JPH04267053A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH04267053A JPH04267053A JP3050487A JP5048791A JPH04267053A JP H04267053 A JPH04267053 A JP H04267053A JP 3050487 A JP3050487 A JP 3050487A JP 5048791 A JP5048791 A JP 5048791A JP H04267053 A JPH04267053 A JP H04267053A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- battery
- lithium secondary
- electrode active
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000011149 active material Substances 0.000 claims description 13
- 229910011620 Lix My Inorganic materials 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 4
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910011625 Lix My Nz Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910010584 LiFeO2 Inorganic materials 0.000 description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910014540 LiMn2O Inorganic materials 0.000 description 1
- 229910011406 Lix MnO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910014205 My Nz O2 Inorganic materials 0.000 description 1
- 229910020040 NbS Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はリチウム二次電池に関す
るもので、さらに詳しくはその正極に関するものである
。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly to a positive electrode thereof.
【０００２】0002
【従来の技術】リチウムを負極活物質として用いるリチ
ウム電池は、高電圧、高エネルギー密度及び高信頼性を
有する特長から広く一般に用いられるようになってきた
が、これらは１次電池である。最近では、２次電池の研
究も盛んに行われ、一部では実用化もされている。しか
し、これらの電池の特性は未だに十分ではない。2. Description of the Related Art Lithium batteries using lithium as a negative electrode active material have come to be widely used because of their characteristics of high voltage, high energy density, and high reliability, but these are primary batteries. Recently, research on secondary batteries has been actively conducted, and some have even been put into practical use. However, the characteristics of these batteries are still not sufficient.
【０００３】従来研究されてきた代表的な正極活物質と
してはＭｏＳ２ ，Ｖ２ Ｏ５ ，ＭｎＯ２ ，ＮｂＳ
ｅ３ ，ＴｉＳ２ などがある。これらの中で、特にＭ
ｎＯ２ は安価であるということから注目され、改質さ
れたマンガン酸化物が種々提案されている。例えば、特
開平２−１８３９６３号公報に開示されているが、これ
らのマンガン酸化物はいずれも作動電圧が３Ｖ程度であ
り、容量はさほど大きくない。Typical positive electrode active materials that have been studied in the past include MoS2, V2O5, MnO2, and NbS.
e3, TiS2, etc. Among these, especially M
nO2 has attracted attention because it is inexpensive, and various modified manganese oxides have been proposed. For example, as disclosed in Japanese Patent Application Laid-Open No. 2-183963, all of these manganese oxides have an operating voltage of about 3 V and a not so large capacity.
【０００４】そこで極最近では容量はマンガン酸化物と
同程度であるが、作動電圧が４Ｖ程度と高いＬｉＣｏＯ
２ が高電圧、高エネルギー密度を得られる活物質とし
て注目され研究されている。現在、４Ｖ近い作動電圧を
示すものとして知られている活物質としては、ＬｉＣｏ
Ｏ２ のほかにＬｉＦｅＯ２ ，ＬｉＮｉＯ２ 及びＬ
ｉＭｎ２ Ｏ４ がある。これらの中でＬｉＦｅＯ２
，ＬｉＣｏＯ２ 及びＬｉＮｉＯ２ はＬｉＭｎ２ Ｏ
４ に比べて理論容量が大きく高エネルギー密度のリチ
ウム二次電池を得られる可能性がある。[0004] Very recently, LiCoO, which has a capacity similar to that of manganese oxide but has a high operating voltage of about 4V, has been developed.
2 has been attracting attention and research as an active material that can provide high voltage and high energy density. Currently, LiCo is an active material known to exhibit an operating voltage close to 4V.
In addition to O2, LiFeO2, LiNiO2 and L
There is iMn2 O4. Among these, LiFeO2
, LiCoO2 and LiNiO2 are LiMn2O
It is possible to obtain a lithium secondary battery with a larger theoretical capacity and higher energy density than 4.
