JP3172388B2 - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP3172388B2 JP3172388B2 JP06497595A JP6497595A JP3172388B2 JP 3172388 B2 JP3172388 B2 JP 3172388B2 JP 06497595 A JP06497595 A JP 06497595A JP 6497595 A JP6497595 A JP 6497595A JP 3172388 B2 JP3172388 B2 JP 3172388B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium
- secondary battery
- lithium secondary
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム−遷移金属複
合酸化物を正極活物質とするリチウム二次電池に係わ
り、詳しくは充放電サイクル特性を改善することを目的
とした、正極の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery using a lithium-transition metal composite oxide as a positive electrode active material, and more particularly to an improvement of a positive electrode for the purpose of improving charge / discharge cycle characteristics. .
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
リチウム二次電池が、水の分解電圧を考慮する必要がな
く、正極活物質を適宜選定することにより高電圧化を達
成することが可能であることから、注目されつつある。2. Description of the Related Art In recent years,
Lithium secondary batteries are attracting attention because they do not need to consider the decomposition voltage of water and can achieve higher voltages by appropriately selecting a positive electrode active material.
【０００３】この種の電池の代表的な正極活物質として
は、容易に作製することができるとともに、容量が大き
いことから、ＬｉＶ3 Ｏ8 、ＬｉＦｅＯ2 、ＬｉＮｉＯ
2 、ＬｉＣｏＯ2 、ＬｉＭｎＯ2 、ＬｉＭｎ2 Ｏ4 など
のリチウム−遷移金属複合酸化物が主に使用されてい
る。As a typical positive electrode active material of this type of battery, LiV 3 O 8 , LiFeO 2 , and LiNiO 2 can be easily produced and have a large capacity.
2, lithium such as LiCoO 2, LiMnO 2, LiMn 2 O 4 - transition metal composite oxide is mainly used.
【０００４】しかしながら、リチウム−遷移金属複合酸
化物を正極活物質として使用したリチウム二次電池に
は、充放電サイクル特性が未だ実用上充分満足の行く程
度のものではないという問題がある。これは、リチウム
−遷移金属複合酸化物を正極活物質とする正極は表面の
活性が高いために、正極表面で電解液（非水電解液）が
分解することによるものである。However, a lithium secondary battery using a lithium-transition metal composite oxide as a positive electrode active material has a problem that the charge / discharge cycle characteristics are still not sufficiently satisfactory for practical use. This is due to the fact that a positive electrode using a lithium-transition metal composite oxide as a positive electrode active material has high surface activity, so that an electrolytic solution (non-aqueous electrolytic solution) is decomposed on the positive electrode surface.
【０００５】本発明は、この問題を解決するべくなされ
たものであって、その目的とするところは、正極表面で
の電解液の分解を抑制することにより、充放電サイクル
特性に優れたリチウム二次電池を提供するにある。The present invention has been made to solve this problem. It is an object of the present invention to suppress the decomposition of an electrolytic solution on the surface of a positive electrode, thereby achieving a lithium secondary battery having excellent charge-discharge cycle characteristics. Next is to provide batteries.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明に係るリチウム二次電池（本発明電池）は、リ
チウム−遷移金属複合酸化物を活物質とする正極を備え
るリチウム二次電池であって、前記正極の表面に、Ｂｅ
Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ａｌ2
Ｏ3 、ＣｅＯ2 、Ａｓ2 Ｏ3 又はこれらの２種以上の混
合物からなる被膜が形成されていることを特徴とする。According to the present invention, there is provided a lithium secondary battery having a positive electrode containing a lithium-transition metal composite oxide as an active material. And Be on the surface of the positive electrode
O, MgO, CaO, SrO, BaO, ZnO, Al 2
It is characterized in that a film made of O 3 , CeO 2 , As 2 O 3 or a mixture of two or more thereof is formed.
