JPH06338347A - Nonaqueous electrolytic secondary battery - Google Patents
Nonaqueous electrolytic secondary batteryInfo
- Publication number
- JPH06338347A JPH06338347A JP5129493A JP12949393A JPH06338347A JP H06338347 A JPH06338347 A JP H06338347A JP 5129493 A JP5129493 A JP 5129493A JP 12949393 A JP12949393 A JP 12949393A JP H06338347 A JPH06338347 A JP H06338347A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- metal
- lithium
- aqueous electrolyte
- complex
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- -1 rare earth ion Chemical class 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 4
- 239000007769 metal material Substances 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract 5
- 239000000126 substance Substances 0.000 claims description 26
- 239000003446 ligand Substances 0.000 claims description 22
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 9
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- XDUUQOQFSWSZSM-UHFFFAOYSA-N 5-chloro-1,10-phenanthroline Chemical compound C1=CC=C2C(Cl)=CC3=CC=CN=C3C2=N1 XDUUQOQFSWSZSM-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 229910052747 lanthanoid Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 229910020366 ClO 4 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- DUXVYPAVCSOXOQ-UHFFFAOYSA-N diethyl carbonate;4-methyl-1,3-dioxolan-2-one Chemical compound CC1COC(=O)O1.CCOC(=O)OCC DUXVYPAVCSOXOQ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- WGZWXARAMMXBKD-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) N,N,5-trimethylcyclopenta-1,3-dien-1-amine Chemical compound [Fe++].c1cc[cH-]c1.CN(C)[c-]1cccc1C WGZWXARAMMXBKD-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QBEGYEWDTSUVHH-UHFFFAOYSA-P diazanium;cerium(3+);pentanitrate Chemical compound [NH4+].[NH4+].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBEGYEWDTSUVHH-UHFFFAOYSA-P 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウムイオンの出入
りにより起電力を得る非水電解液二次電池に関するもの
であり、いわゆるレドックスシャトルによる過充電防止
技術に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery which obtains an electromotive force by the entry and exit of lithium ions, and more particularly to a so-called redox shuttle overcharge prevention technique.
【０００２】[0002]
【従来の技術】リチウム二次電池（非水電解液二次電
池）において、安全性確保は最も重要な課題のひとつで
あり、なかでも過充電保護は重要である。例えば、ニッ
ケル−カドミウム電池においては、充電電圧が上がると
水の化学反応による充電エネルギーの消費により過充電
防止機構が働くが、非水系であるリチウム二次電池では
別の機構が必要になる。2. Description of the Related Art In a lithium secondary battery (non-aqueous electrolyte secondary battery), ensuring safety is one of the most important issues, and above all, overcharge protection is important. For example, in a nickel-cadmium battery, when the charging voltage rises, an overcharge prevention mechanism works due to consumption of charging energy by a chemical reaction of water, but a non-aqueous lithium secondary battery requires another mechanism.
【０００３】リチウム二次電池における過充電防止機構
としては、化学反応による方法と電子回路による方法が
提案され、実用的には後者が主に採用されている。しか
しながら、電子回路による方法では、コスト高になるば
かりか、商品設計上、種々の制約が生ずることになる。As a mechanism for preventing overcharge in a lithium secondary battery, a method by a chemical reaction and a method by an electronic circuit have been proposed, and the latter is mainly adopted practically. However, the method using an electronic circuit not only increases the cost but also causes various restrictions in product design.
【０００４】そこで、化学反応により過充電を防止する
技術の開発も進められており、化学的過充電保護手段と
して、非水系においては適当な酸化還元試薬を電解液に
添加する方法が試みられている。酸化還元試薬の反応の
可逆性が良い場合には、正負極間を往復して過充電電流
を消費する保護機構が成立する。Therefore, the development of a technique for preventing overcharge by a chemical reaction is also in progress, and a method of adding an appropriate redox reagent to an electrolytic solution in a non-aqueous system has been attempted as a chemical overcharge protection means. There is. When the reversibility of the reaction of the redox reagent is good, a protection mechanism that reciprocates between the positive and negative electrodes and consumes the overcharge current is established.
【０００５】このような酸化還元試薬はレドックスシャ
トル等と呼ばれている。レドックスシャトルによってリ
チウム二次電池の安全装置を簡略化することは、電子回
路式より低コストであり、また、安全装置による電池エ
ネルギー密度の低下がない等の利点がある。Such a redox reagent is called a redox shuttle or the like. Simplifying the safety device of the lithium secondary battery by the redox shuttle has advantages that it is lower in cost than the electronic circuit type and that the safety device does not reduce the battery energy density.
