JPH08264179A - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JPH08264179A JPH08264179A JP7094351A JP9435195A JPH08264179A JP H08264179 A JPH08264179 A JP H08264179A JP 7094351 A JP7094351 A JP 7094351A JP 9435195 A JP9435195 A JP 9435195A JP H08264179 A JPH08264179 A JP H08264179A
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- Japan
- Prior art keywords
- positive electrode
- lithium
- battery
- active material
- electrode active
- Prior art date
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Classifications
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- 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
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- 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、リチウム電池に係わ
り、詳しくは高容量なリチウム電池を提供することを目
的とした、正極活物質の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium battery, and more particularly to improvement of a positive electrode active material for the purpose of providing a high capacity lithium battery.
【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図るこ
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,
The lithium battery does not need to consider the decomposition voltage of water,
Attention is being paid because it is possible to increase the voltage by appropriately selecting the positive electrode active material.
【０００３】この種の電池の代表的な正極活物質は金属
酸化物である。例えば、正極活物質としてＬｉＣｏＯ2
（リチウム−コバルト複合酸化物）を使用したリチウム
電池が既に実用化されている。ＬｉＣｏＯ2 は、リチウ
ム原料とコバルト原料との所定の割合の混合物を所定の
温度で焼成する固相法により、１２０ｍＡｈ／ｇ以上の
かなり大きな容量を有するものが容易に得られる。A typical positive electrode active material for this type of battery is a metal oxide. For example, as a positive electrode active material, LiCoO 2
A lithium battery using (lithium-cobalt composite oxide) has already been put into practical use. LiCoO 2 having a considerably large capacity of 120 mAh / g or more can be easily obtained by a solid phase method in which a mixture of a lithium raw material and a cobalt raw material in a predetermined ratio is fired at a predetermined temperature.
【０００４】これに対して、ＬｉＴｉ2 Ｏ4 等のリチウ
ム−チタン複合酸化物については、結晶構造からは充放
電に適していると思われるにもかかわらず、この種の電
池の正極活物質としては従来殆ど検討されていない。こ
れは、リチウム−チタン複合酸化物は、充放電電位が低
いために容量が総じて小さいことによるものである。On the other hand, lithium-titanium composite oxides such as LiTi 2 O 4 are suitable as a positive electrode active material for batteries of this type, although they are considered to be suitable for charge and discharge due to their crystal structure. Has not been studied so far. This is because the lithium-titanium composite oxide has a low charge / discharge potential and therefore has a generally small capacity.
【０００５】そこで、リチウム−チタン複合酸化物の正
極材料としての実用化を図るべく鋭意研究した結果、本
発明者らは、リチウム原料及びチタン原料の混合物を熱
処理する際にさらに特定の化合物を添加するようにすれ
ば、ＬｉＣｏＯ2 と比べても遜色のない大きな容量を有
する複合酸化物が固相法により容易に得られることを見
出した。Then, as a result of earnest research aimed at putting the lithium-titanium composite oxide into practical use as a positive electrode material, the present inventors have further added a specific compound when heat-treating a mixture of a lithium raw material and a titanium raw material. By doing so, it was found that a complex oxide having a large capacity comparable to that of LiCoO 2 can be easily obtained by the solid phase method.
【０００６】本発明は、かかる知見に基づきなされたも
のであって、その目的とするところは、特定の複合酸化
物を正極活物質とする高容量なリチウム電池を提供する
にある。The present invention has been made on the basis of such findings, and an object thereof is to provide a high-capacity lithium battery using a specific composite oxide as a positive electrode active material.