【０００７】上記リチウム−遷移金属複合酸化物として
は、ＬｉＶ3 Ｏ8 、ＬｉＦｅＯ2 、ＬｉＮｉＯ2 、Ｌｉ
ＣｏＯ2 、ＬｉＭｎＯ2 、ＬｉＭｎ2 Ｏ4 が例示され
る。充放電サイクル特性に特に優れた電池を得る上で、
一般式ＬｉX Ｎｉ1-y Ｃｏy Ｏz （但し、０＜ｘ＜１．
３、０≦ｙ≦１、１．８＜ｚ＜２．２）で表されるリチ
ウム−遷移金属複合酸化物が特に好ましい。The lithium-transition metal composite oxides include LiV 3 O 8 , LiFeO 2 , LiNiO 2 and Li
CoO 2 , LiMnO 2 , and LiMn 2 O 4 are exemplified. In order to obtain a battery with excellent charge / discharge cycle characteristics,
General formula Li X Ni 1-y Co y O z (where 0 <x <1.
A lithium-transition metal composite oxide represented by 3, 0 ≦ y ≦ 1, 1.8 <z <2.2) is particularly preferable.
【０００８】上記被膜としては、充放電サイクル特性に
特に優れた電池を得る上で、ＢｅＯ、ＭｇＯ、ＣａＯ、
ＳｒＯ、ＢａＯ、ＺｎＯ又はこれらの２種以上の混合物
からなる被膜が特に好ましい。In order to obtain a battery having particularly excellent charge / discharge cycle characteristics, BeO, MgO, CaO,
A coating composed of SrO, BaO, ZnO or a mixture of two or more thereof is particularly preferred.
【０００９】上記被膜を形成するための方法としては、
ＣＶＤ（Chemical Vapor Deposition)、蒸着法、スパッ
タリングが例示される。As a method for forming the above-mentioned coating,
Examples include CVD (Chemical Vapor Deposition), a vapor deposition method, and sputtering.
【００１０】本発明の特徴は、リチウム−遷移金属複合
酸化物を活物質とする正極の表面に特定の被膜を形成し
た点にある。それゆえ、負極材料、非水電解液など、電
池を構成する他の部材については、従来リチウム二次電
池用として提案され、或いは実用されている種々の材料
を特に制限なく用いることが可能である。A feature of the present invention is that a specific coating is formed on the surface of a positive electrode using a lithium-transition metal composite oxide as an active material. Therefore, as for the other members constituting the battery, such as the negative electrode material and the non-aqueous electrolyte, it is possible to use various materials that have been conventionally proposed or practically used for lithium secondary batteries without any particular limitation. .
【００１１】例えば、負極材料としては、リチウムイオ
ンを電気化学的に吸蔵及び放出することが可能な物質又
は金属リチウムを使用することができる。リチウムイオ
ンを電気化学的に吸蔵及び放出することが可能な物質と
しては、黒鉛、コークス、有機物焼成体等の炭素材料及
びリチウム合金（リチウム−アルミニウム合金、リチウ
ム−鉛合金、リチウム−錫合金）が例示される。For example, as the negative electrode material, a substance capable of electrochemically storing and releasing lithium ions or metallic lithium can be used. Examples of the substance capable of electrochemically storing and releasing lithium ions include carbon materials such as graphite, coke, and fired organic materials, and lithium alloys (lithium-aluminum alloy, lithium-lead alloy, lithium-tin alloy). Is exemplified.
