JPH07134986A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH07134986A JPH07134986A JP5305839A JP30583993A JPH07134986A JP H07134986 A JPH07134986 A JP H07134986A JP 5305839 A JP5305839 A JP 5305839A JP 30583993 A JP30583993 A JP 30583993A JP H07134986 A JPH07134986 A JP H07134986A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- positive electrode
- battery
- composite oxide
- iron composite
- 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.)
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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、非水電解質電池に関す
る。TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte 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、
金属リチウム又はリチウムイオンを吸蔵、放出すること
が可能な合金若しくは炭素材料を負極材料とする非水電
解質電池が、高容量化が可能な電池として注目されてい
る。2. Description of the Related Art In recent years,
A non-aqueous electrolyte battery that uses an alloy or a carbon material capable of inserting and extracting metallic lithium or lithium ions as a negative electrode material has been attracting attention as a battery that can have a high capacity.
【０００３】この種の電池に用いられる正極活物質とし
ては、種々のリチウム−遷移金属複合酸化物が提案され
ており、例えばリチウム−コバルト複合酸化物（ＬｉＣ
ｏＯ2 など）及びリチウム−ニッケル複合酸化物（Ｌｉ
ＮｉＯ2 など）は、既に実用されており、原材料を所定
の割合で混合し、焼成するだけで、１００〜１２０ｍＡ
ｈ／ｇもの大きな容量を有するものが得られる。Various lithium-transition metal composite oxides have been proposed as the positive electrode active material used in this type of battery, for example, lithium-cobalt composite oxide (LiC).
oO 2 ) and lithium-nickel composite oxide (Li
NiO 2 etc.) has already been put to practical use, and 100 to 120 mA can be obtained by simply mixing the raw materials at a predetermined ratio and firing.
Those having a large capacity of h / g can be obtained.
【０００４】しかしながら、リチウム−遷移金属複合酸
化物のうちリチウム−鉄複合酸化物は、鉄が自然に豊富
に存在する資源であることから安価に供給し得るという
製造コスト面での利点があるにもかかわらず、従来、こ
の種の電池の正極活物質として、実用化はもとより、殆
ど検討すらされていなかった。これは、ＬｉＦｅＯ2の
容量が２０ｍＡｈ／ｇ程度と小さいことから、リチウム
−鉄複合酸化物は、総じて容量が小さく非水電解質電池
の正極活物質としては使用し得ないものと誤信されてい
たためである。However, among the lithium-transition metal composite oxides, the lithium-iron composite oxide has an advantage in terms of manufacturing cost that iron can be supplied inexpensively because it is a resource in which iron is naturally abundant. Nonetheless, as a positive electrode active material for this type of battery, it has not been practically studied or even studied so far. This is because the capacity of LiFeO 2 was as small as about 20 mAh / g, and it was mistakenly believed that the lithium-iron composite oxide had a small capacity in general and could not be used as the positive electrode active material of a non-aqueous electrolyte battery. is there.
【０００５】本発明は、以上の事情に鑑みなされたもの
であって、その目的とするところは、ＬｉＮｉＯ2 など
と比較しても遜色のない大きな容量を有するリチウム−
鉄複合酸化物を正極活物質とする新規、有用な非水電解
質電池を提供するにある。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lithium battery having a large capacity comparable to that of LiNiO 2.
It is to provide a new and useful non-aqueous electrolyte battery using an iron composite oxide as a positive electrode active material.
【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
の本発明に係る非水電解質電池（以下「本発明電池」と
称する。）は、正極と、金属リチウム又はリチウムイオ
ンを吸蔵、放出することが可能な物質を負極材料とする
負極とを備える非水電解質電池において、前記正極の活
物質として、式：Ｌｉx ＦｅＯy （但し、１．２５≦ｘ
≦５．０５、１．８≦ｙ≦４．０２５）で表されるリチ
ウム−鉄複合酸化物が用いられてなる。A non-aqueous electrolyte battery according to the present invention (hereinafter referred to as "the battery of the present invention") according to the present invention for achieving the above object stores a positive electrode and metallic lithium or lithium ions. In a non-aqueous electrolyte battery including a negative electrode using a substance that can be used as a negative electrode material, the positive electrode active material has the formula: Li x FeO y (where 1.25 ≦ x
≦ 5.05, 1.8 ≦ y ≦ 4.025) is used.
