JPH06338325A - Nonaqueous electrolytic secondary battery - Google Patents
Nonaqueous electrolytic secondary batteryInfo
- Publication number
- JPH06338325A JPH06338325A JP5151612A JP15161293A JPH06338325A JP H06338325 A JPH06338325 A JP H06338325A JP 5151612 A JP5151612 A JP 5151612A JP 15161293 A JP15161293 A JP 15161293A JP H06338325 A JPH06338325 A JP H06338325A
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- JP
- Japan
- Prior art keywords
- negative electrode
- electrode material
- tin
- battery
- lithium
- 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】本発明は非水系電解質二次電池に
係わり、詳しくはサイクル特性に優れ、しかも放電容量
の大きい二次電池を得ることを目的とした負極材料の改
良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to improvement of a negative electrode material for obtaining a secondary battery having excellent cycle characteristics and large discharge capacity.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
非水系電解質二次電池が、ニッケル・カドミウム二次電
池等の如き含水電解液を使用する水系二次電池と異なり
水の分解電圧を考慮する必要がないため高電圧設計が可
能であるなどの理由から、脚光を浴びつつある。2. Description of the Related Art In recent years,
The reason why a non-aqueous electrolyte secondary battery does not need to consider the decomposition voltage of water unlike an aqueous secondary battery that uses a water-containing electrolyte such as a nickel-cadmium secondary battery is that a high voltage design is possible. Since then, it is in the spotlight.
【０００３】この種の電池の負極材料としては、従来、
金属リチウム等の金属材料が使用されていたが、最近、
樹枝状電析リチウムの成長に因る内部短絡の問題が指摘
されるに至って、このような問題が全く無い充放電時に
単に金属イオンを吸蔵放出するに過ぎない、酸化鉄、酸
化モリブデン等の金属酸化物や黒鉛が、従前の金属リチ
ウムなどに代わる新素材として検討されている。このう
ち、酸化鉄、酸化モリブデン等の金属酸化物はイオンの
内部拡散速度が速いため高率放電特性に優れており、一
方黒鉛はサイクル特性に優れている。Conventionally, as a negative electrode material of this type of battery,
Metallic materials such as metallic lithium were used, but recently
The problem of internal short-circuiting due to the growth of dendritic electrodeposited lithium has been pointed out, and there is no such problem. Metals such as iron oxide and molybdenum oxide, which only occlude and release metal ions during charge and discharge, are not present. Oxides and graphite are being considered as new materials to replace the conventional metallic lithium. Of these, metal oxides such as iron oxide and molybdenum oxide are excellent in high rate discharge characteristics because of high internal diffusion rate of ions, while graphite is excellent in cycle characteristics.
【０００４】しかしながら、金属酸化物については、黒
鉛に比し、放電容量が格段小さく、その上サイクル特性
が良くないという問題があり、一方黒鉛についても、金
属酸化物に比べると３７０ｍＡｈ／ｇ程度と比較的大き
な放電容量を有するものの、近年のポータブル機器用二
次電池に対する充電間隔の長期化の要請に充分応えるほ
どの放電容量を有してはおらず、かなり頻繁に充電しな
くてはならないという問題がある。However, metal oxides have a problem that their discharge capacity is much smaller than that of graphite and their cycle characteristics are not good. On the other hand, graphite is about 370 mAh / g as compared with metal oxides. Although it has a relatively large discharge capacity, it does not have a discharge capacity enough to meet the demand for longer charging intervals for secondary batteries for portable devices in recent years, and the problem is that the battery must be charged quite frequently. There is.
【０００５】本発明は、これら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、実用上
充分満足のいくサイクル特性を有し、しかも黒鉛に比べ
て放電容量が大きいため充電頻度が少なくて済む非水系
電解質二次電池を提供するにある。The present invention has been made to solve these problems, and its purpose is to have sufficiently satisfactory cycle characteristics in practical use and to have a larger discharge capacity than graphite. It is to provide a non-aqueous electrolyte secondary battery that can be charged less frequently.