【００１２】また、非水電解液の溶媒としては、エチレ
ンカーボネート、ビニレンカーボネート、プロピレンカ
ーボネートなどの高誘電率溶媒や、これらとジエチルカ
ーボネート、ジメチルカーボネート、１，２−ジメトキ
シエタン、１，２−ジエトキシエタン、エトキシメトキ
シエタンなどの低沸点溶媒との混合溶媒が、同溶質とし
ては、ＬｉＰＦ6 、ＬｉＣｌＯ4 、ＬｉＣＦ3 ＳＯ3 、
ＬｉＮ（ＣＦ3 ＳＯ2）2 、ＬｉＢＦ4 、ＬｉＡｓＦ6
が、それぞれ例示される。Examples of the solvent for the non-aqueous electrolyte include high dielectric constant solvents such as ethylene carbonate, vinylene carbonate and propylene carbonate, and solvents such as diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane and 1,2-diethyl carbonate. A mixed solvent with a low-boiling solvent such as ethoxyethane or ethoxymethoxyethane may be used as the solute, such as LiPF 6 , LiClO 4 , LiCF 3 SO 3 ,
LiN (CF 3 SO 2 ) 2 , LiBF 4 , LiAsF 6
Are respectively exemplified.
【００１３】[0013]
【作用】正極の表面に特定の金属酸化物からなる被膜が
形成されているので、リチウム−遷移金属複合酸化物と
電解液との反応が起こりにくくなり、正極の表面での電
解液の分解が抑制される。Since a coating made of a specific metal oxide is formed on the surface of the positive electrode, the reaction between the lithium-transition metal composite oxide and the electrolyte does not easily occur, and the decomposition of the electrolyte on the surface of the positive electrode is prevented. Is suppressed.
【００１４】[0014]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
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可能なものである。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention may be practiced by appropriately changing the gist of the invention. Is possible.
【００１５】（実施例１〜１０） 〔正極〕ＬｉＯＨとＮｉ（ＯＨ）2 Ｃｏ（ＯＨ）2 とを
モル比２：１：１で乳鉢にて混合し、乾燥空気雰囲気下
にて７５０°Ｃで２０時間熱処理し、石川式らいかい乳
鉢にて粉砕して、平均粒径５μｍのＬｉＮｉ0.5 Ｃｏ
0.5 Ｏ2 を得た。(Examples 1 to 10) [Positive electrode] LiOH and Ni (OH) 2 Co (OH) 2 were mixed in a mortar at a molar ratio of 2: 1: 1 and dried at 750 ° C. in an atmosphere of dry air. And crushed in a mortar with Ishikawa-type raisin to obtain LiNi 0.5 Co with an average particle size of 5 μm.
0.5 O 2 was obtained.
【００１６】次いで、この正極活物質としてのＬｉＮｉ
0.5 Ｃｏ0.5 Ｏ2 と、導電剤としてのアセチレンブラッ
クと、結着剤としてのポリフッ化ビニリデンとを、重量
比９０：６：４で混合して正極合剤を調製し、この正極
合剤を２トン／ｃｍ2 の成型圧で直径２０ｍｍの円盤状
に加圧成型した後、２５０°Ｃで２時間熱処理して正極
（Ａ）を作製した（実施例１〜９）。Next, LiNi as the positive electrode active material is used.
0.5 Co 0.5 O 2 , acetylene black as a conductive agent, and polyvinylidene fluoride as a binder were mixed at a weight ratio of 90: 6: 4 to prepare a positive electrode mixture. After press-molding into a disc having a diameter of 20 mm with a molding pressure of ton / cm 2 , heat treatment was performed at 250 ° C. for 2 hours to produce positive electrodes (A) (Examples 1 to 9).
【００１７】また、正極活物質としてＬｉＭｎ2 Ｏ4 を
使用したこと以外は上記と同様にして、正極（Ｂ）を作
製した（実施例１０）。A positive electrode (B) was produced in the same manner as described above except that LiMn 2 O 4 was used as the positive electrode active material (Example 10).
【００１８】次いで、下記の条件のスパッタリングを行
って、上記正極（Ａ）又は（Ｂ）の表面に、表１に示す
種々の金属酸化物からなる厚さ約１μｍの被膜を形成し
た。なお、被膜の厚み（金属酸化物の担持量）はスパッ
タリング時間で制御した。Then, sputtering was carried out under the following conditions to form a coating of about 1 μm thick made of various metal oxides shown in Table 1 on the surface of the positive electrode (A) or (B). The thickness of the coating (the amount of the metal oxide carried) was controlled by the sputtering time.