【０００７】式：Ｌｉx ＦｅＯy 中のｘ、すなわちＬｉ
とＦｅとのモル比の値が１．２５〜５．０５に規制され
るのは、ｘがこの範囲を外れると容量が急激に低下する
からである。式：Ｌｉx ＦｅＯy 中のｙは、ｘが大きく
なるにつれて大きくなり、１．２５≦ｘ≦５．０５にお
いて、ｙは１．８〜４．０２５の範囲で変動する。Formula: x in Li x FeO y , that is, Li
The reason why the molar ratio of Fe to Fe is regulated to 1.25 to 5.05 is that when x is out of this range, the capacity sharply decreases. Y in the formula: Li x FeO y increases as x increases, and y changes in the range of 1.8 to 4.025 when 1.25 ≦ x ≦ 5.05.
【０００８】式：Ｌｉx ＦｅＯy 中のｘ及びｙが、それ
ぞれ３．０≦ｘ≦５．０、３．０≦ｙ≦４．０であるリ
チウム−鉄複合酸化物が、容量が１４０ｍＡｈ／ｇ程度
と極めて大きいので、好ましい。Formula: Li x FeO y where x and y are 3.0 ≦ x ≦ 5.0 and 3.0 ≦ y ≦ 4.0, respectively, the lithium-iron composite oxide has a capacity of 140 mAh / Since it is extremely large, about g, it is preferable.
【０００９】本発明におけるリチウム−鉄複合酸化物
は、例えばリチウム化合物（ＬｉＯＨなど）と鉄化合物
（ＦｅＯＯＨなど）とを、ＬｉとＦｅとのモル比がｘ：
１（１．２５≦ｘ≦５．０５）となるように混合し、乾
燥空気雰囲気下で、５００〜９００°Ｃの温度で６〜４
０時間熱処理することにより得られる。The lithium-iron composite oxide in the present invention comprises, for example, a lithium compound (LiOH or the like) and an iron compound (FeOOH or the like), and the molar ratio of Li and Fe is x:
1 (1.25 ≦ x ≦ 5.05) and mixed in a dry air atmosphere at a temperature of 500 to 900 ° C. for 6 to 4
Obtained by heat treatment for 0 hours.
【００１０】本発明においては、負極材料として金属リ
チウム又はリチウムイオンを吸蔵、放出することが可能
な物質が用いられる。リチウムイオンを吸蔵、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
成体等の炭素材料が例示される。In the present invention, a material capable of inserting and extracting metallic lithium or lithium ions is used as the negative electrode material. Examples of the substance capable of occluding and releasing lithium ions include carbon materials such as graphite, coke, and a fired organic material.
【００１１】本発明は、ＬｉとＦｅとのモル比が特定の
範囲内にあるリチウム−鉄複合酸化物がＬｉＮｉＯ2 な
どの従来汎用されているものと比較しても遜色の無い、
大きな容量を有するとの知見に基づきなされたものであ
り、リチウム−鉄複合酸化物の実用化の途を切り開いた
ものである。それゆえ、非水電解質などの電池を構成す
る他の部材については、従来提案され、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。The present invention compares favorably with lithium-iron composite oxides in which the molar ratio of Li and Fe is within a specific range, such as LiNiO 2 which has been conventionally used.
This is based on the finding that it has a large capacity, and has opened the way to the practical application of lithium-iron composite oxides. Therefore, for other members constituting the battery such as the non-aqueous electrolyte, various materials that have been proposed or put into practical use can be used without particular limitation.