【０００６】上記レドックスシャトルのリチウム二次電
池への適用の可能性は、３Ｖ級のリチウム二次電池に関
しては既に報告されている。すなわち、３Ｖ級のリチウ
ム二次電池に対しては、フェロセン類がレドックスシャ
トルとして有用であることが報告されている。（例えば
特開平１−２０６５７１号公報）The possibility of applying the above redox shuttle to a lithium secondary battery has already been reported for a 3V class lithium secondary battery. That is, it has been reported that ferrocenes are useful as redox shuttles for 3V class lithium secondary batteries. (For example, Japanese Patent Laid-Open No. 1-206571)
【０００７】[0007]
【発明が解決しようとする課題】ところで、フェロセン
類についての研究から、次のデータが得られている。 酸化還元電位：Ｅ＝３．１〜３．５Ｖ（対Ｌｉ／Ｌ
ｉ+ ） このように、フェロセン類の酸化還元電位は、対リチウ
ムで３．１〜３．５Ｖであるから、電池電圧が更に大き
い電池には適用できない。例えば、４Ｖ級の電池である
カーボン−ＬｉＣｏＯ2 型のリチウムイオン電池に対し
ては、対リチウムで４．０〜４．５Ｖ程度の酸化還元電
位を示す化合物が必要になる。By the way, the following data have been obtained from research on ferrocenes. Redox potential: E = 3.1 to 3.5 V (vs. Li / L
i + ) As described above, the redox potential of ferrocenes is 3.1 to 3.5 V with respect to lithium, and therefore cannot be applied to a battery having a higher battery voltage. For example, for a carbon-LiCoO 2 type lithium ion battery, which is a 4V class battery, a compound having an oxidation-reduction potential of about 4.0 to 4.5V with respect to lithium is required.
【０００８】しかしながら、これまで、このような高い
電位で反応し、かつ電池添加物として適当である酸化還
元試薬は知られていない。４．２Ｖ程度の酸化還元電位
を有する化合物としては、金属錯体関係の化合物で非常
に多くのものが報告されているが、多くは安定性の点で
問題がある。However, until now, no redox reagent has been known which reacts at such a high potential and is suitable as a battery additive. As a compound having an oxidation-reduction potential of about 4.2 V, a great number of compounds related to metal complexes have been reported, but most of them have problems in stability.
【０００９】そこで本発明は、前述の従来の実情に鑑み
て提案されたものであって、４Ｖ級のリチウム二次電池
の化学的過充電保護手段を提供し、これにより低コスト
でエネルギー密度の高い非水電解液二次電池を提供する
ことを目的とする。Therefore, the present invention has been proposed in view of the above-mentioned conventional circumstances, and provides a chemical overcharge protection means for a 4V class lithium secondary battery. An object is to provide a high non-aqueous electrolyte secondary battery.
【００１０】[0010]
【課題を解決するための手段】本発明は、上述の目的を
達成するため、負極にリチウムを主体とする金属材料ま
たはリチウムをドープ・脱ドープ可能な炭素材料を用
い、正極にリチウムと遷移金属の複合酸化物を用いてな
る非水電解液二次電池において、非水電解液がリチウム
に対して３．８Ｖ〜４．８Ｖの酸化還元電位を示す金属
イオンまたは金属錯体を含有することを特徴とするもの
である。In order to achieve the above-mentioned object, the present invention uses a metallic material mainly containing lithium or a carbon material capable of doping / dedoping lithium in the negative electrode, and using lithium and a transition metal in the positive electrode. In the non-aqueous electrolyte secondary battery using the complex oxide of No. 3, the non-aqueous electrolyte contains a metal ion or a metal complex having a redox potential of 3.8 V to 4.8 V with respect to lithium. It is what
【００１１】非水電解液に添加される金属錯体として
は、リチウムに対して３．８Ｖ〜４．８Ｖの酸化還元電
位を示すものであれば如何なるものであってもよいが、
具体的にはポリピリジン錯体が挙げられる。このポリピ
リジン錯体が、一定の過充電電流を輸送するのに充分な
濃度で非水電解液に溶解していればよい。具体的な濃度
としては、１×１０-3モル／リットル以上であり、１×
１０-2モル／リットル〜１モル／リットルとすることが
好ましい。The metal complex added to the non-aqueous electrolyte may be any metal complex having an oxidation-reduction potential of 3.8 V to 4.8 V with respect to lithium.
Specific examples include polypyridine complexes. It suffices that the polypyridine complex be dissolved in the non-aqueous electrolyte at a concentration sufficient to transport a constant overcharge current. The specific concentration is 1 × 10 −3 mol / liter or more, and 1 ×
It is preferably from 10 -2 mol / liter to 1 mol / liter.
【００１２】ポリピリジン錯体は、文献（Ｃｏｒｄｉｎ
ａｔｉｏｎ ＣｈｅｍｉｓｔｒｙＲｅｖｉｅｗｓ，８
４，８５−２７７（１９８８））等に示されているよう
な一連のポリピリジン配位子と金属イオンとの錯体化合
物を指す。本発明で用いるポリピリジン錯体の具体的な
構造例としては、下記の化５または化６に示す配位子Ｌ
1 乃至Ｌ3 が金属Ｍに配位子してなり一般式Ｍ（Ｌ1 ）
（Ｌ2 ）（Ｌ3 ）Ｘn （ただし、ＸはＰＦ6 、ＣｌＯ4
等のアニオン性分子であり、ｎは整数である。）で表さ
れるポリピリジン錯体が挙げられる。Polypyridine complexes have been described in the literature (Cordin).
ation Chemistry Reviews, 8
4,85-277 (1988)) and the like, which refer to a complex compound of a series of polypyridine ligands and a metal ion. Specific examples of the structure of the polypyridine complex used in the present invention include a ligand L shown in Chemical formula 5 or Chemical formula 6 below.
1 to L 3 are ligands to the metal M and have the general formula M (L 1 )
(L 2 ) (L 3 ) X n (where X is PF 6 , ClO 4
Is an anionic molecule such as n, and n is an integer. ) And the polypyridine complex represented by these.