【０００５】[0005]
【発明が解決しようとする課題】ところで、ＬｉＣｏＯ
２ を用いて深い深度の充放電サイクル試験を行ったと
ころサイクルの進行に伴って容量が劣化することが判っ
た。これはリチウムの挿入脱離に伴う結晶構造の変化が
大きいために、活物質自身の可逆性が低下することと、
電極が膨張収縮を繰り返すうちに活物質と導電剤の接触
が不十分になることが原因であると考えられることから
、結晶構造の変化の小さいＬｉＣｏＯ２ を作製する必
要があるという問題点があった。[Problem to be solved by the invention] By the way, LiCoO
When a deep charge/discharge cycle test was conducted using 2, it was found that the capacity deteriorated as the cycle progressed. This is because the reversibility of the active material itself decreases due to large changes in the crystal structure due to the intercalation and desorption of lithium.
This is thought to be caused by insufficient contact between the active material and the conductive agent as the electrode expands and contracts repeatedly, so there was a problem in that it was necessary to create LiCoO2 with a small change in crystal structure. .
【０００６】本発明は上記問題点を解消するために、深
い深度での充放電サイクルにおいても可逆性に優れ、結
晶構造変化が少なく、４Ｖ前後の作動電圧を示す正極活
物質を提供することを目的とする。[0006] In order to solve the above-mentioned problems, the present invention aims to provide a positive electrode active material that has excellent reversibility even in charge/discharge cycles at deep depths, has little change in crystal structure, and exhibits an operating voltage of around 4V. purpose.
【０００７】[0007]
【課題を解決するための手段】本発明は正極、負極及び
電解質を具備するリチウム二次電池において、前記正極
の活物質が、一般式Ｌｉｘ Ｍｙ Ｎｚ Ｏ２ で表さ
れるものであることを特徴とするリチウム二次電池によ
って構成されるものである。但し、ＭはＦｅ，Ｃｏ，Ｎ
ｉの群から選ばれた少なくとも１種を表し、ＮはＴｉ，
Ｖ，Ｃｒ，Ｍｎの群から選ばれた少なくとも１種を表し
、Ｘ，Ｙ，Ｚはそれぞれ ０．８≦Ｘ≦１．２ ，
０．８≦Ｙ＋Ｚ≦１．２ ， ０＜Ｙ＜１．２ ，０＜
Ｚ＜１．２ の数値を表す。[Means for Solving the Problems] The present invention provides a lithium secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, characterized in that the active material of the positive electrode is represented by the general formula Lix My Nz O2. It is composed of a lithium secondary battery. However, M is Fe, Co, N
represents at least one species selected from the group i, N is Ti,
Represents at least one species selected from the group of V, Cr, and Mn, and X, Y, and Z are each 0.8≦X≦1.2,
0.8≦Y+Z≦1.2, 0<Y<1.2, 0<
Represents a numerical value of Z<1.2.
【０００８】[0008]
【作 用】一般式Ｌｉｘ Ｍｙ Ｎｚ Ｏ２ で表さ
れる活物質を正極に用いることでサイクル特性が改善さ
れる理由は現在のところ明らかではないが、周期律表で
表される第一遷移金属中のＴｉからＮｉまでの元素はい
ずれも層状ロックソルト構造をもつリチウム−遷移金属
−酸素の三元系複合酸化物ＬｉＡＯ２ （ＡはＴｉから
Ｎｉまでの第一遷移金属）として存在しうる。つまりこ
れらの元素は、同じ構造を作るために容易に相互に置換
した形の多元系複合酸化物を得ることができると思われ
る。[Function] The reason why the cycle characteristics are improved by using the active material represented by the general formula Lix My Nz O2 in the positive electrode is not clear at present, but it is All the elements from Ti to Ni can exist as a ternary composite oxide LiAO2 of lithium-transition metal-oxygen (A is the first transition metal from Ti to Ni) having a layered rock-salt structure. In other words, it seems possible to obtain a multi-element composite oxide in which these elements are easily substituted with each other to create the same structure.