【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系電解質二次電池（以下、「本発明
電池」と称する。）は、錫（Ｓｎ）と、リチウム（Ｌ
ｉ）、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、バナジ
ウム（Ｖ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）、モリ
ブデン（Ｍｏ）、タングステン（Ｗ）、マンガン（Ｍ
ｎ）、鉄（Ｆｅ）、ロジウム（Ｒｈ）、イリジウム（Ｉ
ｒ）、銅（Ｃｕ）、ケイ素（Ｓｉ）、ナトリウム（Ｎ
ａ）、カリウム（Ｋ）、マグネシウム（Ｍｇ）、カルシ
ウム（Ｃａ）、ビスマス（Ｂｉ）又はゲルマニウム（Ｇ
ｅ）との複合酸化物が、リチウムイオン等のアルカリ金
属イオン又はカルシウムイオン等のアルカリ土類金属イ
オンを吸蔵放出可能な負極材料として、使用されてな
る。A non-aqueous electrolyte secondary battery according to the present invention (hereinafter referred to as "the present battery") for achieving the above object is tin (Sn) and lithium (L).
i), titanium (Ti), zirconium (Zr), vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), manganese (M)
n), iron (Fe), rhodium (Rh), iridium (I
r), copper (Cu), silicon (Si), sodium (N
a), potassium (K), magnesium (Mg), calcium (Ca), bismuth (Bi) or germanium (G
The composite oxide with e) is used as a negative electrode material capable of occluding and releasing alkali metal ions such as lithium ions or alkaline earth metal ions such as calcium ions.
【０００７】本発明は、サイクル特性に優れ、しかも黒
鉛に比べて放電容量が大きい非水系電解質二次電池を得
るために、結晶構造が層状構造であり、充電時に層間に
リチウムイオン等の金属イオンが侵入して層間化合物を
形成するところの、錫と特定の金属との複合酸化物（複
酸化物）を負極材料として使用した点に特徴を有する。
それゆえ、正極材料、電解液などの電池を構成する他の
部材については特に制限されず、非水系電解質二次電池
用として従来使用され、或いは提案されている種々の材
料を制限無く使用することが可能である。According to the present invention, in order to obtain a non-aqueous electrolyte secondary battery having excellent cycle characteristics and having a large discharge capacity as compared with graphite, the crystal structure is a layered structure, and metal ions such as lithium ions are charged between the layers during charging. Is characterized in that a complex oxide of tin and a specific metal (a complex oxide), which penetrates to form an intercalation compound, is used as a negative electrode material.
Therefore, other members constituting the battery, such as the positive electrode material and the electrolytic solution, are not particularly limited, and various materials conventionally used or proposed for non-aqueous electrolyte secondary batteries should be used without limitation. Is possible.
【０００８】たとえば、正極材料（活物質）としては、
ＬｉＣｏＯ2 等のコバルト複合酸化物、ＬｉＮｉＯ2 、
ＬｉＭｎＯ2 等のマンガン複合酸化物、バナジウム酸化
物、ＬｉＦｅＯ2 が好適なものとして挙げられる。For example, as the positive electrode material (active material),
Cobalt composite oxide such as LiCoO 2 , LiNiO 2 ,
LiMnO manganese composite oxides such as 2, vanadium oxide, LiFeO 2 can be mentioned as preferred.
【０００９】また、電解液としては、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に、ＬｉＰＦ6 、ＬｉＣｌ
Ｏ4 、ＬｉＣＦ3 ＳＯ3 などの電解液溶質を０．７〜
１．５Ｍ（モル／リットル）、就中１Ｍの割合で溶かし
た溶液が例示される。The electrolytic solution may be an organic solvent such as ethylene carbonate, vinylene carbonate or propylene carbonate, or dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,
In a mixed solvent with a low boiling point solvent such as 2-diethoxyethane or ethoxymethoxyethane, LiPF 6 , LiCl
Electrolyte solution solutes such as O 4 and LiCF 3 SO 3 are added to 0.7-
An example is a solution of 1.5M (mol / liter), especially 1M.
【００１０】[0010]
【作用】本発明電池において、充電時には、リチウムイ
オン等の金属イオンが負極材料中に吸蔵され、また放電
時には、負極材料から充電により吸蔵された金属イオン
が放出される。本発明電池では負極材料として錫と特定
の金属との複合酸化物が使用されているので、充放電時
の上記金属イオンの吸蔵放出量が多く、また当該金属イ
オンの吸蔵放出に伴う結晶構造の崩壊が起こりにくい。In the battery of the present invention, metal ions such as lithium ions are occluded in the negative electrode material during charging, and metal ions occluded by charging are released from the negative electrode material during discharging. Since the composite oxide of tin and a specific metal is used as the negative electrode material in the battery of the present invention, the amount of storage and release of the above metal ions during charge and discharge is large, and the crystal structure of the storage and release of the metal ions is Less likely to collapse.