【００１３】[0013]
【化５】 [Chemical 5]
【００１４】[0014]
【化６】 [Chemical 6]
【００１５】このとき、置換基の選択は、錯体の中心金
属及び電池の作用電圧範囲に基づいて、主として置換基
の電子吸引性あるいは電子供与性を考慮することにより
行なわれる。酸化還元電位は、中心金属と配位子の基本
構造によって大まかに決定されるが、実際の電池系にお
ける電解液により数百ｍＶ程度の上下があるため、より
微妙な反応電位の調整が必要となる。金属錯体におい
て、多くの場合に電子吸引性の置換基は酸化還元電位を
上げ、電子供与性の置換基は酸化還元電位を下げること
が知られており、且つ複数の置換基の効果にしばしば加
成性が成り立つ。また、多くのポリピリジン配位子の合
成法が知られており、好ましい置換基を有する配位子化
合物は比較的に容易に得られる。At this time, the substituent is selected mainly by considering the electron withdrawing property or electron donating property of the substituent based on the central metal of the complex and the working voltage range of the battery. The oxidation-reduction potential is roughly determined by the basic structure of the central metal and the ligand, but it depends on the electrolytic solution in the actual battery system, and it may be higher or lower by several hundred mV. Therefore, it is necessary to adjust the reaction potential more delicately. Become. In metal complexes, electron-withdrawing substituents are known to increase the redox potential and electron-donating substituents are known to lower the redox potential in many cases, and they often add to the effect of multiple substituents. Genuity is established. Also, many methods for synthesizing polypyridine ligands are known, and a ligand compound having a preferred substituent can be obtained relatively easily.
【００１６】そこで、置換基の選択によって、適当な酸
化還元電位の化合物を得ることができる。例えば、負極
をリチウムをドープ・脱ドープ可能な炭素材料とし、正
極をリチウム複合酸化物であるＬｉＣｏＯ2 としたカー
ボン−ＬｉＣｏＯ2 型のリチウムイオン二次電池におい
て、特に好ましい酸化還元試薬（ポリピリジン錯体）
は、例えば下記の化７に示す構造の配位子がＦｅに配位
してなるＦｅ（５−Ｃｌ−１，１０−フェナントロリ
ン）3 Ｘn （但し、Ｘは、ＰＦ6 、ＣｌＯ4 等のアニオ
ン性分子を表す。）や、下記の化８に示す構造の配位子
がＲｕに配位してなるＲｕ（１，１０−フェナントロリ
ン）3 Ｘn （但し、Ｘは、ＰＦ6 、ＣｌＯ4等のアニオ
ン性分子を表す。）等である。Therefore, a compound having an appropriate redox potential can be obtained by selecting a substituent. For example, a redox reagent (polypyridine complex) which is particularly preferable in a carbon-LiCoO 2 type lithium ion secondary battery in which the negative electrode is a carbon material capable of being doped / dedoped with lithium and the positive electrode is LiCoO 2 which is a lithium composite oxide.
Is, for example, Fe (5-Cl-1,10-phenanthroline) 3 X n (where X is PF 6 , ClO 4 or the like) in which a ligand having a structure shown in the following chemical formula 7 is coordinated to Fe. It represents an anionic molecule.) or, Ru the ligand having the structure shown in the formula 8 below is coordinated to Ru (1,10-phenanthroline) 3 X n (where, X is, PF 6, ClO 4 Represents an anionic molecule such as).
【００１７】[0017]
【化７】 [Chemical 7]
【００１８】[0018]
【化８】 [Chemical 8]
【００１９】上述のポリピリジン錯体の中心金属として
は、鉄、ルテニウム等が、比較的単純な構造の配位子で
適当な高さの酸化還元電位を示すので好ましいといえる
が、これに限定されるものではない。このような化合物
の酸化還元電位は、対リチウムで４Ｖ以上に達し、ま
た、レドックスシャトルに要求される他の性質にも優れ
ていることが、本発明者らの検討により明らかとなっ
た。即ち、前述のポリピリジン錯体は、電解液への溶解
度が良好であり、酸化種並びに還元種が共に化学的に安
定であって、しかも、電池系内での副反応で電池性能を
低下させることがない。As the central metal of the above-mentioned polypyridine complex, iron, ruthenium, etc. are preferable because they are ligands having a relatively simple structure and exhibit an appropriate level of redox potential, but are not limited thereto. Not a thing. The present inventors have revealed that the redox potential of such a compound reaches 4 V or more with respect to lithium and is excellent in other properties required for the redox shuttle. That is, the above-mentioned polypyridine complex has good solubility in an electrolytic solution, both oxidizing species and reducing species are chemically stable, and moreover, it may deteriorate the battery performance due to side reactions in the battery system. Absent.
【００２０】一方、上述の金属錯体と同様の効果を示す
金属イオンとしては、ランタニド金属イオンが挙げられ
る。したがって、非水電解液中に、これらランタニド金
属の塩（ただし、非水電解液に溶解するものを選択する
必要がある。）を添加してもよい。On the other hand, as a metal ion having the same effect as that of the above-mentioned metal complex, a lanthanide metal ion can be mentioned. Therefore, salts of these lanthanide metals (however, those which are soluble in the non-aqueous electrolyte must be selected) may be added to the non-aqueous electrolyte.