【０００７】[0007]
【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電池（本発明電池）は、式Ｌｉ
x Ｔｉ1-y Ｍy Ｏz （式中、ＭはＢ、Ｎａ、Ｍｇ、Ａ
ｌ、Ｓｉ、Ｋ、Ｃａ、Ｓｃ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｚｒ、Ｎｂ、Ｒ
ｕ、Ａｇ、Ｔａ、Ｂｉ、Ｉｎ、Ｍｏ及びＷよりなる群か
ら選ばれた少なくとも一種の元素、０＜ｘ≦１．３、
０．０２≦ｙ≦０．２０、１．８≦ｚ≦２．２）で表さ
れる複合酸化物を正極活物質とするものである。To achieve the above object, the lithium battery according to the present invention (the battery of the present invention) has the formula Li
x Ti in 1-y M y O z (wherein, M is B, Na, Mg, A
l, Si, K, Ca, Sc, V, Cr, Mn, Fe, C
o, Ni, Cu, Zn, Ga, Ge, Zr, Nb, R
at least one element selected from the group consisting of u, Ag, Ta, Bi, In, Mo and W, 0 <x ≦ 1.3,
The composite oxide represented by 0.02 ≦ y ≦ 0.20 and 1.8 ≦ z ≦ 2.2) is used as the positive electrode active material.
【０００８】本発明電池のリチウムを活物質とする負極
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電極材料に使用して
作製される。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、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）及び正極に対して電位の卑な金属酸化物（例えばニ
オブ酸化物）が例示される。The negative electrode using lithium as an active material of the battery of the present invention is produced by using a material capable of electrochemically absorbing and desorbing lithium ions or metallic lithium as an electrode material. Examples of substances capable of electrochemically absorbing and desorbing lithium ions include carbon materials such as graphite, coke, and organic burned materials, lithium alloys (lithium-aluminum alloys, lithium-lead alloys, lithium-tin alloys) and Examples are base metal oxides having a potential lower than that of the positive electrode (for example, niobium oxide).
【０００９】本発明電池の正極活物質は、式Ｌｉx Ｔｉ
1-y Ｍy Ｏz （式中、ＭはＢ、Ｎａ、Ｍｇ、Ａｌ、Ｓ
ｉ、Ｋ、Ｃａ、Ｓｃ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎ
ｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｚｒ、Ｎｂ、Ｒｕ、Ａ
ｇ、Ｔａ、Ｂｉ、Ｉｎ、Ｍｏ及びＷよりなる群から選ば
れた少なくとも一種の元素、０＜ｘ≦１．３、０．０２
≦ｙ≦０．２０、１．８≦ｚ≦２．２）で表される複合
酸化物である。この複合酸化物は、例えばリチウム化合
物（ＬｉＯＨ、Ｌｉ2 ＣＯ3 など）と、チタン化合物
（ＴｉＯ2 、Ｔｉ（ＯＨ）4 など）と、元素Ｍの酸化
物、水酸化物、炭酸塩又は硝酸塩などとの混合物を乾燥
空気雰囲気下にて４００〜１０００°Ｃの温度で４〜４
０時間熱処理することにより得られる。式中のｙの値
（チタン置換量）が０．０２〜０．２０に規制されるの
は、ｙの値が０．０２未満の場合は充放電電位が充分に
高くならならないため、一方ｙの値が０．２０を越える
とリチウム吸蔵放出量が減少するため、いずれの場合も
複合酸化物の容量が小さくなり、本発明が企図する高容
量なリチウム電池が得られなくなるからである。The positive electrode active material of the battery of the present invention has the formula Li x Ti
1-y M y O z (wherein, M is B, Na, Mg, Al, S
i, K, Ca, Sc, V, Cr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ge, Zr, Nb, Ru, A
at least one element selected from the group consisting of g, Ta, Bi, In, Mo and W, 0 <x ≦ 1.3, 0.02
≦ y ≦ 0.20, 1.8 ≦ z ≦ 2.2). This composite oxide is, for example, a lithium compound (LiOH, Li 2 CO 3, etc.), a titanium compound (TiO 2 , Ti (OH) 4, etc.), an oxide of element M, a hydroxide, a carbonate or a nitrate. 4 to 4 at a temperature of 400 to 1000 ° C under a dry air atmosphere.