【０００９】このことから一般式Ｌｉｘ Ｍｙ Ｎｚ
Ｏ２ で表される多元系複合酸化物は、Ｆｅ，Ｃｏ，Ｎ
ｉの群から選ばれた少なくとも１種の元素が構造中に入
ることにより作動電圧が４Ｖ近くを示し、Ｔｉ，Ｖ，Ｃ
ｒ，Ｍｎの群から選ばれた少なくとも１種の元素が構造
中に入ることにより構造が安定化されたために良好なサ
イクル特性を示すものと考えている。From this, the general formula Lix My Nz
The multi-component complex oxide represented by O2 includes Fe, Co, N
When at least one element selected from the group i is included in the structure, the operating voltage is close to 4V, and Ti, V, C
It is believed that the structure is stabilized by the inclusion of at least one element selected from the group consisting of r and Mn into the structure, thereby exhibiting good cycle characteristics.
【００１０】なぜならば、Ｌｉｘ ＶＯ２ 及びＬｉｘ
ＭｎＯ２ の作動電圧はそれぞれ ２．５Ｖ及び２．
８ Ｖであり、 ３．５Ｖ以上の高電圧を示すことはな
い。また、Ｌｉｘ ＭｎＯ２ のサイクル特性は数百サ
イクルの範囲で良好である。[0010] Because Lix VO2 and Lix
The working voltages of MnO2 are 2.5V and 2.5V, respectively.
8 V, and does not exhibit a high voltage of 3.5 V or higher. Furthermore, the cycle characteristics of Lix MnO2 are good within a range of several hundred cycles.
【００１１】[0011]
【実施例】以下本発明の詳細について実施例に基づき説
明するが、本発明がこれら実施例に限定されるものでは
ないことは言うまでもない。EXAMPLES The details of the present invention will be explained below based on Examples, but it goes without saying that the present invention is not limited to these Examples.
【００１２】（実施例１）正極活物質の調製にあたって
は、市販特級試薬の炭酸リチウムと炭酸コバルトと二酸
化マンガンとをＬｉ：Ｃｏ：Ｍｎのモル比が５：４：１
になるように秤量し、ボールミルで粉砕しながら十分混
合し、混合物をアルミナ坩堝に入れ空気中において６５
０℃で５時間仮焼成した後、９００℃で２０時間焼成し
た。焼成後室温までゆっくり冷却し、粉砕したものを正
極活物質とした。得られた生成物のＸ線回折パターンは
生成物が単一相で得られていることを示した。(Example 1) In preparing a positive electrode active material, commercially available special grade reagents such as lithium carbonate, cobalt carbonate, and manganese dioxide were mixed at a Li:Co:Mn molar ratio of 5:4:1.
Mix thoroughly while grinding with a ball mill, put the mixture in an alumina crucible, and leave it in the air at 65°C.
After pre-baking at 0°C for 5 hours, it was fired at 900°C for 20 hours. After firing, it was slowly cooled to room temperature, and the resulting powder was used as a positive electrode active material. The X-ray diffraction pattern of the product obtained showed that the product was obtained in a single phase.
【００１３】このようにして得られたＬｉＣｏ０．８
Ｍｎ０．２Ｏ２ を正極活物質として電池の試作を行っ
た。電池の作製方法を以下に述べる。LiCo0.8 thus obtained
A battery was prototyped using Mn0.2O2 as a positive electrode active material. The method for manufacturing the battery will be described below.
【００１４】まず正極活物質とアセチレンブラック及び
ポリテトラフルオロエチエン粉末とを重量比８５：１０
：５で混合し、トルエンを加えて十分混練した。これを
ローラープレスにより厚み ０．８ｍｍのシート状に成
形した。次にこれを１６ｍｍの円形に打ち抜き、減圧下
２００℃で１５時間熱処理し、ＬｉＣｏ０．８ Ｍｎ０
．２ Ｏ２ を活物質とした正極を得た。負極は厚み
０．３ｍｍのリチウム箔を直径１５ｍｍの円形に打ち抜
き、集電体を介して負極缶に圧着して用いた。非水電解
液にはγ−ブチロラクトンに１ｍｏｌ／１のＬｉＢＦ４
を溶解したものを用い、セパレータにはポリプロピレ
ン製微孔薄膜を用いた。上記正極、負極、電解液及びセ
パレータを用いて図１に示すような直径２０ｍｍ、厚さ
１．６ ｍｍのボタン型のリチウム電池を作製した。こ
の電池をＡ１とする。なお、図１において、１は絶縁リ
ング、２は負極集電体、３は負極、４は負極集電体、５
はセパレータ、６は正極、７は正極集電板である。First, the positive electrode active material and acetylene black and polytetrafluoroethene powder were mixed in a weight ratio of 85:10.
