解質電池に
比べて劣化率が著しく低くなって、サイクル特性が大き
く向上しており、また１サイクル目の放電容量も１４５
ｍＡｈ以上で、Ｌｉ6 ＣｏＯ4 を２０ｍｏｌ％より多く
添加した実験例３０の非水電解質電池に比べて、１サイ
クル目の放電容量がかなり高く、放電容量の低下もかな
り少なくなっていた。特に、Ｌｉ6 ＣｏＯ4 を０．５〜
１０ｍｏｌ％の範囲で添加させた実験例２５〜２７の各
非水電解質電池においては、その劣化率が３％でかつ１
サイクル目の放電容量が１６０ｍＡｈになっており、正
極材料にＬｉＭｎＯ4 やＬｉＦｅＯ2 を用いた前記の各
実験例のものに比べても、放電容量の低下が少なく、サ
イクル特性をさらに向上させることができた。As is apparent from this result, LiNi 0 in the positive electrode active material. 5 Co 0. 5 in the case of using O 2, as in the case of each of the experimental examples of the above-mentioned Li 6 Co
Each of the nonaqueous electrolyte batteries of Experimental Examples 23 to 29 to which O 4 was added in the range of 0.1 to 20 mol% had a deterioration rate of 10%.
In the following, the non-aqueous electrolyte battery of Experimental Example 21 in which Li 6 CoO 4 was not added and the addition amount of Li 6 CoO 4 was 0.05
Compared to the non-aqueous electrolyte battery of Experimental Example 22, which is extremely low at mol%, the deterioration rate is significantly lower, the cycle characteristics are greatly improved, and the discharge capacity at the first cycle is 145%.
Compared to the non-aqueous electrolyte battery of Experimental Example 30 in which Li 6 CoO 4 was added in an amount of mAh or more in an amount of more than 20 mol%, the discharge capacity at the first cycle was considerably high, and the decrease in discharge capacity was also considerably small. Particularly, Li 6 CoO 4 is 0.5 to
In each of the non-aqueous electrolyte batteries of Experimental Examples 25 to 27 added in the range of 10 mol%, the deterioration rate was 3% and 1
The discharge capacity at the cycle was 160 mAh, and the discharge capacity did not decrease much compared with the above-mentioned experimental examples using LiMnO 4 or LiFeO 2 as the positive electrode material, and the cycle characteristics could be further improved. did it.
【００３５】（実験例３１〜５６）これらの実験例３１
〜５６の各非水電解質電池においては、正極材料とし
て、ＬｉＮｉ0.5 Ｃｏ0.4 Ｍ0.1 Ｏ2 の構造式で示さ
れ、Ｍが下記の表４に示す元素になったものを用い、こ
れら正極材料としてそれぞれ前記のＬｉ6 ＣｏＯ4 を１
０ｍｏｌ％で添加して混合させたものを使用し、それ以
外については、上記の各実験例の場合と同様にして各非
水電解質電池を作製した。(Experimental Examples 31 to 56) These Experimental Examples 31
In each non-aqueous electrolyte battery to 56, as a positive electrode material, shown LiNi 0. 5 Co 0. 4 M 0. Of 1 O 2 in the structural formula, what M is turned elements shown in Table 4 below The above Li 6 CoO 4 is used as the positive electrode material.
Each non-aqueous electrolyte battery was produced in the same manner as in each of the experimental examples described above, except that the mixture added at 0 mol% and mixed was used.
【００３６】そして、上記のようにして作製した実験例
３１〜５６の各非水電解質電池についても、前記の場合
と同様にして、１サイクル目における各非水電解質電池
の放電容量を測定すると共に、１５０サイクル目におけ
る各非水電解質電池の放電容量を測定し、１サイクル目
の放電容量に対する１５０サイクル目の放電容量の劣化
率を求め、その結果を下記の表４に合わせて示した。Then, for each of the nonaqueous electrolyte batteries of Experimental Examples 31 to 56 produced as described above, the discharge capacity of each nonaqueous electrolyte battery in the first cycle was measured in the same manner as described above. The discharge capacity of each non-aqueous electrolyte battery at the 150th cycle was measured, and the deterioration rate of the discharge capacity at the 150th cycle relative to the discharge capacity at the 1st cycle was determined. The results are also shown in Table 4 below.
