JP3258841B2 - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP3258841B2 JP3258841B2 JP33424994A JP33424994A JP3258841B2 JP 3258841 B2 JP3258841 B2 JP 3258841B2 JP 33424994 A JP33424994 A JP 33424994A JP 33424994 A JP33424994 A JP 33424994A JP 3258841 B2 JP3258841 B2 JP 3258841B2
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- lithium secondary
- positive electrode
- present
- mno
- 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
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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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム二次電池に係
わり、詳しくはＬｉＭＯ2 （但し、ＭはＣｏ及びＮｉの
少なくとも一種）を正極活物質とするリチウム二次電池
の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, and more particularly to a charge / discharge cycle characteristic of a lithium secondary battery using LiMO 2 (where M is at least one of Co and Ni) as a positive electrode active material. The present invention relates to improvement of a positive electrode for the purpose of improvement.
【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
いことから、正極活物質を適宜選定することにより高電
圧化が可能である、エネルギー密度が高いなどの利点を
有することから、次世代の二次電池として、注目されて
いる。2. Description of the Related Art In recent years,
Since the lithium secondary battery does not need to consider the decomposition voltage of water, it has the advantages of being able to achieve a higher voltage by appropriately selecting the positive electrode active material and having a high energy density. Has attracted attention as a secondary battery.
【０００３】而して、高電圧型のリチウム二次電池の正
極活物質として、充電状態において高電位を示すＬｉＣ
ｏＯ2 、ＬｉＮｉＯ2 、ＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 等の
一般式ＬｉＭＯ2 （但し、ＭはＣｏ及びＮｉの少なくと
も一種）で表されるリチウム含有遷移金属酸化物が提案
されている。As a positive electrode active material of a high-voltage lithium secondary battery, LiC which exhibits a high potential in a charged state is used.
Lithium-containing transition metal oxides represented by a general formula LiMO 2 (where M is at least one of Co and Ni) such as oO 2 , LiNiO 2 , and LiNi 0.5 Co 0.5 O 2 have been proposed.
【０００４】しかしながら、この種の正極活物質を使用
したリチウム二次電池には、非水電解液の溶媒の分解に
対して正極活物質が高い活性を有することに起因して、
正極の表面で溶媒の分解が起こるために、充放電サイク
ル特性が良くないという問題がある。However, a lithium secondary battery using this kind of positive electrode active material has a problem in that the positive electrode active material has high activity against decomposition of a solvent in a non-aqueous electrolyte.
Since the solvent is decomposed on the surface of the positive electrode, there is a problem that the charge / discharge cycle characteristics are not good.
【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、溶媒の分解
が起こりにくい、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, and an object of the present invention is to provide a lithium secondary battery which does not easily decompose a solvent and has excellent charge / discharge cycle characteristics. .
【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（以下「本発明電池」
と称する。）は、正極と、負極と、溶質及び溶媒からな
る非水電解液とを備えるリチウム二次電池において、前
記正極が、少なくとも粒子表面にＬｉ 2 ＭｎＯ 3 が存在
する、Ｌｉ2 ＭｎＯ3 と、ＬｉＭＯ2 （但し、ＭはＣｏ
及びＮｉから選ばれた少なくとも一種の元素）との複合
体粒子を電極材料とするものである。In order to achieve the above object, a lithium secondary battery according to the present invention (hereinafter referred to as "battery of the present invention")
Called. ) Comprises a positive electrode, a negative electrode, a lithium secondary battery and a nonaqueous electrolyte comprising a solute and a solvent, wherein the positive electrode, the Li 2 MnO 3 on at least the particle surface there
To a Li 2 MnO 3, LiMO 2 (where, M is Co
And at least one element selected from Ni and Ni) as an electrode material.