Obtained by heat treatment for 0 hours. The value of y in the formula (titanium substitution amount) is regulated to 0.02 to 0.20 because the charge / discharge potential does not become sufficiently high when the value of y is less than 0.02. If the value of exceeds 0.20, the amount of lithium occlusion and release decreases, and in any case, the capacity of the composite oxide becomes small, and the high capacity lithium battery contemplated by the present invention cannot be obtained.
【００１０】本発明の特徴は、充放電電位の低いリチウ
ム−チタン複合酸化物に代えて、充放電電位の高い特定
の複合酸化物を正極活物質として使用した点にある。そ
れゆえ、非水電解質など、電池を構成する他の部材につ
いては、従来リチウム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 composite oxide having a high charge / discharge potential is used as a positive electrode active material in place of the lithium-titanium composite oxide having a low charge / discharge potential. Therefore, for the other members constituting the battery such as the non-aqueous electrolyte, various materials conventionally proposed or put into practical use for lithium batteries can be used without particular limitation.
【００１１】例えば、非水電解質として液体電解質を使
用する場合の溶媒としては、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 ＳＯ
2 ）2 、ＬｉＢＦ4 、ＬｉＡｓＦ6 が、それぞれ例示さ
れる。また、固体電解質を使用することも可能である。For example, when the liquid electrolyte is used as the non-aqueous electrolyte, the solvent is a high dielectric constant solvent such as ethylene carbonate, vinylene carbonate or propylene carbonate, or a diethyl carbonate, dimethyl carbonate or 1,2-dimethoxyethane solvent. , 1,2-
A mixed solvent with a low boiling point solvent such as diethoxyethane and ethoxymethoxyethane is LiPF 6 ,
LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO
2 ) 2 , LiBF 4 , and LiAsF 6 are each exemplified. It is also possible to use a solid electrolyte.
【００１２】[0012]
【作用】充放電電位の高い特定の複合酸化物が正極活物
質として使用されているので、本発明電池は、ＬｉＴｉ
2 Ｏ4 等のリチウム−チタン複合酸化物を正極活物質と
して使用したリチウム電池に比べて、容量が格段大き
い。Since a specific composite oxide having a high charge / discharge potential is used as the positive electrode active material, the battery of the present invention is made of LiTi
The capacity is significantly larger than that of a lithium battery using a lithium-titanium composite oxide such as 2 O 4 as a positive electrode active material.
【００１３】[0013]
【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 The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible.
【００１４】（実施例１〜２９） 〔正極の作製〕ＬｉＯＨ（リチウム原料）と、ＴｉＯ2
（チタン原料）と、表１に示す各原料（Ｍ原料）とを種
々の割合で混合し、乾燥空気雰囲気下にて８５０°Ｃで
２０時間熱処理（焼成）し、石川式らいかい乳鉢にて粉
砕して、正極活物質としての種々の複合酸化物粉末を作
製した。表１中のｙは、各複合酸化物粉末の作製におい
てＬｉＯＨとＴｉＯ2 と各Ｍ原料とをＬｉ：Ｔｉ：Ｍの
原子比が０．５：１−ｙ：ｙとなるように混合したこと
を示す。例えば、ｙの値が０．０２の実施例１の複合酸
化物は、ＬｉＯＨとＴｉＯ2 とＢ2 Ｏ3 とをＬｉ：Ｔ
ｉ：Ｍの原子比が０．５：０．９８：０．０２となるよ
うに混合して得た混合物を焼成して得たものであり、組
成式Ｌｉ0.5 Ｔｉ0.98Ｂ0.02Ｏ2 で表されるものであ
る。Examples 1 to 29 [Preparation of Positive Electrode] LiOH (lithium raw material) and TiO 2
(Titanium raw material) and each raw material (M raw material) shown in Table 1 are mixed at various ratios, heat-treated (baked) at 850 ° C. for 20 hours in a dry air atmosphere, and then used in an Ishikawa-type Raikai mortar. It was pulverized to prepare various composite oxide powders as a positive electrode active material. Y in Table 1 is that LiOH, TiO 2 and each M raw material were mixed in the preparation of each composite oxide powder so that the atomic ratio of Li: Ti: M was 0.5: 1-y: y. Indicates. For example, in the composite oxide of Example 1 in which the value of y is 0.02, LiOH, TiO 2, and B 2 O 3 are mixed with Li: T.