【００１２】例えば、液状非水電解質（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有機溶媒や、こ
れらとジメチルカーボネート、ジエチルカーボネート、
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
溶媒が例示され、また、その溶質としては、ＬｉＣｌＯ
4 、ＬｉＰＦ6 、ＬｉＣＦ3 ＳＯ3 が例示される。漏液
の虞れが無い信頼性の高い電池を得るべく固体電解質を
用いることももとより可能である。For example, as the solvent of the liquid non-aqueous electrolyte (non-aqueous electrolyte), organic solvents such as ethylene carbonate, vinylene carbonate and propylene carbonate, dimethyl carbonate and diethyl carbonate,
A mixed solvent with a low boiling point solvent such as 1,2-dimethoxyethane, 1,2-diethoxyethane or ethoxymethoxyethane is exemplified, and its solute is LiClO 2.
4 , LiPF 6 , and LiCF 3 SO 3 are exemplified. It is of course possible to use a solid electrolyte in order to obtain a highly reliable battery without the risk of liquid leakage.
【００１３】[0013]
【作用】正極活物質としてＬｉとＦｅとのモル比が特定
の範囲内にあるリチウム−鉄複合酸化物が用いられてい
るので、ＬｉＦｅＯ2 などを用いた場合に比し、電池容
量が実用可能な程度まで増大する。Since a lithium-iron composite oxide having a molar ratio of Li and Fe within a specific range is used as the positive electrode active material, the battery capacity can be practically used as compared with the case of using LiFeO 2. Increase to any extent.
【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 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.
【００１５】（実施例１）扁平型の非水電解液電池（本
発明電池）を作製した。Example 1 A flat non-aqueous electrolyte battery (the battery of the present invention) was produced.
【００１６】〔正極〕ＬｉＯＨとＦｅＯＯＨとを、Ｌｉ
とＦｅとのモル比が１．２５：１となるように混合した
後、乾燥空気雰囲気下で、６００°Ｃで２０時間焼成し
て、組成式：Ｌｉ1.25ＦｅＯ2.05で表される正極活物質
としてのリチウム−鉄複合酸化物を得た。このリチウム
−鉄複合酸化物をらいかいミキサーで粉砕して得た粉末
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９０：６：４の比率で
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２０ｍｍの円板状に加圧成形し、２５
０°Ｃで２時間熱処理して正極を作製した。[Positive electrode] LiOH and FeOOH are mixed with Li
And Fe so as to have a molar ratio of 1.25: 1, and then baked in a dry air atmosphere at 600 ° C. for 20 hours to obtain a positive electrode active material represented by a composition formula: Li 1.25 FeO 2.05. As a result, a lithium-iron composite oxide was obtained. A powder obtained by crushing the lithium-iron composite oxide with a raix mixer, acetylene black as a conductive agent, and fluororesin powder as a binder are mixed at a weight ratio of 90: 6: 4. To prepare a positive electrode mixture, and the positive electrode mixture is pressure-molded at a molding pressure of 2 ton / cm 2 into a disk shape having a diameter of 20 mm.
A positive electrode was produced by heat treatment at 0 ° C. for 2 hours.
【００１７】〔負極〕所定厚みのリチウム圧延板から直
径２０ｍｍの円板を打ち抜いて負極を作製した。[Negative Electrode] A negative electrode was produced by punching a disk having a diameter of 20 mm from a rolled lithium plate having a predetermined thickness.
【００１８】〔電解液〕プロピレンカーボネート（Ｐ
Ｃ）と１，２−ジメトキシエタン（ＤＭＥ）との等体積
混合溶媒に、ＬｉＣｌＯ4 を１Ｍ（モル／リットル）の
割合で溶かして、非水電解液を調製した。[Electrolyte] Propylene carbonate (P
LiClO 4 was dissolved in an equal volume mixed solvent of C) and 1,2-dimethoxyethane (DME) at a ratio of 1 M (mol / liter) to prepare a non-aqueous electrolytic solution.
【００１９】〔電池の作製〕以上の正負両極及び電解液
を用いて本発明電池Ａ１（電池寸法：直径２４．０ｍ
ｍ、厚さ３．０ｍｍ）を作製した。なお、セパレータと
しては、ポリプロピレン製の微多孔膜（ヘキストセラニ
ーズ社製、商品名「セルガード」）を使用し、これに先
に述べた非水電解液を含浸させた。[Production of Battery] The battery A1 of the present invention (battery size: diameter 24.0 m) using the positive and negative electrodes and the electrolytic solution described above.
m, thickness 3.0 mm). As the separator, a polypropylene microporous film (manufactured by Hoechst Celanese Co., Ltd., trade name “Celgard”) was used and impregnated with the above-mentioned non-aqueous electrolyte.