【００１１】[0011]
【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より何ら限定され
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。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples, and various modifications can be made without departing from the scope of the invention. Is possible.
【００１２】（実施例１）扁平型の非水系電解液二次電
池（本発明電池）を作製した。Example 1 A flat type non-aqueous electrolyte secondary battery (the battery of the present invention) was produced.
【００１３】〔正極の作製〕正極活物質としての改質二
酸化マンガン（リチウム含有二酸化マンガン）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８０：１０：１０で混合して
正極合剤を得た。この正極合剤を成形圧２トン／ｃｍ2
で加圧成形した後、２５０°Ｃで２時間加熱処理して、
円板状の正極を作製した。なお、正極集電体として、ス
テンレス鋼板（ＳＵＳ３０４）を使用した。[Production of Positive Electrode] Modified manganese dioxide (lithium-containing manganese dioxide) as a positive electrode active material, acetylene black as a conductive agent, and fluororesin powder as a binder are mixed in a weight ratio of 80:10: The mixture was mixed at 10 to obtain a positive electrode mixture. This positive electrode mixture is molded at a molding pressure of 2 ton / cm 2.
After pressure molding at, heat treatment at 250 ° C for 2 hours,
A disk-shaped positive electrode was produced. A stainless steel plate (SUS304) was used as the positive electrode current collector.
【００１４】〔負極の作製〕酸化第二錫（ＳｎＯ2 ）と
シュウ酸リチウム（Ｌｉ2 Ｃ2 Ｏ4 ）とのモル比１：１
の混合物を、空気中にて４００°Ｃで３０分間焼成して
複合酸化物を得た。[Preparation of Negative Electrode] Molar ratio of stannic oxide (SnO 2 ) and lithium oxalate (Li 2 C 2 O 4 ) 1: 1
The mixture was baked in air at 400 ° C. for 30 minutes to obtain a composite oxide.
【００１５】このようにして得た負極材料としての複合
酸化物と、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８０：１０：
１０で混合して負極合剤を得た。この負極合剤を成形圧
２トン／ｃｍ2 で加圧成形した後、２５０°Ｃで２時間
加熱処理して、円板状の負極を作製した。なお、負極集
電体として、ステンレス鋼板（ＳＵＳ３０４）を使用し
た。The composite oxide as a negative electrode material thus obtained, acetylene black as a conductive agent, and fluororesin powder as a binder were mixed in a weight ratio of 80:10:
The mixture was mixed at 10 to obtain a negative electrode mixture. This negative electrode mixture was pressure-molded at a molding pressure of 2 ton / cm 2 and then heat-treated at 250 ° C. for 2 hours to prepare a disk-shaped negative electrode. A stainless steel plate (SUS304) was used as the negative electrode current collector.
【００１６】〔電解液の調製〕エチレンカーボネート
（ＥＣ）とジメチルカーボネート（ＤＭＣ）との等体積
混合溶媒に、ＬｉＣｌＯ4 （過塩素酸リチウム）を１モ
ル／リットルの割合で溶かして電解液を調製した。[Preparation of Electrolytic Solution] LiClO 4 (lithium perchlorate) is dissolved in a mixed solvent of equal volume of ethylene carbonate (EC) and dimethyl carbonate (DMC) at a ratio of 1 mol / liter to prepare an electrolytic solution. did.
【００１７】〔電池の作製〕以上の正負両極及び電解液
を用いて扁平型の本発明電池ＢＡ１（電池寸法：直径２
５ｍｍ、厚み：３．０ｍｍ）を作製した。セパレータと
しては、ポリプロピレン不織布を使用し、これに先に述
べた電解液を含浸させた。[Fabrication of Battery] A flat type battery BA1 of the present invention (battery size: diameter 2
5 mm, thickness: 3.0 mm) was produced. As the separator, polypropylene non-woven fabric was used and impregnated with the electrolytic solution described above.
【００１８】図１は作製した本発明電池ＢＡ１を模式的
に示す断面図であり、同図に示す本発明電池ＢＡ１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 sectional view schematically showing the produced battery BA1 of the present invention. The battery BA1 of the present invention shown in FIG.
It comprises a positive electrode 1, a negative electrode 2, a separator 3 separating these electrodes 1 and 2 from each other, a positive electrode can 4, a negative electrode can 5, a positive electrode current collector 6, a negative electrode current collector 7 and an insulating packing 8 made of polypropylene.