It is obtained by firing a mixture obtained by mixing so that the atomic ratio of i: M is 0.5: 0.98: 0.02, and is represented by the composition formula Li 0.5 Ti 0.98 B 0.02 O 2 . It is what is done.
【００１５】[0015]
【表１】 [Table 1]
【００１６】次いで、各複合酸化物粉末と、導電剤とし
てのアセチレンブラックと、結着剤としてのフッ素樹脂
粉末とを、重量比率９０：６：４で混合して正極合剤を
調製し、この正極合剤を成形圧２トン／ｃｍ2 で直径２
０ｍｍの円盤状に加圧成型し、２５０°Ｃで２時間熱処
理して正極を作製した。Next, each composite oxide powder, acetylene black as a conductive agent, and fluororesin powder as a binder are mixed in a weight ratio of 90: 6: 4 to prepare a positive electrode mixture. diameter cathode mixture at a molding pressure of 2 t / cm 2 2
A 0 mm disk shape was pressure-molded and heat-treated at 250 ° C. for 2 hours to prepare a positive electrode.
【００１７】〔負極の作製〕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。[Preparation of Negative Electrode] A rolled lithium metal plate was punched into a disk having a diameter of 20 mm to prepare a negative electrode.
【００１８】〔非水電解液の調製〕プロピレンカーボネ
ートと１，２−ジメトキシエタンとの体積比１：１の混
合溶媒に、ＬｉＣｌＯ4 を１モル／リットル溶かして非
水電解液を調製した。[Preparation of Non-Aqueous Electrolyte] LiClO 4 was dissolved in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane at a volume ratio of 1: 1 to prepare a non-aqueous electrolyte.
【００１９】〔電池の組立〕以上の各正極と負極と非水
電解液とを用いて扁平型のリチウム電池Ａ１〜Ａ２９を
組み立てた（電池寸法：直径２４．０ｍｍ、厚さ３．０
ｍｍ）。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、これに非水電解液を含浸させた。[Battery Assembly] Flat lithium batteries A1 to A29 were assembled using the above positive and negative electrodes and a non-aqueous electrolyte (battery size: diameter 24.0 mm, thickness 3.0).
mm). As the separator, a polypropylene microporous film was used and impregnated with the non-aqueous electrolyte.
【００２０】図１は、組み立てたリチウム電池の模式的
断面図であり、図示のリチウム電池Ａは、正極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 schematic cross-sectional view of the assembled lithium battery. The lithium battery A shown in the drawing has a positive electrode 1, a negative electrode 2, a separator 3 for separating these electrodes 1 and 2 from each other, a positive electrode can 4, a negative electrode. Can 5, positive electrode current collector 6, negative electrode current collector 7
And an insulating packing 8 made of polypropylene.
【００２１】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両極缶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、また負極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 by positive and negative bipolar cans 4 and 5 facing each other through a separator 3 impregnated with a non-aqueous electrolyte solution, and the positive electrode 1 is a positive electrode current collector. 6 to the positive electrode can 4 and the negative electrode 2 to the negative electrode current collector 7
It is connected to the negative electrode can 5 via the so that the chemical energy generated inside the battery can be taken out as electric energy from both terminals of the positive electrode can 4 and the negative electrode can 5.
【００２２】（比較例１）ＬｉＯＨとＴｉＯ2 とをモル
比０．５：１で混合し、８５０°Ｃで２０時間熱処理し
た後、石川式らいかい乳鉢にて粉砕して、組成式ＬｉＴ
ｉ2 Ｏ4 で表されるリチウム−チタン複合酸化物粉末を
作製した。(Comparative Example 1) LiOH and TiO 2 were mixed at a molar ratio of 0.5: 1, heat-treated at 850 ° C. for 20 hours, and then crushed in an Ishikawa-type Raikai mortar to prepare a composition formula LiT.