【００２０】図１は、作製した本発明電池Ａ１を模式的
に示す断面図であり、同図に示す本発明電池Ａ１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 cross-sectional view schematically showing the produced battery A1 of the present invention. The battery A1 of the present invention shown in FIG. 1 includes a positive electrode 1, a negative electrode 2, and a separator for separating these electrodes 1 and 2 from each other. 3, a positive electrode can 4, a negative electrode can 5, a positive electrode current collector 6, a negative electrode current collector 7, an insulating packing 8 made of polypropylene, and the like.
【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】（実施例２）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が１．５：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ1.5 ＦｅＯ2.25で表されるリチウム−鉄複合酸
化物粉末を調製し、このリチウム−鉄複合酸化物粉末を
正極活物質として用いたこと以外は実施例１と同様にし
て、本発明電池Ａ２を作製した。(Example 2) LiOH and FeOOH
A lithium-iron composite oxide represented by a composition formula: Li 1.5 FeO 2.25 was prepared in the same manner as in Example 1 except that Li and Fe were mixed so as to have a molar ratio of 1.5: 1 and fired. A battery A2 of the present invention was produced in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００２３】（実施例３）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が２．２：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ2.2 ＦｅＯ2.6 で表されるリチウム−鉄複合酸
化物粉末を調製し、このリチウム−鉄複合酸化物粉末を
正極活物質として用いたこと以外は実施例１と同様にし
て、本発明電池Ａ３を作製した。(Example 3) LiOH and FeOOH
A lithium-iron composite oxide represented by the composition formula: Li 2.2 FeO 2.6 was prepared in the same manner as in Example 1 except that Li and Fe were mixed so as to have a molar ratio of 2.2: 1 and fired. A battery A3 of the invention was produced in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００２４】（実施例４）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が３．０：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ3.0 ＦｅＯ3.0 で表されるリチウム−鉄複合酸
化物粉末を調製し、このリチウム−鉄複合酸化物粉末を
正極活物質として用いたこと以外は実施例１と同様にし
て、本発明電池Ａ４を作製した。(Example 4) LiOH and FeOOH
A lithium-iron composite oxide represented by the composition formula: Li 3.0 FeO 3.0 , in the same manner as in Example 1 except that Li and Fe were mixed so that the molar ratio was 3.0: 1 and fired. A battery A4 of the present invention was produced in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００２５】（実施例５）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が４．０：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ4.0 ＦｅＯ3.5 で表されるリチウム−鉄複合酸
化物粉末を調製し、このリチウム−鉄複合酸化物粉末を
正極活物質として用いたこと以外は実施例１と同様にし
て、本発明電池Ａ５を作製した。(Example 5) LiOH and FeOOH
A lithium-iron composite oxide represented by a composition formula: Li 4.0 FeO 3.5 was prepared in the same manner as in Example 1 except that Li and Fe were mixed so as to have a molar ratio of 4.0: 1 and fired. A battery A5 of the present invention was produced in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００２６】（実施例６）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が５．０：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ5.0 ＦｅＯ4で表されるリチウム−鉄複合酸化
物粉末を調製し、このリチウム−鉄複合酸化物粉末を正
極活物質として用いたこと以外は実施例１と同様にし
て、本発明電池Ａ６を作製した。(Example 6) LiOH and FeOOH
Lithium-iron composite oxide represented by the composition formula: Li 5.0 FeO 4 in the same manner as in Example 1 except that Li and Fe were mixed so that the molar ratio was 5.0: 1 and fired. A battery A6 of the present invention was produced in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００２７】（実施例７）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が５．０５：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ5.05ＦｅＯ4.025 で表されるリチウム−鉄複合
酸化物粉末を調製し、このリチウム−鉄複合酸化物粉末
を正極活物質として用いたこと以外は実施例１と同様に
して、本発明電池Ａ７を作製した。(Example 7) LiOH and FeOOH
A lithium-iron composite oxide represented by a composition formula: Li 5.05 FeO 4.025 was prepared in the same manner as in Example 1 except that Li and Fe were mixed so that the molar ratio was 5.05: 1 and fired. A battery A7 of the present invention was produced in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００２８】（比較例１）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が１：１となるように混合し、焼
成したこと以外は実施例１と同様にして、組成式：Ｌｉ
ＦｅＯ2 で表されるリチウム−鉄複合酸化物粉末を調製
し、このリチウム−鉄複合酸化物粉末を正極活物質とし
て用いたこと以外は実施例１と同様にして、比較電池Ｂ
１を作製した。(Comparative Example 1) LiOH and FeOOH
Compositional formula: Li was prepared in the same manner as in Example 1 except that Li and Fe were mixed so as to have a molar ratio of 1: 1 and fired.