【０００７】上記複合体粒子としては、例えば、ＬｉＭ
Ｏ2 を粒子内部に、Ｌｉ2 ＭｎＯ3を粒子表面に、それ
ぞれ含有するものや、ＬｉＭＯ2 とＬｉ2 ＭｎＯ3 とが
粒子中に均一に混在するものが挙げられる。ＬｉＭＯ2
を粒子内部に、Ｌｉ2 ＭｎＯ3 を粒子表面に、それぞれ
含有する複合体粒子が、放電容量の大きいリチウム二次
電池を得る上で好ましい。The composite particles include, for example, LiM
Examples include those containing O 2 inside the particle and Li 2 MnO 3 on the particle surface, and those containing LiMO 2 and Li 2 MnO 3 uniformly mixed in the particle. LiMO 2
Are contained in the inside of the particle and Li 2 MnO 3 is contained in the surface of the particle, respectively, in order to obtain a lithium secondary battery having a large discharge capacity.
【０００８】また、本発明電池に於ける複合体粒子は、
Ｍ及びＭｎの総原子数に対するＭｎの原子数の比の値が
０．００５〜０．２のものが好ましい。この比の値が、
この範囲を外れると、充放電サイクル特性が低下する傾
向がある。Further, the composite particles in the battery of the present invention include:
It is preferable that the value of the ratio of the number of Mn atoms to the total number of M and Mn atoms is 0.005 to 0.2. The value of this ratio is
Outside this range, the charge / discharge cycle characteristics tend to decrease.
【０００９】本発明電池の非水電解液の溶媒としては、
充放電サイクル特性に特に優れたリチウム二次電池を得
る上で、環状炭酸エステル、非環状炭酸エステル又は環
状炭酸エステルと非環状炭酸エステルとの混合溶媒が好
ましい。The solvent of the non-aqueous electrolyte of the battery of the present invention includes:
In order to obtain a lithium secondary battery having particularly excellent charge / discharge cycle characteristics, a cyclic carbonate, an acyclic carbonate, or a mixed solvent of a cyclic carbonate and an acyclic carbonate is preferable.
【００１０】環状炭酸エステルとしては、エチレンカー
ボネート、プロピレンカーボネート、ブチレンカーボネ
ート、ビニレンカーボネートが例示され、また非環状炭
酸エステルとしては、ジメチルカーボネート、ジエチル
カーボネート、メチルエチルカーボネートが例示され
る。環状炭酸エステルの中では、エチレンカーボネート
が特に好ましい。Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate, and examples of the non-cyclic carbonate include dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate. Among cyclic carbonates, ethylene carbonate is particularly preferred.
【００１１】本発明電池の非水電解液の溶質としては、
ＬｉＰＦ6 、ＬｉＣｌＯ4 、ＬｉＢＦ4 、ＬｉＣＦ3 Ｓ
Ｏ3 が例示されるが、特に制限されない。The solute of the non-aqueous electrolyte of the battery of the present invention includes:
LiPF 6 , LiClO 4 , LiBF 4 , LiCF 3 S
O 3 is exemplified, but is not particularly limited.
【００１２】本発明電池の負極としては、リチウムイオ
ンを吸蔵及び放出することが可能な物質又は金属リチウ
ムを電極材料とするものが例示される。リチウムイオン
を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や、リチウム−ア
ルミニウム合金、リチウム−錫合金、リチウム−鉛合金
等のリチウム合金が例示される。Examples of the negative electrode of the battery of the present invention include those using a substance capable of inserting and extracting lithium ions or metallic lithium as an electrode material. Materials that can occlude and release lithium ions include graphite,
Examples thereof include carbon materials such as coke and fired organic substances, and lithium alloys such as a lithium-aluminum alloy, a lithium-tin alloy, and a lithium-lead alloy.