【００２１】なかでも、セリウムイオンが好適であり、
具体的な化合物として、Ｃｅ（ＮＨ 4)2(ＮＯ3)5 なる化
学式で表される硝酸二アンモニウムセリウム(III) や、
Ｃｅ（ＮＯ3)3 なる化学式で表される硝酸セリウム(II
I) 等を非水電解液に添加すれば、レドックスシャトル
として効果的に作用する。上記セリウムイオンの酸化還
元電位は、やはり対リチウムで４Ｖ以上に達し、またレ
ドックスシャトルに要求される他の性質にも優れている
ことが確認されている。Of these, cerium ions are preferred,
As a specific compound, Ce (NH Four)2(NO3)FiveBecome
Diammonium cerium (III) nitrate represented by the formula,
Ce (NO3)3Cerium nitrate (II
If I) etc. are added to the non-aqueous electrolyte, the redox shuttle
Acts effectively as. Oxidation of cerium ion
The original potential still reached 4 V or more with respect to lithium, and
Excellent in other properties required of the Docks Shuttle
It has been confirmed.
【００２２】[0022]
【作用】遷移金属は、ｄ軌道あるいはｆ軌道の状態によ
り複数の安定な酸化還元状態を有するため、活性なｄ電
子軌道を安定させ、かつ酸化還元電位を適当に調整する
配位子との錯体とすることにより、レドックスシャトル
として好適なものとなる。そのような配位子としては、
電子供与性と立体化学的な観点及び安定性から、ポリピ
リジン配位子が適当である。The transition metal has a plurality of stable redox states depending on the d-orbital state or the f-orbital state. Therefore, a complex with a ligand that stabilizes the active d-electron orbital and appropriately adjusts the redox potential. By this, it becomes suitable as a redox shuttle. As such a ligand,
From the viewpoint of electron donating property, stereochemistry and stability, polypyridine ligand is suitable.
【００２３】特に、ｄブロック遷移金属において一般的
に、量子化学的な要請から、ｄ軌道における特定の電子
配置が安定となるが、この場合のｄ軌道は原子ないしイ
オンの最外殻に存在するため、この安定性はｄ軌道の周
囲との相互作用に著しく影響される。従って、高い酸化
還元電位を有する化合物ないしは電気化学的に安定な化
合物を得るには、安定なｄ軌道の電子配置を達成し且
つ、ｄ殻を包み込み不活性化させる配位子が有利であ
る。複数の非結合電子対によって立体的に配位し、かつ
ｄ軌道と強い配位結合を形成できるポリピリジン配位子
は、この点で優れている。In particular, in a d-block transition metal, a specific electron configuration in the d orbital is generally stable due to quantum chemical requirements. In this case, the d orbital exists in the outermost shell of an atom or an ion. Therefore, this stability is significantly affected by the interaction with the surroundings of the d orbit. Therefore, in order to obtain a compound having a high redox potential or an electrochemically stable compound, a ligand that achieves a stable d-orbital electron configuration and encloses and inactivates the d-shell is advantageous. A polypyridine ligand that is sterically coordinated by a plurality of non-bonded electron pairs and can form a strong coordinate bond with a d orbital is excellent in this respect.
【００２４】また、レドックスシャトルにおいては、４
〜５Ｖ程度で酸化された錯体は準安定状態をとる必要が
ある。ところが、この酸化において錯体の電子状態は大
きく変わることが多く、しばしば錯体の置換不活性性が
損なわれる。この点、多座配位子であるポリピリジン配
位子は他の物質によって置換されにくい。また芳香族化
合物であることから、電子分布の異なる別の安定状態を
とることができ、酸化による錯体の電子状態の変化に対
応して、配位結合を保つことができる。In the redox shuttle, 4
The complex oxidized at about 5 V needs to be in a metastable state. However, the electronic state of the complex often changes greatly in this oxidation, and the substitution inactivity of the complex is often impaired. In this regard, the polypyridine ligand, which is a polydentate ligand, is unlikely to be replaced by another substance. Further, since it is an aromatic compound, it can have another stable state with a different electron distribution, and can maintain a coordination bond in response to a change in the electronic state of the complex due to oxidation.
【００２５】一方、４ｆブロック遷移金属であるランタ
ノイド元素は、内遷移元素であるために安定性に優れ、
またｆ軌道の状態により複数の安定な酸化還元状態を有
するため、適当な溶媒和状態のイオンか、または酸化還
元電位を適当に調整する配位子との錯体とすることによ
り、レドックスシャトルとして好適なものとなる。On the other hand, the lanthanoid element, which is a 4f block transition metal, is excellent in stability because it is an internal transition element.
Further, since it has a plurality of stable redox states depending on the state of f orbital, it is suitable as a redox shuttle by forming an ion in an appropriate solvation state or a complex with a ligand that appropriately adjusts the redox potential. It will be
【００２６】すなわち、３価のランタノイドイオンはい
ずれも最外殻が希ガス配置をとり、外部との相互作用に
寄与するｆ軌道が大部分内殻に存在するために、電気化
学的に安定で、酸化還元電位が高い。また、一部のｆ軌
道の挙動が準安定状態を成立させ、反応電位が十分に高
く、しかも十分に安定な酸化種を生ずる。That is, in all of the trivalent lanthanoid ions, the outermost shell has a rare gas configuration, and most of the f orbitals contributing to the interaction with the outside are in the inner shell, so that they are electrochemically stable. , High redox potential. In addition, a part of the behavior of f orbital establishes a metastable state, and a reaction potential is sufficiently high and a sufficiently stable oxidizing species is generated.