【００１９】（スパッタリングの条件） 真空度：１×１０-7トール(torr) アルゴン（Ａｒ）圧：１×１０-5トール(Conditions of sputtering) Degree of vacuum: 1 × 10 −7 Torr (torr) Argon (Ar) pressure: 1 × 10 −5 Torr
【００２０】[0020]
【表１】 [Table 1]
【００２１】〔負極〕所定の厚みの金属リチウム圧延板
を直径２０ｍｍの円盤状に打ち抜いて負極を作製した。[Negative Electrode] A rolled metal lithium plate having a predetermined thickness was punched into a disc having a diameter of 20 mm to produce a negative electrode.
【００２２】〔非水電解液〕エチレンカーボネートとジ
エチルカーボネートとの体積比１：１の混合溶媒に、六
フッ化リン酸リチウムを１Ｍ（モル／リットル）溶かし
て非水電解液を調製した。[Non-Aqueous Electrolyte] A non-aqueous electrolyte was prepared by dissolving 1 M (mole / liter) of lithium hexafluorophosphate in a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1.
【００２３】〔電池の組立〕以上の正負極及び非水電解
液を用いて扁平形の本発明電池ＢＡ１〜ＢＡ１０を組み
立てた（電池寸法：直径２４．０ｍｍ、厚さ３．０ｍ
ｍ）。なお、セパレータとしては、ポリプロピレン製の
微多孔膜を使用し、これに先の非水電解液を含浸させ
た。[Assembly of Batteries] Using the positive and negative electrodes and the non-aqueous electrolyte described above, flat batteries BA1 to BA10 of the present invention were assembled (battery dimensions: diameter 24.0 mm, thickness 3.0 m).
m). As a separator, a microporous film made of polypropylene was used, and this was impregnated with the nonaqueous electrolyte.
【００２４】図１は、作製した本発明電池を模式的に示
す断面図であり、図示の本発明電池Ａは、正極（正極
（Ａ）又は（Ｂ）の表面に特定の金属酸化物からなる被
膜を形成したもの。）１、負極２、これら両電極１，２
を互いに離間するセパレータ３、正極缶４、負極缶５、
正極集電体６、負極集電体７及びポリプロピレン製の絶
縁パッキング８などからなる。FIG. 1 is a cross-sectional view schematically showing a manufactured battery of the present invention. The illustrated battery A of the present invention comprises a positive electrode (positive electrode (A) or (B) formed of a specific metal oxide on the surface thereof). 1, a negative electrode 2, both electrodes 1, 2
, A positive electrode can 4, a negative electrode can 5,
It comprises a positive electrode current collector 6, a negative electrode current collector 7, an insulating packing 8 made of polypropylene, and the like.
【００２５】正極１及び負極２は、非水電解液を含浸し
たセパレータ３を介して対向して正負極缶４，５が形成
する電池ケース内に収納されており、正極１は正極集電
体６を介して正極缶４に、又負極２は負極集電体７を介
して負極缶５に接続され、電池内部に生じた化学エネル
ギーを正極缶４及び負極缶５の両端子から電気エネルギ
ーとして外部へ取り出し得るようになっている。The positive electrode 1 and the negative electrode 2 are housed in a battery case formed with positive and negative electrode cans 4 and 5 facing each other via a separator 3 impregnated with a non-aqueous electrolyte. 6 and the negative electrode 2 is connected to the negative electrode can 5 via the negative electrode current collector 7, and the chemical energy generated inside the battery is converted into electric energy from both terminals of the positive electrode can 4 and the negative electrode can 5. It can be taken out.