【００１３】[0013]
【作用】少なくとも粒子表面にＬｉ 2 ＭｎＯ 3 が存在す
る、Ｌｉ2 ＭｎＯ3 とＬｉＭＯ2 （活物質）との複合体
粒子が正極材料として使用されているので、正極の表面
での溶媒の分解が起こりにくくなり、充放電サイクル特
性が向上する。これは、粒子表面に存在するＬｉ2 Ｍｎ
Ｏ3 が、溶媒の分解に対して高い活性を示すＬｉＭＯ2
の活性を低下させるためと考えられる。因みに、Ｌｉ2
ＭｎＯ3 は、充放電には関与しない。[Function] At least Li 2 MnO 3 exists on the particle surface
Since the composite particles of Li 2 MnO 3 and LiMO 2 (active material) are used as the positive electrode material, decomposition of the solvent on the surface of the positive electrode is less likely to occur, and the charge / discharge cycle characteristics are improved. This is because Li 2 Mn present on the particle surface
O 3 is LiMO 2 showing high activity against decomposition of solvent
Is considered to decrease the activity of By the way, Li 2
MnO 3 does not participate in charge and discharge.
【００１４】特に、ＬｉＭＯ2 を粒子内部に、Ｌｉ2 Ｍ
ｎＯ3 を粒子表面に、それぞれ含有する複合体粒子を正
極材料として使用した場合には、充放電サイクル特性が
向上するだけでなく、理由は現在のところ定かでない
が、ＬｉＭＯ2 の利用率が向上して放電容量も増大す
る。In particular, LiMO 2 is contained inside the particles, Li 2 M
When the composite particles containing nO 3 on the particle surface are used as the cathode material, not only the charge-discharge cycle characteristics are improved, but also the reason is not clear at present, but the utilization rate of LiMO 2 is improved. As a result, the discharge capacity also increases.
【００１５】[0015]
【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.
【００１６】（実施例１） 〔正極の作製〕Ｌｉ2 ＣＯ3 とＣｏＣＯ3 とを、Ｌｉ：
Ｃｏの原子比１．２：１．０で混合した後、８５０°Ｃ
で１０時間熱処理して、Ｌｉ1.2 ＣｏＯ2 を得た。次い
で、このＬｉ1.2 ＣｏＯ2 と、ＭｎＯ2 とを、Ｃｏ：Ｍ
ｎの原子比１．０：０．１で混合した後、８５０°Ｃで
１０時間熱処理して、正極材料を作製した。(Example 1) [Preparation of positive electrode] Li 2 CO 3 and CoCO 3 were mixed with Li:
After mixing at an atomic ratio of Co of 1.2: 1.0, 850 ° C.
For 10 hours to obtain Li 1.2 CoO 2 . Next, the Li 1.2 CoO 2 and MnO 2 were converted into Co: M
After mixing at an atomic ratio of n of 1.0: 0.1, the mixture was heat-treated at 850 ° C. for 10 hours to prepare a positive electrode material.
【００１７】この正極材料を、Ｘ線光電子分光法を用い
て、Ａｒイオンエッチングにより徐々に表面から粒子内
部まで分析したところ、Ｍｎが表面にしか存在しないこ
とが分かった。この事実から、この正極材料が、ＬｉＣ
ｏＯ2 を粒子内部に、Ｌｉ2ＭｎＯ3 を粒子表面に、そ
れぞれ含有する複合体粒子からなるものであることを確
認した。When this positive electrode material was gradually analyzed from the surface to the inside of the particles by Ar ion etching using X-ray photoelectron spectroscopy, it was found that Mn was present only on the surface. From this fact, this cathode material is made of LiC
It was confirmed that the particles consisted of composite particles containing oO 2 inside the particles and Li 2 MnO 3 on the particle surfaces.
【００１８】次いで、上記正極材料と、導電剤としての
炭素粉末と、結着剤としてのフッ素樹脂とを、重量比８
０：１０：１０で混合した後、ペレット状に成型して、
正極を作製した。Next, the above positive electrode material, carbon powder as a conductive agent, and a fluororesin as a binder were mixed at a weight ratio of 8%.
After mixing at 0:10:10, the mixture is molded into a pellet,
A positive electrode was produced.
【００１９】〔負極の作製〕金属リチウム圧延板を打ち
抜いて負極を作製した。[Preparation of Negative Electrode] A rolled metal lithium plate was punched to prepare a negative electrode.