【００１９】正極１及び負極２は、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容されており、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、電池内部で生じた化学エネル
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 with a separator 3 impregnated with an electrolytic solution in between, and the positive electrode 1 includes a positive electrode current collector 6. The negative electrode 2 is connected to the positive electrode can 4 via the negative electrode collector 7 and the negative electrode 2 is connected to the negative electrode can 5 via the negative electrode current collector 7. You can take it out.
【００２０】（実施例２）酸化第一錫と酸化第一鉄（Ｆ
ｅＯ）とのモル比２：１の混合物を、真空中にて、５０
０°Ｃで８時間焼成して複合酸化物を作製した。次い
で、この複合酸化物を負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、本発明電池ＢＡ２を作製し
た。(Example 2) Stannous oxide and ferrous oxide (F
eO) in a molar ratio of 2: 1 in a vacuum of 50
A composite oxide was prepared by firing at 0 ° C for 8 hours. Then, a battery BA2 of the invention was produced in the same manner as in Example 1 except that this composite oxide was used as the negative electrode material.
【００２１】（実施例３〜２１）表１に示す原料種、モ
ル比、焼成温度及び焼成時間で、真空中にて焼成して、
錫と種々の金属との複合酸化物を作製した。次いで、こ
れらの複合酸化物を負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、本発明電池ＢＡ３〜２１を作製
した。なお、表１中には、実施例１及び２で作製した本
発明電池ＢＡ１及びＢＡ２の作製において使用した各複
合酸化物の製造条件も併記してある。(Examples 3 to 21) The raw material species, the molar ratio, the firing temperature and the firing time shown in Table 1 were used to perform firing in vacuum,
Composite oxides of tin and various metals were prepared. Then, inventive batteries BA3 to 21 were produced in the same manner as in Example 1 except that these composite oxides were used as the negative electrode material. In addition, in Table 1, the production conditions of the respective composite oxides used in the production of the inventive batteries BA1 and BA2 produced in Examples 1 and 2 are also shown.
【００２２】[0022]
【表１】 [Table 1]
【００２３】（比較例）負極材料としての天然黒鉛と、
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８０：１０：１０で混合
して負極合剤を得た。この負極合剤を使用して得た負極
を使用したこと以外は実施例１と同様にして、比較電池
ＢＣ１を作製した。(Comparative Example) Natural graphite as a negative electrode material,
Acetylene black as a conductive agent and fluororesin powder as a binder were mixed at a weight ratio of 80:10:10 to obtain a negative electrode mixture. Comparative battery BC1 was produced in the same manner as in Example 1 except that the negative electrode obtained by using this negative electrode mixture was used.
【００２４】〔各電池のサイクル特性〕室温（２５°
Ｃ）下、３ｍＡで充電終止電圧４．０Ｖまで充電した
後、１２ｍＡで放電終止電圧２．０Ｖまで放電する工程
を１サイクルとするサイクル試験を行い、本発明電池Ｂ
Ａ１〜ＢＡ２１及び比較電池ＢＣ１のサイクル特性を調
べた。結果を図２に示す。[Cycle characteristics of each battery] Room temperature (25 °
C) Under, a cycle test is performed in which one cycle includes a step of charging to 3V at the end of charge voltage of 4.0V and then discharging at 12mA to the end of discharge voltage of 2.0V.
The cycle characteristics of A1 to BA21 and comparative battery BC1 were examined. The results are shown in Figure 2.
【００２５】図２は、各電池のサイクル特性を、縦軸に
負極材料１ｇ当たりの放電容量（ｍＡｈ／ｇ）を、横軸
にサイクル数（回）をとって示したグラフであり、同図
より錫と特定の金属との複合酸化物を使用した本発明電
池ＢＡ１〜ＢＡ２１は、天然黒鉛を使用した比較電池Ｂ
Ｃ１に比し、大きな放電容量（初期放電容量）を有する
とともに、実用上充分なサイクル特性を有することが分
かる。なかでも、錫とタンタル、ニオブ、タングステ
ン、モリブデン又はロジウムとの複合酸化物を負極材料
として使用した本発明電池ＢＡ６〜ＢＡ９及びＢＡ１１
は、サイクル特性に関しても、天然黒鉛を負極材料とし
て使用した比較電池ＢＣ１を上回っていることが分か
る。FIG. 2 is a graph showing the cycle characteristics of each battery, in which the vertical axis represents the discharge capacity (mAh / g) per 1 g of the negative electrode material and the horizontal axis represents the number of cycles (times). The batteries BA1 to BA21 of the present invention using a composite oxide of tin and a specific metal are comparative batteries B using natural graphite.