【００２６】（比較例１，２）正極の表面に被膜を形成
しなかったこと以外は実施例１〜１０と同様にして、比
較電池ＢＣ１，ＢＣ２を組み立てた。但し、比較電池Ｂ
Ｃ１は、正極（Ａ）を使用したものであり、比較電池Ｂ
Ｃ２は正極（Ｂ）を使用したものである。Comparative Examples 1 and 2 Comparative batteries BC1 and BC2 were assembled in the same manner as in Examples 1 to 10, except that no coating was formed on the surface of the positive electrode. However, comparative battery B
C1 uses the positive electrode (A) and the comparative battery B
C2 uses the positive electrode (B).
【００２７】〔充放電サイクル特性〕本発明電池ＢＡ１
〜ＢＡ１０及び比較電池ＢＣ１，２について、電流密度
１ｍＡ／ｃｍ2 で４．３Ｖまで充電した後、電流密度３
ｍＡ／ｃｍ2 で２．５Ｖまで放電する工程を１サイクル
とする充放電サイクル試験を行い、充放電サイクル特性
を調べた。各電池の１サイクル目の放電容量、４００サ
イクル目の放電容量及び容量維持率〔容量維持率（％）
＝（４００サイクル目の放電容量／１サイクル目の放電
容量）×１００〕を先の表１に示す。[Charge / Discharge Cycle Characteristics] Battery BA1 of the present invention
-BA10 and comparative batteries BC1 and BC2 were charged to 4.3 V at a current density of 1 mA / cm 2 and then charged at a current density of 3 mA.
A charge / discharge cycle test was performed in which a step of discharging to 2.5 V at mA / cm 2 was defined as one cycle, and charge / discharge cycle characteristics were examined. Discharge capacity at 1st cycle, discharge capacity at 400th cycle and capacity retention rate of each battery [Capacity maintenance rate (%)
= (Discharge capacity at 400th cycle / discharge capacity at 1st cycle) × 100] is shown in Table 1 above.
【００２８】表１に示すように、正極表面に特定の被膜
を形成した本発明電池ＢＡ１〜ＢＡ１０は、正極表面に
被膜を形成しなかった比較電池ＢＣ１，ＢＣ２に比べ
て、容量維持率が大きい。特に、正極が同じ本発明電池
ＢＡ１〜ＢＡ９のうちＢＡ４〜ＢＡ９の容量維持率が特
に大きい。このことから、被膜形成材料としてはＢｅ
Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ又はＺｎＯが特に
好ましいことが分かる。また、本発明電池ＢＡ９と本発
明電池ＢＡ１０との比較から、正極活物質としては、Ｌ
ｉＭｎ2 Ｏ4 よりもＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 に代表さ
れる式ＬｉX Ｎｉ1-y Ｃｏy Ｏz （但し、０＜ｘ＜１．
３、０≦ｙ≦１、１．８＜ｚ＜２．２）で表されるリチ
ウム−遷移金属複合酸化物を使用することが好ましいこ
とが分かる。As shown in Table 1, the batteries BA1 to BA10 of the present invention in which a specific coating was formed on the positive electrode surface had a larger capacity retention ratio than the comparative batteries BC1 and BC2 in which no coating was formed on the positive electrode surface. . In particular, among the batteries BA1 to BA9 of the present invention having the same positive electrode, the capacity retention ratio of BA4 to BA9 is particularly large. Therefore, Be is used as a film forming material.
It can be seen that O, MgO, CaO, SrO, BaO or ZnO are particularly preferred. From the comparison between the battery BA9 of the present invention and the battery BA10 of the present invention, the positive electrode active material was L
Formula Li X Ni 1-y Co y O z represented by LiNi 0.5 Co 0.5 O 2 rather than iMn 2 O 4 (where 0 <x <1.
It can be seen that it is preferable to use a lithium-transition metal composite oxide represented by 3, 0 ≦ y ≦ 1, 1.8 <z <2.2).
【００２９】上記実施例では、リチウム−遷移金属複合
酸化物としてＬｉＮｉ0.5 Ｃｏ0.5Ｏ2 又はＬｉＭｎ2
Ｏ4 を使用したが、本発明は、種々のリチウム−遷移金
属複合酸化物を正極活物質とするリチウム二次電池に適
用し得るものである。In the above embodiment, LiNi 0.5 Co 0.5 O 2 or LiMn 2 was used as the lithium-transition metal composite oxide.