【００２０】〔非水電解液の調製〕エチレンカーボネー
ト（ＥＣ）にＬｉＰＦ6 を１モル／リットル溶かして非
水電解液を調製した。[Preparation of Nonaqueous Electrolyte] A nonaqueous electrolyte was prepared by dissolving LiPF 6 in ethylene carbonate (EC) at 1 mol / L.
【００２１】〔電池の組立〕上記の正極、負極及び非水
電解液を用いて扁平型の正極支配の本発明電池Ａ１を組
み立てた（電池寸法：外径２４．０ｍｍ、厚み３．０ｍ
ｍ）。なお、セパレータとしては、ポリプロピレン製の
微多孔膜を使用した。[Assembly of Battery] Using the above-mentioned positive electrode, negative electrode and non-aqueous electrolyte, a flat type positive electrode-dominated battery A1 of the present invention was assembled (battery dimensions: outer diameter 24.0 mm, thickness 3.0 m).
m). In addition, a microporous film made of polypropylene was used as the separator.
【００２２】（実施例２）Ｌｉ2 ＣＯ3 とＣｏＣＯ3 と
ＭｎＯ2 とを、Ｌｉ：Ｃｏ：Ｍｎの原子比１．２：１．
０：０．１で混合した後、８５０°Ｃで２０時間熱処理
して、正極材料を作製した。(Example 2) Li 2 CO 3 , CoCO 3 and MnO 2 were mixed at an atomic ratio of Li: Co: Mn of 1.2: 1.
After mixing at 0: 0.1, the mixture was heat-treated at 850 ° C. for 20 hours to prepare a positive electrode material.
【００２３】この正極材料を、先と同様のＸ線光電子分
光法により分析したところ、Ｍｎが表面から内部にわた
って均一に分布していることが分かった。この事実か
ら、この正極材料が、ＬｉＣｏＯ2 とＬｉ2 ＭｎＯ3 と
が粒子中に均一に混在した複合体粒子からなるものであ
ることを確認した。When this cathode material was analyzed by the same X-ray photoelectron spectroscopy method as above, it was found that Mn was uniformly distributed from the surface to the inside. From this fact, it was confirmed that this positive electrode material was composed of composite particles in which LiCoO 2 and Li 2 MnO 3 were uniformly mixed in the particles.
【００２４】次いで、この正極材料を使用したこと以外
は実施例１と同様にして、本発明電池Ａ２を組み立て
た。Next, a battery A2 of the present invention was assembled in the same manner as in Example 1 except that this positive electrode material was used.
【００２５】（実施例３）Ｌｉ2 ＣＯ3 とＣｏＣＯ3 と
Ｎｉ（ＯＨ）2 とを、Ｌｉ：Ｃｏ：Ｎｉの原子比１．
２：０．５：０．５で混合した後、８５０°Ｃで１０時
間熱処理して、Ｌｉ 1.2 Ｃｏ0.5 Ｎｉ0.5 Ｏ2 を得た。
次いで、このＬｉ1.2 Ｃｏ0.5 Ｎｉ0.5 Ｏ2と、ＭｎＯ
2 とを、Ｃｏ＋Ｎｉ：Ｍｎの原子比１．０：０．１で混
合した後、８５０°Ｃで１０時間熱処理して、正極材料
を作製した。Example 3 LiTwoCOThreeAnd CoCOThreeWhen
Ni (OH)TwoAnd an atomic ratio of Li: Co: Ni of 1.
After mixing at 2: 0.5: 0.5, 10 hours at 850 ° C
Heat treatment for Li 1.2Co0.5Ni0.5OTwoI got
Then, this Li1.2Co0.5Ni0.5OTwoAnd MnO
TwoAre mixed at an atomic ratio of Co + Ni: Mn of 1.0: 0.1.
After being combined, heat-treated at 850 ° C for 10 hours,
Was prepared.