A lithium-titanium composite oxide powder represented by i 2 O 4 was produced.
【００２３】次いで、このリチウム−チタン複合酸化物
粉末を正極活物質として使用したこと以外は実施例１〜
２９と同様にして、比較電池Ｂ１を組み立てた。Then, Examples 1 to 1 were repeated except that this lithium-titanium composite oxide powder was used as a positive electrode active material.
A comparative battery B1 was assembled in the same manner as 29.
【００２４】（比較例２〜２７）ＬｉＯＨと、ＴｉＯ2
と、表２に示す各原料（Ｍ原料）とを、Ｌｉ：Ｔｉ：Ｍ
の原子比が０．５：０．７５：０．２５となるように混
合し、乾燥空気雰囲気下にて８５０°Ｃで２０時間熱処
理（焼成）し、石川式らいかい乳鉢にて粉砕して、正極
活物質としての種々の複合酸化物粉末を作製した。(Comparative Examples 2 to 27) LiOH and TiO 2
And each raw material (M raw material) shown in Table 2, Li: Ti: M
Are mixed to have an atomic ratio of 0.5: 0.75: 0.25, heat-treated (baked) for 20 hours at 850 ° C in a dry air atmosphere, and crushed in an Ishikawa-type Raikai mortar. Various composite oxide powders as positive electrode active materials were prepared.
【００２５】[0025]
【表２】 [Table 2]
【００２６】次いで、これらの各複合酸化物粉末を正極
活物質として使用したこと以外は実施例１〜２９と同様
にして、比較電池Ｂ２〜Ｂ２７を組み立てた。Next, comparative batteries B2 to B27 were assembled in the same manner as in Examples 1 to 29 except that each of these composite oxide powders was used as the positive electrode active material.
【００２７】〔放電容量〕各電池を１ｍＡで４．３Ｖま
で充電した後、３ｍＡで２．０Ｖまで放電して、各正極
活物質の放電容量を求めた。結果を先の表１又は表２に
示す。また、本発明電池Ａ１〜Ａ４及び比較電池Ｂ１，
Ｂ２の結果については、図２にも示す。図２は、使用せ
る複合酸化物を表す組成式Ｌｉ0.5 Ｔｉ1-y Ｂy Ｏ2 中
のｙの値と放電容量の関係を、縦軸に正極活物質の単位
重量当たりの放電容量を、また横軸にｙの値をとって、
示したグラフである。さらに、本発明電池Ａ２と比較電
池Ｂ１の各放電曲線を図３に示す。図３は、縦軸に電池
電圧（Ｖ）を、また横軸に放電容量（ｍＡｈ／ｇ）をと
って示したグラフである。[Discharge Capacity] Each battery was charged to 4.3 V at 1 mA and then discharged to 2.0 V at 3 mA to determine the discharge capacity of each positive electrode active material. The results are shown in Table 1 or Table 2 above. Further, the present invention batteries A1 to A4 and the comparative battery B1,
The result of B2 is also shown in FIG. FIG. 2 shows the relationship between the value of y in the composition formula Li 0.5 Ti 1- y By O 2 representing the complex oxide to be used and the discharge capacity, and the vertical axis represents the discharge capacity per unit weight of the positive electrode active material. Also, taking the value of y on the horizontal axis,
It is the graph shown. Further, each discharge curve of the present battery A2 and the comparative battery B1 is shown in FIG. FIG. 3 is a graph in which the vertical axis represents the battery voltage (V) and the horizontal axis represents the discharge capacity (mAh / g).