It can be seen that, in comparison with C1, it has a large discharge capacity (initial discharge capacity) and also has practically sufficient cycle characteristics. Among them, the batteries BA6 to BA9 and BA11 of the present invention using a composite oxide of tin and tantalum, niobium, tungsten, molybdenum or rhodium as a negative electrode material.
It can be seen that also in terms of cycle characteristics is higher than that of the comparative battery BC1 using natural graphite as the negative electrode material.
【００２６】叙上の実施例では、本発明を扁平型の非水
系電解質二次電池に適用する場合を例に挙げて説明した
が、電池の形状は特に限定されず、円筒型、角型など種
々の形状の非水系電池に適用し得るものである。In the above embodiments, the case where the present invention is applied to the flat type non-aqueous electrolyte secondary battery has been described as an example, but the shape of the battery is not particularly limited, and the shape is cylindrical, square, etc. It can be applied to non-aqueous batteries of various shapes.
【００２７】また、実施例では、リチウムイオンを電荷
担体とするリチウム二次電池を例に挙げて説明したが、
本発明は、ナトリウムイオン等の他のアルカリ金属イオ
ン又はカルシウムイオン等のアルカリ土類金属イオンを
電荷担体とする非水系電解質二次電池についても適用し
得るものである。Further, in the embodiment, the description has been given by taking the lithium secondary battery using lithium ions as the charge carrier as an example.
The present invention can also be applied to a non-aqueous electrolyte secondary battery using other alkali metal ions such as sodium ions or alkaline earth metal ions such as calcium ions as charge carriers.
【００２８】さらに、液体電解質に代えて固体電解質を
使用することも可能であり、また導電剤として、アセチ
レンブラックに代えて黒鉛、カーボンブラック、コーク
ス、ポリアクリロニトリルなどを使用することも可能で
ある。Further, it is possible to use a solid electrolyte instead of the liquid electrolyte, and it is also possible to use graphite, carbon black, coke, polyacrylonitrile or the like as the conductive agent instead of acetylene black.
【００２９】[0029]
【発明の効果】本発明電池は、負極材料としてリチウム
イオンなどの吸蔵放出量が多く、しかも充放電の繰り返
しに伴う結晶構造の崩壊が起こりにくい錫と特定の金属
との複合酸化物が使用されているので、実用上充分満足
のいくサイクル特性を有するとともに、放電容量が極め
て大きいなど、本発明は優れた特有の効果を奏する。INDUSTRIAL APPLICABILITY In the battery of the present invention, a composite oxide of tin and a specific metal is used as a negative electrode material, which has a large amount of occlusion and release of lithium ions and the like, and is less likely to collapse the crystal structure due to repeated charging and discharging. Therefore, the present invention has excellent peculiar effects such as having sufficiently satisfactory cycle characteristics in practical use and extremely large discharge capacity.
【図１】扁平型の非水系電解質二次電池（本発明電池）
の断面図である。FIG. 1 is a flat type non-aqueous electrolyte secondary battery (the battery of the present invention).
FIG.
【図２】実施例及び比較例で作製した各電池のサイクル
特性を示すグラフである。FIG. 2 is a graph showing cycle characteristics of each battery manufactured in Examples and Comparative Examples.
ＢＡ１ 非水系電解質二次電池（本発明電池） １ 正極 ２ 負極 ３ セパレータ BA1 non-aqueous electrolyte secondary battery (the 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18番地 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18番地 三洋 電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Nishio 2-18 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Toshihiko Saito 2-18-18 Keihanhondori, Moriguchi-shi, Osaka Sanyo Denki Within the corporation
Claims (2)
バナジウム、ニオブ、タンタル、モリブデン、タングス
テン、マンガン、鉄、ロジウム、イリジウム、銅、ケイ
素、ナトリウム、カリウム、マグネシウム、カルシウ
ム、ビスマス又はゲルマニウムとの複合酸化物が、リチ
ウムイオン等のアルカリ金属イオン又はカルシウムイオ
ン等のアルカリ土類金属イオンを吸蔵放出可能な負極材
料として、使用されていることを特徴とする非水系電解
質二次電池。1. Tin, lithium, titanium, zirconium,
Complex oxides of vanadium, niobium, tantalum, molybdenum, tungsten, manganese, iron, rhodium, iridium, copper, silicon, sodium, potassium, magnesium, calcium, bismuth or germanium are alkali metal ions such as lithium ions or calcium ions. A non-aqueous electrolyte secondary battery, which is used as a negative electrode material capable of occluding and releasing alkaline earth metal ions such as.