【００２６】この正極材料を、先と同様のＸ線光電子分
光法により分析したところ、Ｍｎが表面にしか存在しな
いことが分かった。この事実から、この正極材料が、Ｌ
ｉＣｏ0.5 Ｎｉ0.5 Ｏ2 を粒子内部に、Ｌｉ2 ＭｎＯ3
を粒子表面に、それぞれ含有する複合体粒子からなるも
のであることを確認した。When this positive electrode material was analyzed by the same X-ray photoelectron spectroscopy method as above, it was found that Mn was present only on the surface. From this fact, this cathode material is
iCo 0.5 Ni 0.5 O 2 inside the particles, Li 2 MnO 3
On the surface of the particles was confirmed to be composed of composite particles.
【００２７】次いで、この正極材料を使用したこと以外
は実施例１と同様にして、本発明電池Ａ３を組み立て
た。Next, a battery A3 of the present invention was assembled in the same manner as in Example 1 except that this positive electrode material was used.
【００２８】（比較例１）Ｌｉ2 ＣＯ3 とＣｏＣＯ3 と
を、Ｌｉ：Ｃｏの原子比１．０：１．０で混合した後、
８５０°Ｃで２０時間熱処理して、ＬｉＣｏＯ2 を得
た。このＬｉＣｏＯ2 を正極材料として使用したこと以
外は実施例１と同様にして、比較電池Ｂ１を組み立て
た。(Comparative Example 1) Li 2 CO 3 and CoCO 3 were mixed at an atomic ratio of Li: Co of 1.0: 1.0.
Heat treatment was performed at 850 ° C. for 20 hours to obtain LiCoO 2 . A comparative battery B1 was assembled in the same manner as in Example 1 except that this LiCoO 2 was used as a positive electrode material.
【００２９】（比較例２）Ｌｉ2 ＣＯ3 とＣｏＣＯ3 と
Ｎｉ（ＯＨ）2 とを、Ｌｉ：Ｃｏ：Ｎｉの原子比１．
０：０．５：０．５で混合した後、８５０°Ｃで２０時
間熱処理して、ＬｉＣｏ0.5 Ｎｉ0.5 Ｏ2 を得た。この
ＬｉＣｏ0.5 Ｎｉ0.5 Ｏ2 を正極材料として使用したこ
と以外は実施例１と同様にして、比較電池Ｂ２を組み立
てた。Comparative Example 2 Li 2 CO 3 , CoCO 3, and Ni (OH) 2 were prepared by mixing Li: Co: Ni at an atomic ratio of 1.
After mixing at 0: 0.5: 0.5, the mixture was heat-treated at 850 ° C. for 20 hours to obtain LiCo 0.5 Ni 0.5 O 2 . A comparative battery B2 was assembled in the same manner as in Example 1 except that this LiCo 0.5 Ni 0.5 O 2 was used as a positive electrode material.
【００３０】〔充放電サイクル試験〕本発明電池Ａ１〜
Ａ３及び比較電池Ｂ１，Ｂ２について、３ｍＡで４．１
Ｖまで充電した後、３ｍＡで３．０Ｖ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、各電池
の充放電サイクル特性を調べた。結果を図１に示す。図
１は、各電池の充放電サイクル特性を、縦軸に放電容量
（ｍＡｈ）を、また横軸にサイクル数（回）をとって示
したグラフである。また、表１に、各電池の１サイクル
目及び１００サイクル目の各放電容量を示す。[Charge / Discharge Cycle Test] Batteries A1 to A4 of the present invention
For A3 and comparative batteries B1 and B2, 4.1 mA at 3 mA
After the battery was charged to V, a charge / discharge cycle test was performed in which the process of discharging to 3.0 V at 3 mA was one cycle, and the charge / discharge cycle characteristics of each battery were examined. The results are shown in FIG. FIG. 1 is a graph showing the charge / discharge cycle characteristics of each battery, the vertical axis representing the discharge capacity (mAh), and the horizontal axis representing the number of cycles (times). Table 1 shows the discharge capacity at the first cycle and the 100th cycle of each battery.