【００２８】表１及び表２より、本発明電池Ａ１〜Ａ２
９に使用した各正極活物質は、比較電池Ｂ１に使用した
正極活物質（ＬｉＴｉ2 Ｏ4 ：リチウム−チタン複合酸
化物）よりもはるかに大きな放電容量を有することが分
かる。本発明電池Ａ２及びＡ５〜Ａ２９（いずれもｙの
値は０．１）のうちＡ２、Ａ７、Ａ８、Ａ９、Ａ１２〜
Ａ１７、Ａ２４及びＡ２６の正極活物質の放電容量が１
３０ｍＡｈ／ｇ以上と特に大きいことから、Ｔｉの置換
元素ＭとしてはＢ、Ａｌ、Ｓｉ、Ｋ、Ｖ、Ｃｒ、Ｍｎ、
Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ及びＩｎが特に好ましいことが
分かる。また、図２及び表２より、放電容量の大きい正
極活物質を得る上で、ｙの値は０．０２〜０．２０の範
囲内とする必要があることが分かる。なお、Ｂ以外の他
の元素でＴｉを置換する場合についてもｙの値が０．０
２〜０．２０の範囲内とした場合に放電容量の大きい正
極活物質が得られることを確認した。また、ｙの値はリ
チウム量すなわちｘの値に関係なく０．０２〜０．２０
の範囲内とする必要があることも確認した。さらに、図
３より、本発明電池の正極活物質が比較電池の正極活物
質に比べて放電容量が大きい理由が、放電電圧が高いこ
とによるものであることが分かる。From Tables 1 and 2, the batteries A1 and A2 of the present invention are shown.
It can be seen that each positive electrode active material used in No. 9 has a much larger discharge capacity than the positive electrode active material (LiTi 2 O 4 : lithium-titanium composite oxide) used in Comparative Battery B1. A2, A7, A8, A9, A12-of the batteries A2 and A5-A29 of the present invention (y values are 0.1)
The discharge capacity of the positive electrode active material of A17, A24 and A26 is 1
Since it is particularly large at 30 mAh / g or more, the substitutional element M of Ti is B, Al, Si, K, V, Cr, Mn,
It can be seen that Fe, Co, Ni, Ru and In are particularly preferable. Further, it can be seen from FIG. 2 and Table 2 that the value of y needs to be in the range of 0.02 to 0.20 in order to obtain a positive electrode active material having a large discharge capacity. When y is replaced with an element other than B, the value of y is 0.0
It was confirmed that a positive electrode active material having a large discharge capacity was obtained when the content was in the range of 2 to 0.20. The value of y is 0.02 to 0.20 regardless of the amount of lithium, that is, the value of x.
It was also confirmed that it should be within the range. Further, FIG. 3 shows that the reason why the positive electrode active material of the battery of the present invention has a larger discharge capacity than the positive electrode active material of the comparative battery is that the discharge voltage is high.
【００２９】（実施例３０〜３３）ＬｉＯＨとＴｉＯ2
とＢ2 Ｏ3 とＮａＯＨとをＬｉ：Ｔｉ：Ｂ：Ｎａの原子
比が０．５：０．８：０．２−ｐ：ｐ（ｐ＝０．１８、
０．１、０．０５又は０．０２）となるように混合し、
乾燥空気雰囲気下にて８５０°Ｃで２０時間熱処理（焼
成）し、石川式らいかい乳鉢にて粉砕して、正極活物質
としての組成式Ｌｉ0.5 Ｔｉ0.8 Ｂ0.2-p Ｎａp Ｏ2 で
表される４種の複合酸化物粉末を作製した。(Examples 30 to 33) LiOH and TiO 2
And B 2 O 3 and NaOH, the atomic ratio of Li: Ti: B: Na is 0.5: 0.8: 0.2-p: p (p = 0.18,
0.1, 0.05 or 0.02) to mix,
Heat-treated (baked) at 850 ° C for 20 hours in a dry air atmosphere, crushed in an Ishikawa type Raikai mortar, and expressed as a composition formula Li 0.5 Ti 0.8 B 0.2-p Na p O 2 as a positive electrode active material. 4 types of composite oxide powders were prepared.