: 5, toluene was added, and the mixture was thoroughly kneaded. This was molded into a sheet with a thickness of 0.8 mm using a roller press. Next, this was punched into a 16 mm circle and heat treated at 200°C under reduced pressure for 15 hours to form LiCo0.8 Mn0.
．． A positive electrode using 2 O2 as an active material was obtained. The thickness of the negative electrode
A 0.3 mm lithium foil was punched out into a circle with a diameter of 15 mm, and used by pressing it onto a negative electrode can via a current collector. The non-aqueous electrolyte contains 1 mol/1 LiBF4 in γ-butyrolactone.
A microporous thin film made of polypropylene was used as a separator. A button-shaped lithium battery with a diameter of 20 mm and a thickness of 1.6 mm as shown in FIG. 1 was produced using the above positive electrode, negative electrode, electrolyte, and separator. This battery is designated as A1. In addition, in FIG. 1, 1 is an insulating ring, 2 is a negative electrode current collector, 3 is a negative electrode, 4 is a negative electrode current collector, and 5
is a separator, 6 is a positive electrode, and 7 is a positive current collector plate.
【００１５】（実施例２）二酸化マンガンの代わりに金
属バナジウムを用いたことを除いては、実施例１と同様
の工程で正極活物質を得た。さらにこの活物質を用いて
実施例１と同様の工程で電池を作製した。この電池をＡ
２とする。(Example 2) A positive electrode active material was obtained in the same process as in Example 1, except that metal vanadium was used instead of manganese dioxide. Furthermore, a battery was produced using this active material in the same steps as in Example 1. This battery is A
Set it to 2.
【００１６】（実施例３）正極活物質の調製にあたって
は、市販特級試薬の炭酸リチウムと炭酸コバルトと酸化
ニッケルと二酸化マンガンとをＬｉ：Ｃｏ：Ｎｉ：Ｍｎ
のモル比が５：２：２：１になるように秤量したことを
除いては、実施例１と同様の工程で正極活物質を得た。
さらにこの活物質を用いて実施例１と同様の工程で電池
を作製した。この電池をＡ３とする。(Example 3) In preparing a positive electrode active material, commercially available special grade reagents such as lithium carbonate, cobalt carbonate, nickel oxide, and manganese dioxide were mixed into Li:Co:Ni:Mn
A positive electrode active material was obtained in the same manner as in Example 1, except that the molar ratio of the two was weighed to be 5:2:2:1. Furthermore, a battery was produced using this active material in the same steps as in Example 1. This battery is called A3.
【００１７】（実施例４）正極活物質の調製にあたって
は、市販特級試薬の炭酸リチウムと炭酸コバルトと酸化
ニッケルと二酸化マンガンと金属バナジウムとをＬｉ：
Ｃｏ：Ｎｉ：Ｍｎ：Ｖのモル比が１０：４：４：１：１
になるように秤量したことを除いては、実施例１と同様
の工程で正極活物質を得た。さらにこの活物質を用いて
実施例１と同様の工程で電池を作製した。この電池をＡ
４とする。(Example 4) In preparing a positive electrode active material, commercially available special grade reagents such as lithium carbonate, cobalt carbonate, nickel oxide, manganese dioxide, and metal vanadium were mixed with Li:
The molar ratio of Co:Ni:Mn:V is 10:4:4:1:1
A positive electrode active material was obtained in the same process as in Example 1, except that it was weighed so that Furthermore, a battery was produced using this active material in the same steps as in Example 1. This battery is A
Set it to 4.