【００２７】これらランタノイドイオンにおいて、希ガ
ス配置による安定性以外に、特定の電子数の４ｆ殻の安
定性が指摘されている。４価のセリウムは、４ｆ0 殻の
電子配置によって特に明確な安定性を示す。したがっ
て、セリウムは裸のイオンに近い状態、あるいは弱く配
位された状態で、対リチウムで４〜５Ｖと高い酸化還元
電位を有し、酸化種、還元種共に安定である。It has been pointed out that in these lanthanoid ions, in addition to the stability due to the rare gas arrangement, the stability of the 4f shell with a specific electron number is pointed out. Tetravalent cerium exhibits particularly clear stability due to the electronic configuration of the 4f 0 shell. Therefore, cerium has a high redox potential of 4 to 5 V with respect to lithium in a state close to bare ions or in a state of being weakly coordinated, and both oxidizing species and reducing species are stable.
【００２８】この他、４ｆ0 殻ほど明確ではないが、４
ｆ7 殻、４ｆ14殻の安定性を指摘されている。ｆ軌道状
態の配位子によるコントロールにおいては、ｄブロック
遷移金属ほどの多様性はないが、イオン自体の電気化学
的安定性がｄブロック遷移金属より優れているため、特
殊な多坐配位子を用いなくとも、レドックスシャトルと
しての双安定性が達成される。Other than this, although not as clear as the 4f 0 shell, 4
The stability of f 7 shell and 4f 14 shell is pointed out. The control of the f orbital state by the ligand is not as diverse as the d block transition metal, but because the electrochemical stability of the ion itself is superior to that of the d block transition metal, it is a special polydentate ligand. Bistability as a redox shuttle is achieved without using.
【００２９】[0029]
【実施例】以下、本発明を具体的な実験結果に基づいて
詳細に説明する。なお、以下の実験においては、標準容
量１０００ｍＡｈの筒型カーボン−ＬｉＣｏＯ2 型二次
電池または金属リチウムを負極としたコイン型電池を用
い、標準的な充放電サイクリング装置及びサイクリック
ボルタンメトリー測定装置を用いて評価した。EXAMPLES The present invention will be described in detail below based on specific experimental results. In the following experiments, a cylindrical carbon-LiCoO 2 type secondary battery with a standard capacity of 1000 mAh or a coin type battery with a negative electrode of metallic lithium was used, and a standard charge / discharge cycling device and a cyclic voltammetry measuring device were used. Evaluated.
【００３０】実施例１ 筒型カーボン−ＬｉＣｏＯ2 型二次電池の製造におい
て、約５ｇの電解液（１．０モルＬｉＰＦ6 炭酸プロピ
レン−炭酸ジエチル１：１溶液）に対し０．１モル／リ
ットルの濃度で［Ｆｅ（５−Ｃｌ−１，１０−フェナン
トロリン）3 ］（ＰＦ6 ）2 を溶解させ、電池に注入し
封口した。 Example 1 In the production of a tubular carbon-LiCoO 2 type secondary battery, 0.1 mol / liter was added to about 5 g of an electrolytic solution (1.0 mol LiPF 6 propylene carbonate-diethyl carbonate 1: 1 solution). [Fe (5-Cl-1,10-phenanthroline) 3 ] (PF 6 ) 2 was dissolved at a concentration of, and the solution was injected into the battery and sealed.
【００３１】前記［Ｆｅ（５−Ｃｌ−１，１０−フェナ
ントロリン）3 ］（ＰＦ6 ）2 の構造式は化９に示す通
りである。The structural formula of [Fe (5-Cl-1,10-phenanthroline) 3 ] (PF 6 ) 2 is as shown in Chemical formula 9.
【００３２】[0032]
【化９】 [Chemical 9]
【００３３】この電池の充放電サイクル試験を０．７５
ｍＡ／ｃｍ2 の定電流で、４．１〜２．５Ｖの間で室温
にて行なった。初期容量は、正極の理論容量の約８０％
であり、１００サイクル後の容量は、正極の理論容量の
約７０％であった。A charge / discharge cycle test of this battery was conducted to 0.75.
It was carried out at room temperature between 4.1 and 2.5 V with a constant current of mA / cm 2 . The initial capacity is about 80% of the theoretical capacity of the positive electrode.
The capacity after 100 cycles was about 70% of the theoretical capacity of the positive electrode.
【００３４】次に、同様に製作した電池の充放電を３サ
イクル行った後、上限電圧を４．８Ｖに設定し、０．２
ｍＡ／ｃｍ2 の定電流で過充電した。図１から明らかな
ように、電池電圧４．３〜４．４Ｖの間で電池電圧は一
定に保持された。電圧の保持された間の過充電電気量は
［Ｆｅ（５−Ｃｌ−１，１０−フェナントロリン）3 ］
（ＰＦ6 ）2 の一電子酸化に対応する量の１００倍を越
えていた。Next, after charging and discharging a battery manufactured in the same manner for 3 cycles, the upper limit voltage was set to 4.8 V and 0.2
It was overcharged at a constant current of mA / cm 2 . As is clear from FIG. 1, the battery voltage was kept constant between the battery voltages of 4.3 to 4.4V. The amount of electricity for overcharge while the voltage is held is [Fe (5-Cl-1,10-phenanthroline) 3 ].