【００３７】[0037]
【表４】 [Table 4]
【００３８】この結果から明らかなように、ＬｉＮｉ0.
5 Ｃｏ0.4 Ｍ0.1 Ｏ2 で表わされ、Ｍが前記の表５に示
される元素からなる正極活物質を使用した場合において
も、正極活物質にＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 を用いた前
記の実験例２１〜３０の場合と略同様に、Ｌｉ6 ＣｏＯ
4 を１０ｍｏｌ％添加させた上記の各実験例の非水電解
質電池は、いずれもその劣化率が４％と低くなってお
り、また１サイクル目の放電容量も１４５ｍＡｈ以上と
高く、放電容量の低下が少なく、サイクル特性に優れた
非水電解質電池が得られた。As is clear from this result, LiNi 0 ..
5 Co 0. 4 M 0. 1 represented by O 2, in the case of using a positive electrode active material consisting of elements M are shown in Table 5 of the well, LiNi 0. 5 Co 0 in the positive electrode active material. 5 Almost the same as in the case of Experimental Examples 21 to 30 using O 2 , Li 6 CoO
In each of the above non-aqueous electrolyte batteries containing 10 mol% of 4 added thereto, the deterioration rate was low at 4%, and the discharge capacity at the first cycle was as high as 145 mAh or more, and the discharge capacity was lowered. And a non-aqueous electrolyte battery having excellent cycle characteristics was obtained.
【００３９】（実験例５７〜８３）これらの実験例５７
〜８３の各非水電解質電池においては、正極材料とし
て、ＬｉＦｅ0.9 Ｍ0.1 Ｏ2 の構造式で示され、Ｍが下
記の表５に示す元素になったものを用い、これら正極材
料としてそれぞれ前記のＬｉ6 ＣｏＯ4 を１０ｍｏｌ％
で添加して混合させたものを使用し、それ以外について
は、上記の各実験例の場合と同様にして各非水電解質電
池を作製した。(Experimental Examples 57 to 83) These Experimental Examples 57
In each non-aqueous electrolyte battery to 83, as a positive electrode material, LiFe 0. 9 M 0. Indicated by 1 O 2 of the structural formula, used as the M becomes an element shown in Table 5 below, positive electrode The above-mentioned Li 6 CoO 4 was used as a material in an amount of 10 mol%
Each non-aqueous electrolyte battery was produced in the same manner as in each of the above-described experimental examples, except that the mixture added and mixed in was used.
【００４０】そして、上記のようにして作製した実験例
５７〜８３の各非水電解質電池についても、前記の場合
と同様にして、１サイクル目における各非水電解質電池
の放電容量を測定すると共に、１５０サイクル目におけ
る各非水電解質電池の放電容量を測定し、１サイクル目
の放電容量に対する１５０サイクル目の放電容量の劣化
率を求め、その結果を下記の表５に合わせて示した。The discharge capacities of the non-aqueous electrolyte batteries in the first cycle were measured in the same manner as in the case of the non-aqueous electrolyte batteries of Experimental Examples 57 to 83 produced as described above. The discharge capacity of each non-aqueous electrolyte battery at the 150th cycle was measured, and the deterioration rate of the discharge capacity at the 150th cycle with respect to the discharge capacity at the 1st cycle was determined. The results are also shown in Table 5 below.
【００４１】[0041]
【表５】 [Table 5]
【００４２】この結果から明らかなように、ＬｉＦｅ0.