【００１８】（比較例）市販特級試薬の炭酸リチウムと
炭酸コバルトとをＬｉ：Ｃｏのモル比が１：１になるよ
うに秤量し、ボールミルで粉砕しながら十分混合し、混
合物をアルミナ坩堝に入れ空気中において６５０℃で５
時間仮焼成した後、９５０℃で２０時間焼成した。焼成
後室温までゆっくり冷却し、粉砕したものを正極活物質
とした。得られた生成物のＸ線回折パターンをＪＣＰＤ
Ｓカードに記載されたＬｉＣｏＯ２ のＸ線回折パター
ンと比較したところ、得られた生成物がＬｉＣｏＯ２
であることが判った。このようにして得られた活物質を
用いて、実施例１と同様の工程で電池を作製した。この
電池をＢとする。(Comparative Example) Lithium carbonate and cobalt carbonate, which are commercially available special grade reagents, were weighed so that the molar ratio of Li:Co was 1:1, thoroughly mixed while pulverizing with a ball mill, and the mixture was placed in an alumina crucible. 5 at 650℃ in air
After being pre-baked for an hour, it was fired at 950°C for 20 hours. After firing, it was slowly cooled to room temperature, and the resulting powder was used as a positive electrode active material. The X-ray diffraction pattern of the obtained product was determined by JCPD.
When compared with the X-ray diffraction pattern of LiCoO2 written on the S card, the obtained product was found to be LiCoO2
It turned out to be. Using the active material thus obtained, a battery was produced in the same steps as in Example 1. This battery is called B.
【００１９】このようにして作製した電池Ａ１，Ａ２，
Ａ３，Ａ４，Ｂを用いて、充放電サイクル試験を行った
。試験条件は、充電電流３ｍＡ，充電終止電圧４．５
Ｖ、放電電流３ｍＡ、放電終止電圧３．０ Ｖとした。
この結果を図２に示した。[0019] Batteries A1, A2, and
A charge/discharge cycle test was conducted using A3, A4, and B. Test conditions are charging current 3mA, charge end voltage 4.5
V, discharge current 3 mA, and discharge end voltage 3.0 V. The results are shown in FIG.
【００２０】図２より、本発明電池Ａ１〜Ａ４はいずれ
も比較電池Ｂよりもサイクル特性が向上していることが
判る。また、Ａ１〜Ａ４はいずれも放電時の平均電圧が
３．５ Ｖから ４．０Ｖの間であり、活物質としての
エネルギー密度も従来のものに比べて大きいものとなっ
ている。From FIG. 2, it can be seen that all of the batteries A1 to A4 of the present invention have better cycle characteristics than comparative battery B. Further, in all of A1 to A4, the average voltage during discharge is between 3.5 V and 4.0 V, and the energy density as an active material is also larger than that of conventional materials.
【００２１】以上のように、本発明は広く一般式Ｌｉｘ
Ｍｙ Ｎｚ Ｏ２ で表される多元系複合酸化物につ
いて応用が可能である。As described above, the present invention broadly covers the general formula Lix
Application is possible to a multi-component complex oxide represented by My Nz O2.