The amount exceeded 100 times the amount corresponding to one-electron oxidation of (PF 6 ) 2 .
【００３５】実施例２ 遷移金属錯体を、２０ミリモル／リットルになるよう
に、１．０モルＬｉＰＦ 6 炭酸プロピレン−炭酸ジメチ
ル（体積比１：１）混合溶媒非水電解液に溶解し、サイ
クリックボルタンメトリーによる酸化還元電位の測定を
行なった。Ｒｕ，Ｆｅの錯体及び誘導体について測定を
行なった結果は、下記の通りである。[0035]Example 2 20 mM / l of transition metal complex
1.0 mol LiPF 6Propylene carbonate-dimethy carbonate
Solution (volume ratio 1: 1) in a mixed solvent non-aqueous electrolyte,
Measurement of redox potential by click voltammetry
I did. Measurement of Ru and Fe complexes and derivatives
The results obtained are as follows.
【００３６】 試薬 Ｅ1/2 ／Ｖ（対リチウム） ［Fe(1,10-フェナントロリン)3］(PF6)2 ３．９４ ［Fe(5-Cl-1,10- フェナントロリン)3］(PF6)2 ４．０２ ［Fe(5-NO2-1,10-フェナントロリン)3］(PF6)2 ４．１２ ［Fe(2,2'-ビピリジル)3］(PF6)2 ３．８７ ［Ru(1,10-フェナントロリン)3］(PF6)2 ４．１６ なお、試薬及び試薬〜の構造式は下記の通りであ
る。Reagent E 1/2 / V (vs. lithium) [Fe (1,10-phenanthroline) 3 ] (PF 6 ) 2 3.94 [Fe (5-Cl-1,10-phenanthroline) 3 ] (PF 6 ) 2 4.02 [Fe (5-NO 2 -1,10-phenanthroline) 3 ] (PF 6 ) 2 4.12 [Fe (2,2′-bipyridyl) 3 ] (PF 6 ) 2 3.87 [Ru (1,10-phenanthroline) 3 ] (PF 6 ) 2 4.16 The chemical formulas of the reagents and reagents are as follows.
【００３７】[0037]
【化１０】 [Chemical 10]
【００３８】[0038]
【化１１】 [Chemical 11]
【００３９】[0039]
【化１２】 [Chemical 12]
【００４０】[0040]
【化１３】 [Chemical 13]
【００４１】実施例４ ［Ｆｅ（５−Ｃｌ−１，１０−フェナントロリン）3 ］
（ＰＦ6 ）2 を、２０ミリモル／リットルになるよう
に、１．０モル／リットルＬｉＰＦ6 炭酸プロピレン−
炭酸ジメチル（体積比１：１）混合溶媒非水電解液に溶
解し、金属リチウムを負極、ＬｉＣｏＯ2 を正極とした
コイン型リチウム電池を作製した。極板の直径は１５．
５ｍｍとした。充電は、約１５０μＡで、セル電圧が
４．５Ｖになるまで行なった。比較として、試薬を投入
していないセルについても同様の実験を行なった。 Example 4 [Fe (5-Cl-1,10-phenanthroline) 3 ]
(PF 6 ) 2 so as to be 20 mmol / liter, 1.0 mol / liter LiPF 6 propylene carbonate-
A coin-type lithium battery was prepared by dissolving in dimethyl carbonate (volume ratio 1: 1) mixed solvent non-aqueous electrolytic solution and using metallic lithium as a negative electrode and LiCoO 2 as a positive electrode. The diameter of the electrode plate is 15.
It was set to 5 mm. Charging was performed at about 150 μA until the cell voltage reached 4.5V. As a comparison, the same experiment was performed for cells to which no reagent was added.
【００４２】試薬を投入したセルは、試薬を投入してい
ないセルと比較して、充電電気量に対する電圧上昇の変
化率が小さくなり、充電時にＬｉ+ の脱ドープ以外に消
費された電気量は、［Ｆｅ（５−Ｃｌ−１，１０−フェ
ナントロリン）3 ］（ＰＦ6）2 が１電子酸化されるの
に要する電気量の約２８０倍であった。The cell charged with the reagent has a smaller rate of change in voltage increase with respect to the amount of electricity charged, as compared with the cell not charged with the reagent, and the amount of electricity consumed other than Li + dedoping during charging is was about 280 times the quantity of electricity required for [Fe (5-Cl-1,10- phenanthroline) 3] (PF 6) 2 is one-electron oxidation.
【００４３】実施例５ 筒型カーボン−ＬｉＣｏＯ2 型二次電池の製造におい
て、約５ｇの電解液（１．０モル／リットルＬｉＰＦ6
炭酸プロピレン−炭酸ジエチル１：１溶液）に対し０．
１モル／リットルの濃度でＣｅ（ＮＨ4)2(ＮＯ3)5 を溶
解させ、電池に注入し封口した。 Example 5 In the manufacture of a tubular carbon-LiCoO 2 type secondary battery, about 5 g of electrolytic solution (1.0 mol / liter LiPF 6
Propylene carbonate-diethyl carbonate 1: 1 solution).