9 Ｍ0.1 Ｏ2 で表わされ、Ｍが前記の表５に示される元
素からなる正極活物質を使用した場合においても、正極
活物質にＬｉＦｅＯ2 を用いた前記の実験例１１〜２０
の場合と略同様に、Ｌｉ6 ＣｏＯ4 を１０ｍｏｌ％添加
させた上記の各実験例の非水電解質電池は、いずれも劣
化率が１５％と低くなっており、また１サイクル目の放
電容量も１３０ｍＡｈ以上と高くなり、放電容量の低下
が少なく、サイクル特性に優れた非水電解質電池が得ら
れた。As is clear from this result, LiFe 0 ..
9 M 0. 1 represented by O 2, in the case of using a positive electrode active material consisting of elements M are shown in Table 5 of the well, the experimental examples using the LiFeO 2 as the positive electrode active material 11 to 20
In the same manner as in the above case, the non-aqueous electrolyte batteries of each of the above-described experimental examples in which 10 mol% of Li 6 CoO 4 was added had a low deterioration rate of 15%, and the discharge capacity at the first cycle was also low. It was as high as 130 mAh or more, a decrease in discharge capacity was small, and a non-aqueous electrolyte battery excellent in cycle characteristics was obtained.
【００４３】（実験例８４〜１１０）これらの実験例８
４〜１１０の各非水電解質電池においては、正極材料と
して、ＬｉＭｎ1.8 Ｍ0.2 Ｏ4 の構造式で示され、Ｍが
下記の表６に示す元素になったものを用い、これら正極
材料としてそれぞれ前記のＬｉ6 ＣｏＯ4 を１０ｍｏｌ
％で添加して混合させたものを使用し、それ以外につい
ては、上記の各実験例の場合と同様にして各非水電解質
電池を作製した。(Experimental Examples 84 to 110) These Experimental Examples 8
In each non-aqueous electrolyte battery of 4-110, as a positive electrode material, indicated by LiMn 1. 8 M 0. The structural formula of 2 O 4, using what M is turned elements shown in Table 6 below, these 10 mol of each of the above Li 6 CoO 4 was used as a positive electrode material.
The non-aqueous electrolyte battery was produced in the same manner as in the above-mentioned experimental examples except that the mixture was added and mixed in%.
【００４４】そして、上記のようにして作製した実験例
８４〜１１０の各非水電解質電池についても、前記の場
合と同様にして、１サイクル目における各非水電解質電
池の放電容量を測定すると共に、１５０サイクル目にお
ける各非水電解質電池の放電容量を測定し、１サイクル
目の放電容量に対する１５０サイクル目の放電容量の劣
化率を求め、その結果を下記の表６に合わせて示した。The discharge capacities of the non-aqueous electrolyte batteries in the first cycle were measured in the same manner as in the case of the non-aqueous electrolyte batteries of Experimental Examples 84 to 110 produced as described above. The discharge capacity of each non-aqueous electrolyte battery at the 150th cycle was measured, and the deterioration rate of the discharge capacity at the 150th cycle relative to the discharge capacity at the 1st cycle was determined. The results are also shown in Table 6 below.
【００４５】[0045]
【表６】 [Table 6]
【００４６】この結果から明らかなように、ＬｉＭｎ1.
8 Ｍ0.2 Ｏ4 で表わされ、Ｍが前記の表６に示される元
素からなる正極活物質を使用した場合においても、正極
活物質にＬｉＭｎ2 Ｏ4 を用いた前記の実験例１〜１０
の場合と略同様に、Ｌｉ6 ＣｏＯ4 を１０ｍｏｌ％添加
させた上記の各実験例の非水電解質電池は、いずれも劣
化率が１５％と低くなっており、また１サイクル目の放
電容量も１５０ｍＡｈ以上と高くなり、放電容量の低下
が少なく、サイクル特性に優れた非水電解質電池が得ら
れた。As is clear from this result, LiMn 1 .
8 M 0. 2 O is represented by 4, in the case of using the positive electrode active material consisting of elements M are shown in Table 6 of the well, experimental examples of the using LiMn 2 O 4 as the positive electrode active material 1 -10
In the same manner as in the above case, the non-aqueous electrolyte batteries of each of the above-described experimental examples in which 10 mol% of Li 6 CoO 4 was added had a low deterioration rate of 15%, and the discharge capacity at the first cycle was also low. It was as high as 150 mAh or more, a decrease in discharge capacity was small, and a non-aqueous electrolyte battery excellent in cycle characteristics was obtained.