【００２２】[0022]
【発明の効果】上述した如く、一般式Ｌｉｘ Ｍｙ Ｎ
ｚＯ２ （但し、ＭはＦｅ，Ｃｏ，Ｎｉの群から選ばれ
た少なくとも１種を表し、ＮはＴｉ，Ｖ，Ｃｒ，Ｍｎの
群から選ばれた少なくとも１種を表す。Ｘ，Ｙ，Ｚはそ
れぞれ ０．８≦Ｘ≦１．２ ， ０．８≦Ｙ＋Ｚ≦１
．２ ，０＜Ｙ＜１．２ ，０＜Ｚ＜１．２ の数値を
表す。）で表される正極活物質を用いた電池は、ＬｉＣ
ｏＯ２ を正極活物質として用いた電池に比べて充放電
サイクルにともなう容量劣化が小さい。その結果、本発
明による正極と負極及び電解質とを具備したリチウム二
次電池は、従来のリチウム二次電池に比べサイクル特性
が大幅に改善されたエネルギー密度の大きいものとなる
。[Effect of the invention] As mentioned above, the general formula Lix My N
zO2 (However, M represents at least one selected from the group of Fe, Co, and Ni; N represents at least one selected from the group of Ti, V, Cr, and Mn; X, Y, and Z are 0.8≦X≦1.2, 0.8≦Y+Z≦1, respectively
．． 2, 0<Y<1.2, 0<Z<1.2. ) A battery using a positive electrode active material represented by LiC
Compared to batteries using oO2 as the positive electrode active material, capacity deterioration due to charge/discharge cycles is small. As a result, a lithium secondary battery including a positive electrode, a negative electrode, and an electrolyte according to the present invention has significantly improved cycle characteristics and high energy density compared to conventional lithium secondary batteries.
【００２３】なお、本発明は実施例に記載された負極、
電解質、セパレータ及び電池形状などに限定されるもの
ではなく、負極に有機焼成体を用いるものや、電解液、
セパレータの代わりに固体電解質を用いたものなどにも
適用可能である。[0023] The present invention also applies to the negative electrodes described in the Examples,
It is not limited to electrolytes, separators, battery shapes, etc., but may also include those using an organic fired body for the negative electrode, electrolytes,
It is also applicable to those using solid electrolytes instead of separators.
【図１】本発明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 lithium secondary battery of the present invention.
【図２】本発明電池及び比較例電池のサイクル数と容量
保持率との関係図である。FIG. 2 is a diagram showing the relationship between the number of cycles and the capacity retention rate of a battery of the present invention and a battery of a comparative example.
１ 絶縁リング ２ 負極集電板 ３ 負極 ４ 負極集電体 ５ セパレータ ６ 正極 ７ 正極集電板 1 Insulation ring 2 Negative electrode current collector plate 3 Negative electrode 4 Negative electrode current collector 5 Separator 6 Positive electrode 7 Positive electrode current collector plate
Claims (1)
Ｎｚ Ｏ２ で表されるものであることを特徴とする
リチウム二次電池。但し、ＭはＦｅ，Ｃｏ，Ｎｉの群か
ら選ばれた少なくとも１種を表し、ＮはＴｉ，Ｖ，Ｃｒ
，Ｍｎの群から選ばれた少なくとも１種を表す。[Claim 1] The active material of the positive electrode has the general formula Lix My
A lithium secondary battery characterized by being represented by NzO2. However, M represents at least one species selected from the group of Fe, Co, and Ni, and N represents Ti, V, and Cr.
, Mn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3050487A JPH04267053A (en) | 1991-02-21 | 1991-02-21 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3050487A JPH04267053A (en) | 1991-02-21 | 1991-02-21 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04267053A true JPH04267053A (en) | 1992-09-22 |
Family
ID=12860277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3050487A Pending JPH04267053A (en) | 1991-02-21 | 1991-02-21 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04267053A (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0831408A (en) * | 1994-05-13 | 1996-02-02 | Matsushita Electric Ind Co Ltd | Positive electrode for non-aqueous electrolyte lithium secondary battery and manufacture thereof |
| US6120707A (en) * | 1997-06-19 | 2000-09-19 | Matsushita Electric Industrial Co., Ltd. | Secondary battery |
| EP1130665A1 (en) * | 2000-03-03 | 2001-09-05 | Nissan Motor Company, Limited | Positive electrode material for battery and nonaqueous electrolyte secondary battery |
| EP1130664A1 (en) * | 2000-03-03 | 2001-09-05 | Nissan Motor Company, Limited | Positive electrode material and cell for nonaqueous electrolyte secondary battery |
| US6506520B1 (en) | 1998-12-02 | 2003-01-14 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| US6605386B1 (en) | 1998-12-02 | 2003-08-12 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| US6653019B1 (en) | 1998-06-03 | 2003-11-25 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| US6821675B1 (en) | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