Comparative battery B was prepared in the same manner as in Example 1 except that a lithium-iron composite oxide powder represented by FeO 2 was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
1 was produced.
【００２９】（比較例２）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が１．２：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ1.2 ＦｅＯ2.05で表されるリチウム−鉄複合酸
化物粉末を調製し、このリチウム−鉄複合酸化物粉末を
正極活物質として用いたこと以外は実施例１と同様にし
て、比較電池Ｂ２を作製した。(Comparative Example 2) LiOH and FeOOH
A lithium-iron composite oxide represented by a composition formula: Li 1.2 FeO 2.05 was prepared in the same manner as in Example 1 except that Li and Fe were mixed so as to have a molar ratio of 1.2: 1 and fired. A comparative battery B2 was prepared in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００３０】（比較例３）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が５．０７：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ5.07ＦｅＯ4.035 で表されるリチウム−鉄複合
酸化物粉末を調製し、このリチウム−鉄複合酸化物粉末
を正極活物質として用いたこと以外は実施例１と同様に
して、比較電池Ｂ３を作製した。Comparative Example 3 LiOH and FeOOH
A lithium-iron composite oxide represented by a composition formula: Li 5.07 FeO 4.035 was prepared in the same manner as in Example 1 except that Li and Fe were mixed so as to have a molar ratio of 5.07: 1 and fired. A comparative battery B3 was produced in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００３１】（比較例４）ＬｉＯＨとＦｅＯＯＨとを、
ＬｉとＦｅとのモル比が５．１：１となるように混合
し、焼成したこと以外は実施例１と同様にして、組成
式：Ｌｉ5.1 ＦｅＯ4.05で表されるリチウム−鉄複合酸
化物粉末を調製し、このリチウム−鉄複合酸化物粉末を
正極活物質として用いたこと以外は実施例１と同様にし
て、比較電池Ｂ４を作製した。Comparative Example 4 LiOH and FeOOH
A lithium-iron composite oxide represented by a composition formula: Li 5.1 FeO 4.05 was prepared in the same manner as in Example 1 except that Li and Fe were mixed so as to have a molar ratio of 5.1: 1 and fired. Comparative Battery B4 was prepared in the same manner as in Example 1 except that a powder was prepared and this lithium-iron composite oxide powder was used as the positive electrode active material.
【００３２】本発明電池Ａ１〜Ａ７及び比較電池Ｂ１〜
Ｂ４の作製に用いた各リチウム−鉄複合酸化物の組成を
表１にまとめて示す。Inventive batteries A1 to A7 and comparative batteries B1 to
Table 1 collectively shows the composition of each lithium-iron composite oxide used for the production of B4.
【００３３】[0033]
【表１】 [Table 1]
【００３４】〔放電容量特性〕本発明電池Ａ１〜Ａ７及
び比較電池Ｂ１〜Ｂ４について、充電電流１ｍＡで充電
終止電圧４．３Ｖまで充電した後、放電電流３ｍＡで放
電終止電圧３Ｖまで放電して、各電池の放電容量特性を
調べた。結果を先の表１及び図２に示す。[Discharge Capacity Characteristics] The batteries A1 to A7 of the present invention and the comparative batteries B1 to B4 were charged at a charging current of 1 mA to a charge end voltage of 4.3 V, and then discharged at a discharge current of 3 mA to a discharge end voltage of 3 V. The discharge capacity characteristics of each battery were examined. The results are shown in Table 1 and FIG. 2 above.