Ce (NH 4 ) 2 (NO 3 ) 5 was dissolved at a concentration of 1 mol / liter, poured into the battery and sealed.
【００４４】この電池の充放電サイクル試験を０．７５
ｍＡ／ｃｍ2 の定電流で、４．１〜２．５Ｖの間で室温
にて行なった。初期容量は、正極の理論容量の約８０％
であり、１００サイクル後の容量は、正極の理論容量の
約７０％であった。A charge / discharge cycle test of this battery was conducted at 0.75.
It was carried out at room temperature between 4.1 and 2.5 V with a constant current of mA / cm 2 . The initial capacity is about 80% of the theoretical capacity of the positive electrode.
The capacity after 100 cycles was about 70% of the theoretical capacity of the positive electrode.
【００４５】次に、同様に製作した電池の充放電を３サ
イクル行った後、上限電圧を４．８Ｖに設定し、０．２
ｍＡ／ｃｍ2 の定電流で過充電した。図２から明らかな
ように、電池電圧４．３〜４．４Ｖの間で電池電圧は一
定に保持された。電圧の保持された間の過充電電気量は
セリウムイオンの一電子酸化に対応する量の３倍を越え
ていた。Next, after charging and discharging a battery manufactured in the same manner for 3 cycles, the upper limit voltage was set to 4.8 V and 0.2
It was overcharged at a constant current of mA / cm 2 . As is clear from FIG. 2, the battery voltage was kept constant between the battery voltages 4.3 and 4.4V. The amount of overcharge electricity while the voltage was held exceeded three times the amount corresponding to one-electron oxidation of cerium ions.
【００４６】実施例６ 筒型カーボン−ＬｉＣｏＯ2 型二次電池の製造におい
て、約５ｇの電解液（１．０モル／リットルＬｉＰＦ6
炭酸プロピレン−炭酸ジエチル１：１溶液）に対し０．
１モル／リットルの濃度でＣｅ（ＮＯ3)3 を溶解させ、
電池に注入し封口した。 Example 6 In the manufacture of a tubular carbon-LiCoO 2 type secondary battery, about 5 g of electrolytic solution (1.0 mol / liter LiPF 6
Propylene carbonate-diethyl carbonate 1: 1 solution).
Ce (NO 3 ) 3 was dissolved at a concentration of 1 mol / liter,
It was injected into the battery and sealed.
【００４７】次に、同様に製作した電池の充放電を１０
サイクル行った後、上限電圧を４．８Ｖに設定し、０．
２ｍＡ／ｃｍ2 の定電流で過充電した。電池電圧４．５
〜４．６Ｖの間で電池電圧は一定に保持された。電圧の
保持された間の過充電電気量はセリウムイオンの一電子
酸化に対応する量の３倍を越えていた。Next, charge and discharge of a battery manufactured in the same manner is carried out for 10 minutes.
After cycling, set the upper limit voltage to 4.8V,
It was overcharged at a constant current of 2 mA / cm 2 . Battery voltage 4.5
The battery voltage was held constant between ˜4.6V. The amount of overcharge electricity while the voltage was held exceeded three times the amount corresponding to one-electron oxidation of cerium ions.
【００４８】比較例１ 前記筒型電池を電解液に何ら添加物を加えることなく電
池に注入封口したもの対して、実施例１と同様に過充電
した。即ち、電池の充放電を３サイクル行なった後、上
限電圧を４．８Ｖに設定し、０．２ｍＡ／ｃｍ2 の定電
流で電池を過充電したところ、電圧は速やかに上昇し、
約１．５Ａｈの過充電で４．８Ｖに達した。 Comparative Example 1 The cylindrical battery was overcharged in the same manner as in Example 1 except that the battery was injected and sealed without adding any additive to the electrolytic solution. That is, when the battery was charged / discharged for 3 cycles, the upper limit voltage was set to 4.8 V, and the battery was overcharged with a constant current of 0.2 mA / cm 2 , the voltage rapidly increased,
It reached 4.8 V with an overcharge of about 1.5 Ah.
【００４９】比較例２ 前記筒型電池の製造において、約５ｇの電解液に対し
０．１モルの濃度でジメチルアミノメチルフェロセンを
溶解させ、電池に注入封口した。この電池の充電を試み
たが、初充電時の標準的充電電流では電池電圧を４Ｖ以
上にすることができず、充電不可能であった。 Comparative Example 2 In the production of the cylindrical battery, dimethylaminomethylferrocene was dissolved in a concentration of 0.1 mol with respect to about 5 g of the electrolytic solution, and the battery was injected and sealed. An attempt was made to charge this battery, but it was impossible to charge it because the battery voltage could not be increased to 4 V or higher with the standard charging current during the initial charging.