【００３１】[0031]
【表１】 [Table 1]
【００３２】図１及び表１より、本発明電池Ａ１〜Ａ３
は、比較電池Ｂ１，Ｂ２に比べて、充放電の繰り返しに
伴う放電容量の低下が少なく、充放電サイクル特性に優
れていることが分かる。FIG. 1 and Table 1 show that the batteries A1 to A3 of the present invention were obtained.
It can be seen that, compared to the comparative batteries B1 and B2, the decrease in the discharge capacity due to the repetition of charge / discharge was small and the charge / discharge cycle characteristics were excellent.
【００３３】特に、ＬｉＭＯ2 を粒子内部に、Ｌｉ2 Ｍ
ｎＯ3 を粒子表面に、それぞれ含有する複合体粒子を正
極材料として使用した本発明電池Ａ１及びＡ３では、充
放電サイクル初期の放電容量も増大することが分かる。In particular, LiMO 2 is contained inside the particles, and Li 2 M
It can be seen that in the batteries A1 and A3 of the present invention using the composite particles each containing nO 3 on the particle surface as a positive electrode material, the discharge capacity at the beginning of the charge / discharge cycle is also increased.
【００３４】〔非水電解液の溶媒の種類と充放電サイク
ル特性の関係〕非水電解液の溶媒として、エチレンカー
ボネートに代えて表２に示す種々の溶媒を使用したこと
以外は実施例１と同様にして、溶媒のみが異なる１２種
の本発明電池Ａ４〜Ａ１５を組み立てた。次いで、これ
らの各電池について、先と同じ条件で充放電サイクル試
験を行い、各電池の１サイクル目及び１００サイクル目
の各放電容量を求めた。結果を表２に示す。なお、表２
には、実施例１で組み立てた本発明電池Ａ１の結果も、
表１より転記して示してある。[Relationship between Type of Solvent of Nonaqueous Electrolyte and Charge / Discharge Cycle Characteristics] The procedure of Example 1 was repeated except that various solvents shown in Table 2 were used instead of ethylene carbonate as the solvent of the nonaqueous electrolyte. Similarly, twelve kinds of batteries A4 to A15 of the present invention differing only in the solvent were assembled. Next, a charge / discharge cycle test was performed on each of these batteries under the same conditions as above, and the respective discharge capacities at the first cycle and the 100th cycle of each battery were determined. Table 2 shows the results. Table 2
Shows the result of the battery A1 of the present invention assembled in Example 1,
It is transcribed and shown from Table 1.
【００３５】[0035]
【表２】 [Table 2]
【００３６】表２に示すように、本発明電池Ａ１，Ａ４
〜Ａ１１は、本発明電池Ａ１２〜Ａ１５に比べて、１０
０サイクル目の放電容量が特に大きく、充放電サイクル
特性に極めて優れている。この事実から、本発明に於け
る非水電解液の溶媒としては、環状炭酸エステル、非環
状炭酸エステル又は環状炭酸エステルと非環状炭酸エス
テルとの混合溶媒を使用することが好ましいことが分か
る。As shown in Table 2, the batteries A1 and A4 of the present invention
To A11 are 10 times smaller than the batteries A12 to A15 of the present invention.
The discharge capacity at the 0th cycle is particularly large, and the charge / discharge cycle characteristics are extremely excellent. From this fact, it is understood that it is preferable to use a cyclic carbonate, a non-cyclic carbonate, or a mixed solvent of a cyclic carbonate and a non-cyclic carbonate as a solvent of the non-aqueous electrolyte in the present invention.