【００３５】図２は、各電池の放電容量特性を、縦軸に
リチウム−鉄複合酸化物１ｇ当たりの放電容量（ｍＡｈ
／ｇ）を、また横軸に用いたリチウム−鉄複合酸化物中
のＬｉとＦｅとのモル比の値ｘ（ｘ in Ｌｉx Ｆｅ
Ｏy ）をとって示したグラフであり、同図に示すように
本発明電池Ａ１〜Ａ７は、放電容量が１２０〜１４０ｍ
Ａｈ／ｇと大きいのに対して、比較電池Ｂ１〜Ｂ４は放
電容量が２０〜６０ｍＡｈ／ｇと小さい。このことか
ら、ＬｉとＦｅとのモル比の値ｘが１．２５〜５．０５
のリチウム−鉄複合酸化物を用いることにより、放電容
量の大きい非水電解質電池が得られることが分かる。な
かでも、ＬｉとＦｅとのモル比の値ｘが３．０〜５．０
であるリチウム−鉄複合酸化物を用いた本発明電池Ａ４
〜Ａ６は、放電容量が１４０ｍＡｈ／ｇと極めて大き
く、このことからｘが３．０〜５．０のリチウム−鉄複
合酸化物を用いることが、高容量の非水電解質電池を得
る上で好ましいことが分かる。FIG. 2 shows the discharge capacity characteristics of each battery, with the vertical axis representing the discharge capacity per 1 g of lithium-iron composite oxide (mAh).
/ G), and the value x (x in Li x Fe) of the molar ratio of Li and Fe in the lithium-iron composite oxide used on the horizontal axis.
O y ), the discharge capacities of the batteries A1 to A7 of the present invention are 120 to 140 m as shown in FIG.
The comparative batteries B1 to B4 have small discharge capacities of 20 to 60 mAh / g, while they are large as Ah / g. From this, the value x of the molar ratio of Li and Fe is 1.25 to 5.05.
It can be seen that a non-aqueous electrolyte battery having a large discharge capacity can be obtained by using the above lithium-iron composite oxide. Above all, the value x of the molar ratio of Li and Fe is 3.0 to 5.0.
Battery A4 of the present invention using the lithium-iron composite oxide
-A6 have an extremely large discharge capacity of 140 mAh / g. Therefore, it is preferable to use a lithium-iron composite oxide having x of 3.0 to 5.0 in order to obtain a high capacity non-aqueous electrolyte battery. I understand.
【００３６】叙上の実施例では、本発明を非水電解液電
池に適用する場合を例に挙げて説明したが、本発明は固
体電解質を用いた一次又は二次電池にも適用し得るもの
であり、この場合においても実施例で示したものと同様
の高容量の非水電解質電池が得られる。In the above embodiments, the case where the present invention is applied to a non-aqueous electrolyte battery has been described as an example, but the present invention can also be applied to a primary or secondary battery using a solid electrolyte. Even in this case, a high capacity non-aqueous electrolyte battery similar to that shown in the examples can be obtained.
【００３７】[0037]
【発明の効果】正極活物質としてＬｉとＦｅとのモル比
が特定の範囲内にあるリチウム−鉄複合酸化物が用いら
れているので、電池容量が大きい。Since the lithium-iron composite oxide having a molar ratio of Li and Fe within a specific range is used as the positive electrode active material, the battery capacity is large.
【図１】扁平型の本発明電池の断面図である。FIG. 1 is a cross-sectional view of a flat type battery of the present invention.
【図２】本発明電池及び比較電池の各放電容量特性を示
すグラフである。FIG. 2 is a graph showing respective discharge capacity characteristics of a battery of the present invention and a comparative battery.
【符号の説明】 Ａ１ 本発明電池 １ 正極 ２ 負極 ３ セパレータDESCRIPTION OF SYMBOLS A1 Battery of the present invention 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 2-5 Keihan-hondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd.