While using O 4, the present invention provides a variety of lithium - it is capable of applying a transition metal complex oxide in the lithium secondary battery positive electrode active material.
【００３０】また、上記実施例では、本発明を扁平形の
リチウム二次電池に適用する場合を例に挙げて説明した
が、本発明電池の形状に特に制限はない。In the above embodiment, the case where the present invention is applied to a flat lithium secondary battery has been described as an example. However, the shape of the battery of the present invention is not particularly limited.
【００３１】[0031]
【発明の効果】本発明電池は、充電時に正極の表面で非
水電解液の分解が起こりにくいので、充放電サイクル特
性に優れる。The battery of the present invention is excellent in charge-discharge cycle characteristics because the non-aqueous electrolyte does not easily decompose on the surface of the positive electrode during charging.
【図１】実施例で組み立てた扁平形のリチウム二次電池
の断面図である。FIG. 1 is a cross-sectional view of a flat lithium secondary battery assembled in an example.
１ 正極 ２ 負極 ３ セパレータ 1 positive electrode 2 negative electrode 3 separator
───────────────────────────────────────────────────── 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 (72)発明者 斎藤 俊彦 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 (56)参考文献 特開 昭61−7577（ＪＰ，Ａ) 特開 平６−150928（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/02 H01M 10/40 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Nishio, Inventor 2-5-5, Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Toshihiko Saito 2-5-2, Keihanhondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd. (56) References JP-A-61-7577 (JP, A) JP-A-6-150928 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/02 H01M 10/40
Claims (3)
する正極を備えるリチウム二次電池において、前記正極
の表面に、ＢｅＯ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、
ＺｎＯ、Ａｌ2 Ｏ3 、ＣｅＯ2 、Ａｓ2 Ｏ3 又はこれら
の２種以上の混合物からなる被膜が形成されていること
を特徴とするリチウム二次電池。1. A lithium secondary battery comprising a positive electrode comprising a lithium-transition metal composite oxide as an active material, wherein BeO, MgO, CaO, SrO, BaO,
A lithium secondary battery having a coating formed of ZnO, Al 2 O 3 , CeO 2 , As 2 O 3 or a mixture of two or more thereof.
する正極を備えるリチウム二次電池において、前記正極
の表面に、ＢｅＯ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、
ＺｎＯ又はこれらの２種以上の混合物からなる被膜が形
成されていることを特徴とするリチウム二次電池。2. A lithium secondary battery provided with a positive electrode using a lithium-transition metal composite oxide as an active material, wherein BeO, MgO, CaO, SrO, BaO,
A lithium secondary battery, wherein a coating made of ZnO or a mixture of two or more thereof is formed.
ＬｉX Ｎｉ1-y Ｃｏy Ｏz （但し、０＜ｘ＜１．３、０
≦ｙ≦１、１．８＜ｚ＜２．２）で表されるものである
請求項１又は２記載のリチウム二次電池。3. The lithium-transition metal composite oxide has the formula Li x Ni 1 -y Co y O z (where 0 <x <1.3, 0
3. The lithium secondary battery according to claim 1, which is represented by ≦ y ≦ 1, 1.8 <z <2.2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06497595A JP3172388B2 (en) | 1995-02-27 | 1995-02-27 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06497595A JP3172388B2 (en) | 1995-02-27 | 1995-02-27 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08236114A JPH08236114A (en) | 1996-09-13 |
| JP3172388B2 true JP3172388B2 (en) | 2001-06-04 |
Family
ID=13273567
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06497595A Expired - Fee Related JP3172388B2 (en) | 1995-02-27 | 1995-02-27 | Lithium secondary battery |
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| Country | Link |
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| JP (1) | JP3172388B2 (en) |
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