【００４７】[0047]
【発明の効果】以上詳述したように、この発明における
非水電解質電池においては、正極材料に使用するリチウ
ム遷移金属複合酸化物にＬｉ6 ＣｏＯ4 を添加させるよ
うにしたため、このＬｉ6 ＣｏＯ4 がリチウム遷移金属
複合酸化物の表面に付着し、これによりリチウム遷移金
属複合酸化物における触媒作用が弱くなって、非水電解
液等との接触による反応が抑制され、保存性やサイクル
特性に優れた非水電解質電池が得られるようになった。As described above in detail, in the non-aqueous electrolyte battery in the present invention, since so as to addition of Li 6 CoO 4 lithium transition metal composite oxide used in the positive electrode material, the Li 6 CoO 4 Adheres to the surface of the lithium-transition metal composite oxide, which weakens the catalytic action of the lithium-transition metal composite oxide and suppresses the reaction due to contact with a non-aqueous electrolyte solution, which is excellent in storage stability and cycle characteristics. A non-aqueous electrolyte battery is now available.
【図１】各実験例における非水電解質電池の内部構造を
示した断面説明図である。FIG. 1 is a cross-sectional explanatory view showing the internal structure of a non-aqueous electrolyte battery in each experimental example.
１ 正極 ２ 負極 1 Positive electrode 2 Negative electrode
フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内Front Page Continuation (72) Inventor Koji Nishio 2-5-5 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd.
Claims (3)
の吸蔵，放出が可能な材料を用いると共に、正極にリチ
ウムイオンの吸蔵，放出が可能なリチウム遷移金属複合
酸化物を用いた非水電解質電池において、上記の正極に
使用するリチウム遷移金属複合酸化物に対してＬｉ6 Ｃ
ｏＯ4 を添加させたことを特徴とする非水電解質電池。1. A non-aqueous electrolyte battery using a material capable of occluding and releasing metallic lithium or lithium ions for the negative electrode and a lithium transition metal composite oxide capable of occluding and releasing lithium ions for the positive electrode. Li 6 C is added to the lithium transition metal composite oxide used for the positive electrode.
A non-aqueous electrolyte battery containing oO 4 .
いて、上記の正極に使用するリチウム遷移金属複合酸化
物が、下記の構造式（１）〜（３）の何れかのリチウム
遷移金属複合酸化物で構成されていることを特徴とする
非水電解質電池。 Ｌｉx Ｎｉy Ｃｏz Ｍ1-y-z Ｏa （１） ［この構造式（１）中において、ＭはＢ，Ｎａ，Ｍｇ，
Ａｌ，Ｓｉ，Ｋ，Ｃａ，Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，
Ｆｅ，Ｃｕ，Ｚｎ，Ｇａ，Ｇｅ，Ｚｒ，Ｎｂ，Ｒｕ，Ａ
ｇ，Ｔａ，Ｂｉ，Ｉｎ，Ｍｏ，Ｗの中から選ばれる少な