Claims (2)
を吸蔵、放出することが可能な物質を負極材料とする負
極とを備える非水電解質電池において、前記正極の活物
質として、式：Ｌｉx ＦｅＯy （但し、１．２５≦ｘ≦
５．０５、１．８≦ｙ≦４．０２５）で表されるリチウ
ム−鉄複合酸化物が用いられていることを特徴とする非
水電解質電池。1. A non-aqueous electrolyte battery comprising a positive electrode and a negative electrode comprising a material capable of inserting and extracting metallic lithium or lithium ions as a negative electrode material, wherein the positive electrode active material has the formula: Li x FeO 2. y (however, 1.25 ≦ x ≦
5.05, 1.8 ≤ y ≤ 4.025), which is a non-aqueous electrolyte battery using a lithium-iron composite oxide.
を吸蔵、放出することが可能な物質を負極材料とする負
極とを備える非水電解質電池において、前記正極の活物
質として、式：Ｌｉx ＦｅＯy （但し、３．０≦ｘ≦
５．０、３．０≦ｙ≦４．０）で表されるリチウム−鉄
複合酸化物が用いられていることを特徴とする非水電解
質電池。2. A non-aqueous electrolyte battery comprising a positive electrode and a negative electrode using, as a negative electrode material, a material capable of occluding and releasing metallic lithium or lithium ions, a positive electrode active material having the formula: Li x FeO 2. y (However, 3.0 ≦ x ≦
5.0, 3.0 ≦ y ≦ 4.0) A non-aqueous electrolyte battery comprising a lithium-iron composite oxide represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30583993A JP3268924B2 (en) | 1993-11-11 | 1993-11-11 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30583993A JP3268924B2 (en) | 1993-11-11 | 1993-11-11 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07134986A true JPH07134986A (en) | 1995-05-23 |
| JP3268924B2 JP3268924B2 (en) | 2002-03-25 |
Family
ID=17949998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30583993A Expired - Fee Related JP3268924B2 (en) | 1993-11-11 | 1993-11-11 | Non-aqueous electrolyte battery |
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| Country | Link |
|---|---|
| JP (1) | JP3268924B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002008668A (en) * | 2000-06-21 | 2002-01-11 | Toshiba Battery Co Ltd | Alkaline battery |
| JP2002008669A (en) * | 2000-06-23 | 2002-01-11 | Toshiba Battery Co Ltd | Battery |
| JP2012030988A (en) * | 2010-07-28 | 2012-02-16 | Tayca Corp | Method for producing iron-containing lithium titanate |
| JP2020053315A (en) * | 2018-09-27 | 2020-04-02 | 株式会社豊田自動織機 | Method of manufacturing composite particles |
| JP2020053314A (en) * | 2018-09-27 | 2020-04-02 | 株式会社豊田自動織機 | Method of manufacturing composite particles |
| JPWO2021029357A1 (en) * | 2019-08-09 | 2021-02-18 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445210B (en) * | 2017-07-03 | 2020-03-27 | 电子科技大学 | High-capacity iron-based lithium ion battery anode material α -LiFeO2Preparation method of (1) |
-
1993
- 1993-11-11 JP JP30583993A patent/JP3268924B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002008668A (en) * | 2000-06-21 | 2002-01-11 | Toshiba Battery Co Ltd | Alkaline battery |
| JP2002008669A (en) * | 2000-06-23 | 2002-01-11 | Toshiba Battery Co Ltd | Battery |
| JP2012030988A (en) * | 2010-07-28 | 2012-02-16 | Tayca Corp | Method for producing iron-containing lithium titanate |
| JP2020053315A (en) * | 2018-09-27 | 2020-04-02 | 株式会社豊田自動織機 | Method of manufacturing composite particles |
| JP2020053314A (en) * | 2018-09-27 | 2020-04-02 | 株式会社豊田自動織機 | Method of manufacturing composite particles |
| JPWO2021029357A1 (en) * | 2019-08-09 | 2021-02-18 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3268924B2 (en) | 2002-03-25 |
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