【００３０】次いで、これらの各複合酸化物粉末を正極
活物質として使用したこと以外は実施例１〜２９と同様
にして、本発明電池Ａ３０（ｐ＝０．１８，ｙ＝０．２
０）、Ａ３１（ｐ＝０．１，ｙ＝０．２０）、Ａ３２
（ｐ＝０．０５，ｙ＝０．２０）、Ａ３３（ｐ＝０．０
２，ｙ＝０．２０）を組み立てた。Then, the battery A30 of the present invention (p = 0.18, y = 0.2) was prepared in the same manner as in Examples 1 to 29 except that each of these composite oxide powders was used as the positive electrode active material.
0), A31 (p = 0.1, y = 0.20), A32
(P = 0.05, y = 0.20), A33 (p = 0.0
2, y = 0.20) was assembled.
【００３１】（比較例２８）ＬｉＯＨとＴｉＯ2 とＢ2
Ｏ3 とＮａＯＨとをＬｉ：Ｔｉ：Ｂ：Ｎａの原子比が
０．５：０．７５：０．２：０．０５となるように混合
し、乾燥空気雰囲気下にて８５０°Ｃで２０時間熱処理
（焼成）し、石川式らいかい乳鉢にて粉砕して、正極活
物質としての複合酸化物粉末（ｙ＝０．２５）を作製し
た。(Comparative Example 28) LiOH, TiO 2 and B 2
O 3 and NaOH were mixed so that the atomic ratio of Li: Ti: B: Na was 0.5: 0.75: 0.2: 0.05, and 20 at 850 ° C in a dry air atmosphere. It was heat-treated (calcined) for a period of time and crushed in an Ishikawa type mortar mortar to prepare a composite oxide powder (y = 0.25) as a positive electrode active material.
【００３２】次いで、この複合酸化物粉末を正極活物質
として使用したこと以外は実施例１〜２９と同様にし
て、比較電池Ｂ２８を組み立てた。Then, a comparative battery B28 was assembled in the same manner as in Examples 1 to 29 except that this composite oxide powder was used as the positive electrode active material.
【００３３】〔放電容量〕各電池を先と同じ条件で充放
電して、放電容量を求めた。結果を表３に示す。[Discharge Capacity] Each battery was charged and discharged under the same conditions as above to determine the discharge capacity. The results are shown in Table 3.
【００３４】[0034]
【表３】 [Table 3]
【００３５】表３に示すように、本発明電池Ａ３０〜Ａ
３３に使用した正極活物質の放電容量が大きいのに対し
て比較電池Ｂ２８に使用した正極活物質の放電容量は極
めて小さい。このことから、正極活物質として使用する
複合酸化物はチタンの一部を２種以上の置換元素Ｍで置
換したものであってもよいが、置換元素ＭによるＴｉの
トータル置換量を式Ｌｉx Ｔｉ1-y Ｍy Ｏz 中のｙの値
が０．０２〜０．２０の範囲となるようにする必要があ
ることが分かる。なお、他の置換元素Ｍについてもｙの
値がこの範囲を外れると、正極活物質の放電容量が低下
することを確認した。As shown in Table 3, the batteries of the present invention A30 to A30
The discharge capacity of the positive electrode active material used for 33 is large, whereas the discharge capacity of the positive electrode active material used for Comparative Battery B28 is extremely small. From this fact, the composite oxide used as the positive electrode active material may be one obtained by substituting a part of titanium with two or more substitution elements M, but the total substitution amount of Ti by the substitution element M is represented by the formula Li x. It can be seen that it is necessary to set the value of y in Ti 1-y M y O z within the range of 0.02 to 0.20. It was confirmed that the discharge capacity of the positive electrode active material was also reduced when the value of y was out of this range for the other substitutional elements M.
【００３６】上記実施例では、本発明を扁平型のリチウ
ム二次電池に適用する場合を例に挙げて説明したが、本
発明は電池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とともに、一次電池にも適用可能な
ものである。In the above embodiments, the case where the present invention is applied to the flat type lithium secondary battery has been described as an example, but the present invention is not particularly limited in the shape of the battery, and is a cylindrical type or a square type. The present invention can be applied to various other shapes of lithium secondary batteries, and can also be applied to primary batteries.