くとも１種の元素であり、ｘ，ｙ，ｚ及びａは、０＜ｘ
＜１．３、０．５≦ｙ＋ｚ≦１、１．８≦ａ≦２．２で
あり、ｘは充放電によって変化する。］ Ｌｉx Ｆｅy Ｍ1-y Ｏa （２） ［この構造式（２）中において、ＭはＢ，Ｎａ，Ｍｇ，
Ａｌ，Ｓｉ，Ｋ，Ｃａ，Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，
Ｃｕ，Ｚｎ，Ｇａ，Ｇｅ，Ｚｒ，Ｎｂ，Ｒｕ，Ａｇ，Ｔ
ａ，Ｂｉ，Ｉｎ，Ｍｏ，Ｗ，Ｃｏ，Ｎｉの中から選ばれ
る少なくとも１種の元素であり、ｘ，ｙ及びａは、０＜
ｘ＜１．３、０．５≦ｙ≦１、１．８≦ａ≦２．２であ
り、ｘは充放電によって変化する。］ Ｌｉx Ｍｎy Ｍ2-y Ｏa （３） ［この構造式（３）中において、ＭはＢ，Ｎａ，Ｍｇ，
Ａｌ，Ｓｉ，Ｋ，Ｃａ，Ｓｃ，Ｖ，Ｃｒ，Ｆｅ，Ｔｉ，
Ｃｕ，Ｚｎ，Ｇａ，Ｇｅ，Ｚｒ，Ｎｂ，Ｒｕ，Ａｇ，Ｔ
ａ，Ｂｉ，Ｉｎ，Ｍｏ，Ｗ，Ｃｏ，Ｎｉの中から選ばれ
る少なくとも１種の元素であり、ｘ，ｙ及びａは、０＜
ｘ＜２．６、１≦ｙ≦２、３．６≦ａ≦４．４であり、
ｘは充放電によって変化する。］2. The non-aqueous electrolyte battery according to claim 1, wherein the lithium transition metal composite oxide used for the positive electrode is a lithium transition metal composite oxide represented by any one of the following structural formulas (1) to (3). A non-aqueous electrolyte battery comprising an oxide. Lix Niy Coz M1-yz Oa (1) [In the structural formula (1), M is B, Na, Mg,
Al, Si, K, Ca, Sc, Ti, V, Cr, Mn,
Fe, Cu, Zn, Ga, Ge, Zr, Nb, Ru, A
At least one element selected from g, Ta, Bi, In, Mo and W, and x, y, z and a are 0 <x.
<1.3, 0.5 ≦ y + z ≦ 1, 1.8 ≦ a ≦ 2.2, and x changes depending on charge and discharge. ] Lix Fey M1-y Oa (2) [In this structural formula (2), M is B, Na, Mg,
Al, Si, K, Ca, Sc, Ti, V, Cr, Mn,
Cu, Zn, Ga, Ge, Zr, Nb, Ru, Ag, T
at least one element selected from a, Bi, In, Mo, W, Co and Ni, and x, y and a are 0 <
x <1.3, 0.5 ≦ y ≦ 1, 1.8 ≦ a ≦ 2.2, and x changes due to charge / discharge. Lix Mny M2-y Oa (3) [In the structural formula (3), M is B, Na, Mg,
Al, Si, K, Ca, Sc, V, Cr, Fe, Ti,
Cu, Zn, Ga, Ge, Zr, Nb, Ru, Ag, T
at least one element selected from a, Bi, In, Mo, W, Co and Ni, and x, y and a are 0 <
x <2.6, 1 ≦ y ≦ 2, 3.6 ≦ a ≦ 4.4,
x changes with charge and discharge. ]
解質電池において、上記の正極に使用するリチウム遷移
金属複合酸化物に対して、Ｌｉ6 ＣｏＯ4 を０．１〜２
０モル％の範囲で添加させたことを特徴とする非水電解
質電池。 【０００１】3. The non-aqueous electrolyte battery according to claim 1 or 2, wherein 0.1 to 2 of Li 6 CoO 4 is added to the lithium transition metal composite oxide used for the positive electrode.