モリブデン又はロジウムとの複合酸化物が、リチウムイ
オン等のアルカリ金属イオン又はカルシウムイオン等の
アルカリ土類金属イオンを吸蔵放出可能な負極材料とし
て、使用されていることを特徴とする非水系電解質二次
電池。2. Tin, tantalum, niobium, tungsten,
A non-aqueous electrolyte secondary, characterized in that a composite oxide with molybdenum or rhodium is used as a negative electrode material capable of occluding and releasing alkali metal ions such as lithium ions or alkaline earth metal ions such as calcium ions. battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15161293A JP3197684B2 (en) | 1993-03-30 | 1993-05-27 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-96873 | 1993-03-30 | ||
| JP9687393 | 1993-03-30 | ||
| JP15161293A JP3197684B2 (en) | 1993-03-30 | 1993-05-27 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06338325A true JPH06338325A (en) | 1994-12-06 |
| JP3197684B2 JP3197684B2 (en) | 2001-08-13 |
Family
ID=26438037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15161293A Expired - Lifetime JP3197684B2 (en) | 1993-03-30 | 1993-05-27 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3197684B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997001870A1 (en) * | 1995-06-28 | 1997-01-16 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
| EP0880187A3 (en) * | 1997-05-22 | 2000-05-24 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| US6132903A (en) * | 1997-07-17 | 2000-10-17 | Sanyo Electric Co., Ltd. | Lithium secondary battery comprising a negative electrode consisting essentially of B2 O3 |
| US6423448B1 (en) * | 1997-05-22 | 2002-07-23 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| EP0823741A4 (en) * | 1995-04-19 | 2004-06-30 | Ube Industries | Nonaqueous secondary battery |
| EP1679756A1 (en) * | 1995-03-06 | 2006-07-12 | Ube Industries, Ltd. | Nonaqueous secondary lithium battery |
| JP2007305596A (en) * | 1995-03-06 | 2007-11-22 | Ube Ind Ltd | Non-aqueous secondary battery |
| JP2008103344A (en) * | 1995-06-28 | 2008-05-01 | Ube Ind Ltd | Non-aqueous secondary battery |
| JP2009170428A (en) * | 2009-03-23 | 2009-07-30 | Ube Ind Ltd | Non-aqueous secondary battery |
| CN109768270A (en) * | 2018-11-21 | 2019-05-17 | 上海紫剑化工科技有限公司 | Carbon coating tin base cathode material, sodium-ion battery and its preparation method and application |
-
1993
- 1993-05-27 JP JP15161293A patent/JP3197684B2/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1679756A1 (en) * | 1995-03-06 | 2006-07-12 | Ube Industries, Ltd. | Nonaqueous secondary lithium battery |
| JP2007305596A (en) * | 1995-03-06 | 2007-11-22 | Ube Ind Ltd | Non-aqueous secondary battery |
| EP0823741A4 (en) * | 1995-04-19 | 2004-06-30 | Ube Industries | Nonaqueous secondary battery |
| WO1997001870A1 (en) * | 1995-06-28 | 1997-01-16 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
| US6365299B1 (en) | 1995-06-28 | 2002-04-02 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
| US7105251B2 (en) | 1995-06-28 | 2006-09-12 | Ube Industries, Ltd. | Nonaqueous secondary battery |
| JP2008103344A (en) * | 1995-06-28 | 2008-05-01 | Ube Ind Ltd | Non-aqueous secondary battery |
| EP0880187A3 (en) * | 1997-05-22 | 2000-05-24 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| US6423448B1 (en) * | 1997-05-22 | 2002-07-23 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| US6132903A (en) * | 1997-07-17 | 2000-10-17 | Sanyo Electric Co., Ltd. | Lithium secondary battery comprising a negative electrode consisting essentially of B2 O3 |
| JP2009170428A (en) * | 2009-03-23 | 2009-07-30 | Ube Ind Ltd | Non-aqueous secondary battery |
| CN109768270A (en) * | 2018-11-21 | 2019-05-17 | 上海紫剑化工科技有限公司 | Carbon coating tin base cathode material, sodium-ion battery and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3197684B2 (en) | 2001-08-13 |
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