【００３７】また、上記実施例では、非水電解質として
液体電解質を使用したが、本発明は固体電解質電池にも
適用可能なものである。Further, although the liquid electrolyte is used as the non-aqueous electrolyte in the above-mentioned embodiment, the present invention can be applied to the solid electrolyte battery.
【００３８】[0038]
【発明の効果】正極活物質として充放電電位の高い特定
の複合酸化物が使用されているので、本発明電池は容量
が大きい。Since the specific composite oxide having a high charge / discharge potential is used as the positive electrode active material, the battery of the present invention has a large capacity.
【図１】実施例で組み立てた扁平型のリチウム電池の断
面図である。FIG. 1 is a cross-sectional view of a flat type lithium battery assembled in an example.
【図２】式Ｌｉ0.5 Ｔｉ1-y Ｂy Ｏ2 中のｙの値と放電
容量の関係を示すグラフである。2 is a graph showing the relationship between the value and the discharge capacity of the formula Li 0.5 Ti 1-y B y O 2 in of y.
【図３】本発明電池及び比較電池の放電曲線を示すグラ
フである。FIG. 3 is a graph showing discharge curves of a battery of the present invention and a comparative battery.
Ａ リチウム電池 １ 正極 ２ 負極 ３ セパレータ A lithium battery 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 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koji Nishio 2-5-5 Keihan Hondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Toshihiko Saito 2-chome, Keihanhondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd.
Claims (2)
Ｂ、Ｎａ、Ｍｇ、Ａｌ、Ｓｉ、Ｋ、Ｃａ、Ｓｃ、Ｖ、Ｃ
ｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇ
ｅ、Ｚｒ、Ｎｂ、Ｒｕ、Ａｇ、Ｔａ、Ｂｉ、Ｉｎ、Ｍｏ
及びＷよりなる群から選ばれた少なくとも一種の元素、
０＜ｘ≦１．３、０．０２≦ｙ≦０．２０、１．８≦ｚ
≦２．２）で表される複合酸化物を正極活物質とするリ
チウム電池。1. The formula Li x Ti 1-y M y O z (wherein M is B, Na, Mg, Al, Si, K, Ca, Sc, V, C).
r, Mn, Fe, Co, Ni, Cu, Zn, Ga, G
e, Zr, Nb, Ru, Ag, Ta, Bi, In, Mo
And at least one element selected from the group consisting of W,
0 <x ≦ 1.3, 0.02 ≦ y ≦ 0.20, 1.8 ≦ z
A lithium battery using the composite oxide represented by ≦ 2.2) as a positive electrode active material.
Ｂ、Ａｌ、Ｓｉ、Ｋ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎ
ｉ、Ｒｕ及びＩｎよりなる群から選ばれた少なくとも一
種の元素、０＜ｘ≦１．３、０．０２≦ｙ≦０．２０、
１．８≦ｚ≦２．２）で表される複合酸化物を正極活物
質とするリチウム電池。2. The formula Li x Ti 1-y M y O z (wherein M is B, Al, Si, K, V, Cr, Mn, Fe, Co, N
at least one element selected from the group consisting of i, Ru and In, 0 <x ≦ 1.3, 0.02 ≦ y ≦ 0.20,
A lithium battery comprising a composite oxide represented by 1.8 ≦ z ≦ 2.2) as a positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09435195A JP3197779B2 (en) | 1995-03-27 | 1995-03-27 | Lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09435195A JP3197779B2 (en) | 1995-03-27 | 1995-03-27 | Lithium battery |
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| Publication Number | Publication Date |
|---|---|
| JPH08264179A true JPH08264179A (en) | 1996-10-11 |
| JP3197779B2 JP3197779B2 (en) | 2001-08-13 |
Family
ID=14107869
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09435195A Expired - Fee Related JP3197779B2 (en) | 1995-03-27 | 1995-03-27 | Lithium battery |
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| Country | Link |
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