A non-aqueous electrolyte battery which is added in an amount of 0 mol%. [0001]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7329511A JPH09147863A (en) | 1995-11-24 | 1995-11-24 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7329511A JPH09147863A (en) | 1995-11-24 | 1995-11-24 | Nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09147863A true JPH09147863A (en) | 1997-06-06 |
Family
ID=18222199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7329511A Pending JPH09147863A (en) | 1995-11-24 | 1995-11-24 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09147863A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000113884A (en) * | 1998-10-01 | 2000-04-21 | Ngk Insulators Ltd | Lithium secondary battery |
| EP1069075A1 (en) * | 1999-07-14 | 2001-01-17 | NBT GmbH | Method for producing lithium spinell |
| JP2001345102A (en) * | 2000-03-30 | 2001-12-14 | Sony Corp | Secondary battery |
| JP2002507313A (en) * | 1997-06-27 | 2002-03-05 | エルジー・ケミカル・リミテッド | Lithium ion secondary battery and method of manufacturing the same |
| US6670076B1 (en) * | 1997-06-19 | 2003-12-30 | Tosoh Corporation | Spinel-type lithium-manganese oxide containing heteroelements preparation process and use thereof |
| KR100681465B1 (en) * | 2004-07-30 | 2007-02-09 | 주식회사 엘지화학 | Electrode active material with high capacity and good cycleability and lithium secondary cell comprising the same |
| WO2015011884A1 (en) * | 2013-07-25 | 2015-01-29 | 株式会社豊田自動織機 | Positive electrode for non-aqueous secondary battery, and non-aqueous secondary battery |
| US20150372304A1 (en) * | 2013-01-31 | 2015-12-24 | Sanyo Electric Co., Ltd. | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| JP2016091633A (en) * | 2014-10-30 | 2016-05-23 | 住友金属鉱山株式会社 | Substituent element select method, battery positive electrode material manufacturing method, and battery positive electrode material |
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-
1995
- 1995-11-24 JP JP7329511A patent/JPH09147863A/en active Pending
Cited By (14)
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|---|---|---|---|---|
| US6670076B1 (en) * | 1997-06-19 | 2003-12-30 | Tosoh Corporation | Spinel-type lithium-manganese oxide containing heteroelements preparation process and use thereof |
| JP2002507313A (en) * | 1997-06-27 | 2002-03-05 | エルジー・ケミカル・リミテッド | Lithium ion secondary battery and method of manufacturing the same |
| JP2000113884A (en) * | 1998-10-01 | 2000-04-21 | Ngk Insulators Ltd | Lithium secondary battery |
| EP1069075A1 (en) * | 1999-07-14 | 2001-01-17 | NBT GmbH | Method for producing lithium spinell |
| JP2001345102A (en) * | 2000-03-30 | 2001-12-14 | Sony Corp | Secondary battery |
| KR100681465B1 (en) * | 2004-07-30 | 2007-02-09 | 주식회사 엘지화학 | Electrode active material with high capacity and good cycleability and lithium secondary cell comprising the same |
| US20150372304A1 (en) * | 2013-01-31 | 2015-12-24 | Sanyo Electric Co., Ltd. | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| US9692043B2 (en) | 2013-03-27 | 2017-06-27 | Tokyo University Of Science Educational Foundation Administrative Organization | Active material for nonaqueous electrolyte energy storage device |
| WO2015011884A1 (en) * | 2013-07-25 | 2015-01-29 | 株式会社豊田自動織機 | Positive electrode for non-aqueous secondary battery, and non-aqueous secondary battery |
| JP2016091633A (en) * | 2014-10-30 | 2016-05-23 | 住友金属鉱山株式会社 | Substituent element select method, battery positive electrode material manufacturing method, and battery positive electrode material |
| KR20190064424A (en) * | 2017-11-30 | 2019-06-10 | 주식회사 엘지화학 | Additives for cathode, manufacturing method of the same, cathode including the same, and lithium recharegable battery including the same |
| US10403929B2 (en) | 2017-11-30 | 2019-09-03 | Lg Chem, Ltd. | Additive for cathode, method for preparing the same, cathode including the same, and lithium secondary battery including the same |
| JP2022510983A (en) * | 2018-11-30 | 2022-01-28 | ポスコ | Positive electrode additive for lithium secondary battery, its manufacturing method, positive electrode for lithium secondary battery including it and lithium secondary battery containing it |
| WO2022255665A1 (en) * | 2021-05-31 | 2022-12-08 | 주식회사 엘지에너지솔루션 | Master batch comprising positive electrode active material and irreversible additive, and positive electrode slurry, for lithium secondary battery, containing same |
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