【００３７】〔複合体粒子のＬｉ2 ＭｎＯ3 含有量と充
放電サイクル特性の関係〕実施例１と同様の方法によ
り、複合体粒子のＬｉ2 ＭｎＯ3 含有量が異なる９種の
正極材料を作製し、これらの正極材料を各同量使用した
こと以外は実施例１と同様にして、リチウム二次電池を
組み立てた。次いで、これらの各電池について、先と同
じ条件で充放電サイクル試験を行い、各電池の１サイク
ル目及び１００サイクル目の各放電容量を求めた。結果
を図２に示す。[Relationship between Li 2 MnO 3 content of composite particles and charge / discharge cycle characteristics] Nine kinds of positive electrode materials having different Li 2 MnO 3 contents of composite particles were produced in the same manner as in Example 1. Then, a lithium secondary battery was assembled in the same manner as in Example 1 except that the same amount of each of these positive electrode materials was used. Next, a charge / discharge cycle test was performed on each of these batteries under the same conditions as above, and the respective discharge capacities at the first cycle and the 100th cycle of each battery were determined. The results are shown in FIG.
【００３８】図２は、各電池に使用した複合体粒子のＬ
ｉ2 ＭｎＯ3 含有量と充放電サイクル特性の関係を、縦
軸に１サイクル目又は１００サイクル目の放電容量（ｍ
Ａｈ）を、横軸に複合体粒子中のＣｏ及びＭｎの総原子
数に対するＭｎの原子数の比の値〔Ｍｎの原子数／（Ｃ
ｏの原子数＋Ｍｎの原子数）〕をとって示したグラフで
ある。同図より、充放電サイクル特性に特に優れたリチ
ウム二次電池を得るためには、Ｃｏ及びＭｎの総原子数
に対するＭｎの原子数の比の値が０．００５〜０．２で
ある特定のＬｉ2 ＭｎＯ3 含有量の複合体粒子からなる
正極材料を使用することが好ましいことが分かる。FIG. 2 shows the L of the composite particles used for each battery.
The vertical axis indicates the relationship between the i 2 MnO 3 content and the charge / discharge cycle characteristics.
Ah) represents the value of the ratio of the number of Mn atoms to the total number of Co and Mn atoms in the composite particles [the number of Mn atoms / (C
o is the number of atoms of O + the number of atoms of Mn)]. As shown in the figure, in order to obtain a lithium secondary battery having particularly excellent charge / discharge cycle characteristics, a specific value of the ratio of the number of Mn atoms to the total number of Co and Mn atoms of 0.005 to 0.2 is required. It can be seen that it is preferable to use a positive electrode material composed of composite particles having a Li 2 MnO 3 content.
【００３９】上記実施例では、本発明を扁平型電池に適
用する場合を例に挙げて説明したが、本発明は電池の形
状に特に制限があるわけではなく、円筒型、角型など、
他の種々の形状のリチウム二次電池に適用し得るもので
ある。In the above embodiment, the case where the present invention is applied to a flat type battery has been described as an example. However, the present invention is not particularly limited in the shape of the battery.
The present invention can be applied to other various shapes of lithium secondary batteries.
【００４０】[0040]
【発明の効果】非水電解液の溶媒の分解に対して高い活
性を有するＬｉＭＯ2 の活性が粒子表面に存在するＬｉ
2 ＭｎＯ 3 により低下しているので、正極の表面での溶
媒の分解が起こりにくく、充放電を繰り返しても非水電
解液が劣化しにくい。このため、本発明電池は充放電サ
イクル特性に優れる。 Li activity of LiMO 2 is present on the particle surface with a high activity for decomposition of the solvent of the nonaqueous electrolytic solution according to the present invention
Since the concentration is lowered by 2 MnO 3 , the solvent is hardly decomposed on the surface of the positive electrode, and the non-aqueous electrolyte is hardly deteriorated even if charge and discharge are repeated. For this reason, the battery of the present invention is excellent in charge / discharge cycle characteristics.
【図１】実施例で組み立てた本発明電池及び比較電池の
充放電サイクル特性を示すグラフである。FIG. 1 is a graph showing charge / discharge cycle characteristics of a battery of the present invention and a comparative battery assembled in an example.