| US6824920B1 (en) | 1997-06-03 | 2004-11-30 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| JP2005251756A (en) * | 2005-04-04 | 2005-09-15 | Nippon Chem Ind Co Ltd | Lithium secondary battery positive electrode active substance, its manufacturing method, and lithium secondary battery |
| US7579114B2 (en) | 2001-09-13 | 2009-08-25 | Panasonic Corporation | Method of preparing positive electrode active material |
| US7592100B2 (en) | 2001-03-22 | 2009-09-22 | Panasonic Corporation | Positive-electrode active material and nonaqueous-electrolyte secondary battery containing the same |
| US7935443B2 (en) | 2001-06-27 | 2011-05-03 | Panasonic Corporation | Lithium nickel-manganese-cobalt oxide positive electrode active material |
| US8153297B2 (en) | 2002-08-05 | 2012-04-10 | Panasonic Corporation | Positive electrode active material and non-aqueous electrolyte secondary battery containing the same |
| US8257865B2 (en) | 2001-11-20 | 2012-09-04 | Tdk Corporation | Electrode active material, electrode, lithium-ion secondary battery, method of making electrode active material, and method of making lithium-ion secondary battery |
| US8349287B2 (en) | 2001-10-25 | 2013-01-08 | Panasonic Corporation | Positive electrode active material and non-aqueous electrolyte secondary battery containing the same |
| US9716265B2 (en) | 2014-08-01 | 2017-07-25 | Apple Inc. | High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries |
| US10084187B2 (en) | 2016-09-20 | 2018-09-25 | Apple Inc. | Cathode active materials having improved particle morphologies |
| US10141572B2 (en) | 2016-03-14 | 2018-11-27 | Apple Inc. | Cathode active materials for lithium-ion batteries |
| US10297821B2 (en) | 2015-09-30 | 2019-05-21 | Apple Inc. | Cathode-active materials, their precursors, and methods of forming |
| US10597307B2 (en) | 2016-09-21 | 2020-03-24 | Apple Inc. | Surface stabilized cathode material for lithium ion batteries and synthesizing method of the same |
| US10615413B2 (en) | 2013-03-12 | 2020-04-07 | Apple Inc. | High voltage, high volumetric energy density li-ion battery using advanced cathode materials |
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|---|---|---|---|---|
| JPH0831408A (en) * | 1994-05-13 | 1996-02-02 | Matsushita Electric Ind Co Ltd | Positive electrode for non-aqueous electrolyte lithium secondary battery and manufacture thereof |
| US6824920B1 (en) | 1997-06-03 | 2004-11-30 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| US6120707A (en) * | 1997-06-19 | 2000-09-19 | Matsushita Electric Industrial Co., Ltd. | Secondary battery |
| US6653019B1 (en) | 1998-06-03 | 2003-11-25 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| US6821675B1 (en) | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
| US6506520B1 (en) | 1998-12-02 | 2003-01-14 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| US6605386B1 (en) | 1998-12-02 | 2003-08-12 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
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| US7579114B2 (en) | 2001-09-13 | 2009-08-25 | Panasonic Corporation | Method of preparing positive electrode active material |
| US7670723B2 (en) | 2001-09-13 | 2010-03-02 | Panasonic Corporation | Positive electrode active material, production method thereof and non-aqueous electrolyte secondary battery |
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| JP4487194B2 (en) * | 2005-04-04 | 2010-06-23 | 日本化学工業株式会社 | Lithium secondary battery positive electrode active material, method for producing the same, and lithium secondary battery |
| US10615413B2 (en) | 2013-03-12 | 2020-04-07 | Apple Inc. | High voltage, high volumetric energy density li-ion battery using advanced cathode materials |
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| US10128494B2 (en) | 2014-08-01 | 2018-11-13 | Apple Inc. | High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries |
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| US11362331B2 (en) | 2016-03-14 | 2022-06-14 | Apple Inc. | Cathode active materials for lithium-ion batteries |
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