【００５０】[0050]
【発明の効果】以上の説明からも明らかなように、本発
明によれば、エネルギー密度の高い４Ｖ以上の電圧のリ
チウム二次電池（非水電解液二次電池）の過充電保護を
低コストで、しかもエネルギー密度を低下させる保護装
置なしに提供することができる。従って、軽量にして高
容量かつ長寿命の二次電池を安価に供給することがで
き、しかも電池の安全性や信頼性にすぐれていることか
ら、広く、二次電池を必要とするポータブル機器、自動
車用バッテリ、電気自動車、ロードレベリングなどの用
途に使用することができ、その効果は非常に大きいもの
である。As is apparent from the above description, according to the present invention, overcharge protection of a lithium secondary battery (non-aqueous electrolyte secondary battery) having a high energy density of 4 V or more at a low cost can be achieved. In addition, it can be provided without a protective device that lowers the energy density. Therefore, a lightweight, high-capacity, long-life secondary battery can be supplied at a low cost, and since the battery is excellent in safety and reliability, it is widely used in portable devices requiring a secondary battery, It can be used in applications such as automobile batteries, electric vehicles, and road leveling, and its effect is very large.
【図１】ポリピリジン錯体を添加したリチウム二次電池
における充電電気量に対する電圧変化を示す特性図であ
る。FIG. 1 is a characteristic diagram showing a voltage change with respect to a charge electricity quantity in a lithium secondary battery to which a polypyridine complex is added.
【図２】セリウムイオンを添加したリチウム二次電池に
おける充電電気量に対する電圧変化を示す特性図であ
る。FIG. 2 is a characteristic diagram showing a voltage change with respect to a charge electricity amount in a lithium secondary battery to which cerium ions are added.
Claims (8)
はリチウムをドープ・脱ドープ可能な炭素材料を用い、
正極にリチウムと遷移金属の複合酸化物を用いてなる非
水電解液二次電池において、 非水電解液がリチウムに対して３．８Ｖ〜４．８Ｖの酸
化還元電位を示す金属イオンまたは金属錯体を含有する
ことを特徴とする非水電解液二次電池。1. A negative electrode is made of a metallic material mainly containing lithium or a carbon material capable of being doped and dedoped with lithium,
In a non-aqueous electrolyte secondary battery using a composite oxide of lithium and a transition metal for the positive electrode, the non-aqueous electrolyte is a metal ion or metal complex that exhibits a redox potential of 3.8 V to 4.8 V with respect to lithium. A non-aqueous electrolyte secondary battery comprising:
体であることを特徴とする請求項１記載の非水電解液二
次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the metal complex is a complex of a transition metal or a rare earth element.
れる配位子Ｌ1 ，Ｌ2，Ｌ3 が金属Ｍ（ただし、Ｍは遷
移金属または希土類元素）に配位してなり一般式Ｍ（Ｌ
1 ）（Ｌ2 ）（Ｌ3 ）Ｘn （ただし、式中のＸはアニオ
ン性分子であり、ｎは整数である。）で表されるポリピ
リジン錯体であることを特徴とする請求項２記載の非水
電解液二次電池。 【化１】 【化２】 3. A metal complex in which ligands L 1 , L 2 and L 3 represented by the following chemical formula 1 or chemical formula 2 are coordinated to a metal M (where M is a transition metal or a rare earth element). General formula M (L
3. A polypyridine complex represented by 1 ) (L 2 ) (L 3 ) X n (wherein, X is an anionic molecule and n is an integer). Non-aqueous electrolyte secondary battery. [Chemical 1] [Chemical 2]
がＦｅに配位してなり一般式Ｆｅ（Ｌ）3 Ｘn （ただ
し、式中のＸはアニオン性分子であり、ｎは整数であ
る。）で表されるポリピリジン錯体であることを特徴と
する請求項１記載の非水電解液二次電池。 【化３】 4. A ligand L having a metal complex represented by the following chemical formula 3.
Is a polypyridine complex represented by the general formula Fe (L) 3 X n (wherein X is an anionic molecule and n is an integer). The non-aqueous electrolyte secondary battery according to claim 1. [Chemical 3]
がＲｕに配位してなり一般式Ｒｕ（Ｌ）3 Ｘn （ただ
し、式中のＸはアニオン性分子であり、ｎは整数であ
る。）で表されるポリピリジン錯体であることを特徴と
する請求項１記載の非水電解液二次電池。 【化４】 5. A ligand L represented by the following chemical formula 4 wherein the metal complex is
Is a polypyridine complex represented by the general formula Ru (L) 3 X n (wherein X is an anionic molecule and n is an integer). The non-aqueous electrolyte secondary battery according to claim 1. [Chemical 4]
徴とする請求項１記載の非水電解液二次電池。6. The non-aqueous electrolyte secondary battery according to claim 1, wherein the metal ions are rare earth ions.
特徴とする請求項６記載の非水電解液二次電池。7. The non-aqueous electrolyte secondary battery according to claim 6, wherein the metal ions are cerium ions.
3)3 を添加することによりセリウムイオンを含有せしめ
てなる請求項７記載の非水電解液二次電池。8. Ce (NH 4 ) 2 (NO 3 ) 5 or Ce (NO
The non-aqueous electrolyte secondary battery according to claim 7, wherein the cerium ion is contained by adding 3 ) 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12949393A JP3259436B2 (en) | 1993-05-31 | 1993-05-31 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12949393A JP3259436B2 (en) | 1993-05-31 | 1993-05-31 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06338347A true JPH06338347A (en) | 1994-12-06 |
| JP3259436B2 JP3259436B2 (en) | 2002-02-25 |
Family
ID=15010847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12949393A Expired - Fee Related JP3259436B2 (en) | 1993-05-31 | 1993-05-31 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3259436B2 (en) |
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