【図２】複合体粒子のＬｉ2 ＭｎＯ3 含有量と充放電サ
イクル特性の関係を示したグラフである。FIG. 2 is a graph showing the relationship between the Li 2 MnO 3 content of composite particles and charge / discharge cycle characteristics.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０１Ｇ 53/00 Ｃ０１Ｇ 53/00 Ａ (56)参考文献 特開 平５−28995（ＪＰ，Ａ) 特開 昭63−114064（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/58 H01M 4/02 H01M 10/40 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 7 Identification symbol FI C01G 53/00 C01G 53/00 A (56) References JP-A-5-28995 (JP, A) JP-A-63-114064 ( JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) H01M 4/58 H01M 4/02 H01M 10/40
Claims (5)
水電解液とを備えるリチウム二次電池において、前記正
極が、少なくとも粒子表面にＬｉ 2 ＭｎＯ 3 が存在す
る、Ｌｉ2 ＭｎＯ3 と、ＬｉＭＯ2 （但し、ＭはＣｏ及
びＮｉから選ばれた少なくとも一種の元素）との複合体
粒子を電極材料とす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, a negative electrode, and a non-aqueous electrolyte comprising a solute and a solvent, wherein the positive electrode has Li 2 MnO 3 at least on the particle surface .
That, and Li 2 MnO 3, LiMO 2 (where, M represents at least one element selected from Co and Ni) lithium secondary battery, characterized in that the electrode material of the composite particles with.
に、Ｌｉ2 ＭｎＯ3 を粒子表面に、それぞれ含有してな
るものである請求項１記載のリチウム二次電池。2. The lithium secondary battery according to claim 1, wherein the composite particles contain LiMO 2 inside the particles and Li 2 MnO 3 on the particle surfaces.
ｎＯ3 とが粒子中に均一に混在してなるものである請求
項１記載のリチウム二次電池。3. The composite particles are composed of LiMO 2 and Li 2 M.
2. The lithium secondary battery according to claim 1, wherein nO 3 is uniformly mixed in the particles.
に対するＭｎの原子数の比の値が０．００５〜０．２の
ものである請求項１記載のリチウム二次電池。4. The lithium secondary battery according to claim 1, wherein the composite particles have a ratio of the number of Mn atoms to the total number of M and Mn atoms of 0.005 to 0.2.
酸エステル又は環状炭酸エステルと非環状炭酸エステル
との混合溶媒である請求項１〜４のいずれかに記載のリ
チウム二次電池。5. The lithium secondary battery according to claim 1, wherein the solvent is a cyclic carbonate, an acyclic carbonate, or a mixed solvent of a cyclic carbonate and an acyclic carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33424994A JP3258841B2 (en) | 1994-12-16 | 1994-12-16 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33424994A JP3258841B2 (en) | 1994-12-16 | 1994-12-16 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08171935A JPH08171935A (en) | 1996-07-02 |
| JP3258841B2 true JP3258841B2 (en) | 2002-02-18 |
Family
ID=18275222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33424994A Expired - Fee Related JP3258841B2 (en) | 1994-12-16 | 1994-12-16 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3258841B2 (en) |
Cited By (3)
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|---|---|---|---|---|
| WO2009063838A1 (en) | 2007-11-12 | 2009-05-22 | Gs Yuasa Corporation | Active material for lithium rechargeable battery, lithium rechargeable battery, and process for producing the same |
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| DE102017207683A1 (en) | 2016-05-09 | 2017-11-09 | Nichia Corporation | A process for producing a nickel-cobalt composite hydroxide and a process for producing an active material of a positive electrode for an anhydrous electrolyte secondary battery |
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-
1994
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Cited By (5)
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| WO2009063838A1 (en) | 2007-11-12 | 2009-05-22 | Gs Yuasa Corporation | Active material for lithium rechargeable battery, lithium rechargeable battery, and process for producing the same |
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| EP3486978A1 (en) * | 2017-11-15 | 2019-05-22 | Ecopro Bm Co., Ltd. | Cathode active material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08171935A (en) | 1996-07-02 |
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