JPH084015B2 - Organic electrolyte secondary battery - Google Patents
Organic electrolyte secondary batteryInfo
- Publication number
- JPH084015B2 JPH084015B2 JP62291104A JP29110487A JPH084015B2 JP H084015 B2 JPH084015 B2 JP H084015B2 JP 62291104 A JP62291104 A JP 62291104A JP 29110487 A JP29110487 A JP 29110487A JP H084015 B2 JPH084015 B2 JP H084015B2
- Authority
- JP
- Japan
- Prior art keywords
- organic electrolyte
- battery
- discharge
- succinic anhydride
- organic
- 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.)
- Expired - Fee Related
Links
- 239000005486 organic electrolyte Substances 0.000 title claims description 46
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims description 21
- 159000000002 lithium salts Chemical class 0.000 claims description 21
- 229940014800 succinic anhydride Drugs 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 15
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 10
- 150000002170 ethers Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000010494 dissociation reaction Methods 0.000 description 7
- 230000005593 dissociations Effects 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- -1 LiClO 2 Chemical class 0.000 description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910013684 LiClO 4 Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- HOBNHEYUHWCGMG-UHFFFAOYSA-M [O-2].[OH-].O.O.O.[Cr+3] Chemical compound [O-2].[OH-].O.O.O.[Cr+3] HOBNHEYUHWCGMG-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、負極にリチウムなどを用いた有機電解質二
次電池の改良に関するものであり、特に有機電解質の改
良により、電池の過放電特性の向上を目指すものであ
る。TECHNICAL FIELD The present invention relates to an improvement in an organic electrolyte secondary battery using lithium or the like as a negative electrode, and in particular, improvement in an organic electrolyte improves the overdischarge characteristics of the battery. It is what we aim for.
従来の技術 負極にリチウムやリチウム合金、正極に、活物質とし
ての二硫化チタン（TiS2）や、二酸化マンガン（Mn
O2），五二酸化クロム（Cr2O5）に、導電剤としてのア
セチレンブラックなどの炭素粉を混合して作製された電
極を用いた有機電解質二次電池の研究が活発に行われて
いる。これらの電池には、プロピレンカーボネート（P
C）やエチレンカーボネート（EC）などのカーボネート
類に、ジメトキシエタン（DME）や、２−メチルテトラ
ヒドロフラン（２−Me−THF）などのエーテル類を混合
した有機溶媒に、過塩素リチウム（LiClO4）やリチウム
ヘキサクロロアルシネート（LiAsF6）をリチウム塩とし
て溶解した有機電解質が用いられて来た。Conventional technology Lithium or lithium alloy for the negative electrode, titanium disulfide (TiS 2 ) or manganese dioxide (Mn
O 2 ), chromium pentaoxide (Cr 2 O 5 ) and carbon powder such as acetylene black as a conductive agent are mixed, and research is being actively conducted on an organic electrolyte secondary battery using an electrode prepared. . Propylene carbonate (P
C), ethylene carbonate (EC) and other carbonates, dimethoxyethane (DME) and 2-methyltetrahydrofuran (2-Me-THF) and other ethers mixed in an organic solvent, lithium perchlorate (LiClO 4 ) Organic electrolytes in which lithium hexachloroarsinate (LiAsF 6 ) is dissolved as a lithium salt have been used.
発明が解決しようとする問題点 従来のPCは誘電率が大であり、LiClO2などのリチウム
塩をイオン解離させる能力は大きいが、PCそのものの粘
度が大であるため、有機電解質の有機溶媒にこれを用い
た電池では、高率放電時に電圧の低下、正極の利用率の
低下が起こる。一方、DMEや２−Me−THFなどのエーテル
類では粘度は小さいが誘電率が小さいため、LiClO4など
のリチウム塩を十分な割合でイオン解離させることがで
きず、これら有機溶媒を用いた有機電解質二次電池では
高率放電時に、電池電圧の低下や利用率の低下が起こっ
た。このため、PCやECなどのカーボネート類と、エーテ
ル類を混合して、十分なリチウム塩のイオン解離を得る
とともに、粘度の低下を図って、電池の放電特性を向上
させて来た。しかし、これらの電解質中で電池を過放電
させると、正極の電位の低下に伴い、活物質表面や、導
電剤に使用している炭素粉の表面で有機電解質を構成し
ているPCやECなどカーボネート類の有機溶媒の分解が起
こり、分解生成物が正極粒子表面を覆って、以後の充放
電特性は、急激に低下した。Problems to be Solved by the Invention Conventional PC has a large dielectric constant and has a large ability to ionically dissociate a lithium salt such as LiClO 2 , but since the PC itself has a large viscosity, it can be used as an organic solvent for an organic electrolyte. In a battery using this, the voltage drops and the utilization factor of the positive electrode drops at a high rate discharge. On the other hand, in ethers such as DME and 2-Me-THF, the viscosity is small but the dielectric constant is small, so that it is not possible to ionically dissociate a lithium salt such as LiClO 4 in a sufficient ratio, and organic compounds using these organic solvents In the electrolyte secondary battery, the battery voltage and the utilization factor decreased at high rate discharge. Therefore, by mixing carbonates such as PC and EC with ethers, sufficient ionic dissociation of the lithium salt is obtained, the viscosity is reduced, and the discharge characteristics of the battery have been improved. However, when the battery is over-discharged in these electrolytes, the potential of the positive electrode decreases and the organic electrolyte is composed of the active material surface or the surface of the carbon powder used as the conductive agent. Decomposition of the organic solvent of the carbonates occurred, the decomposition product covered the surface of the positive electrode particles, and the subsequent charge / discharge characteristics drastically deteriorated.
したがって、カーボネート類を使わない有機電解質、
または使用量を減らした有機電解質の利用が考えられる
が、先に示したように電池電圧の低下などの問題があっ
た。Therefore, organic electrolytes that do not use carbonates,
Alternatively, it is conceivable to use an organic electrolyte with a reduced usage amount, but as mentioned above, there was a problem such as a decrease in battery voltage.
本発明は上記従来技術の問題点に鑑み、有機電解質を
改良して、高率放電で電池電圧や利用率の低下のない、
かつ過放電特性にも優れた有機電解質二次電池を提供す
ることを目的とする。The present invention, in view of the above problems of the prior art, by improving the organic electrolyte, without a decrease in battery voltage or utilization rate at high rate discharge,
It is an object of the present invention to provide an organic electrolyte secondary battery having excellent overdischarge characteristics.
問題点を解決するための手段 本発明は、無水コハク酸を添加した有機電解質を使用
することを特徴とする有機電解質電池である。Means for Solving the Problems The present invention is an organic electrolyte battery characterized by using an organic electrolyte to which succinic anhydride is added.
作用 本発明はECを用いた有機電解質を発想の基としてい
る。先に述べたようにエーテル類のみの溶媒にリチウム
塩を溶解した有機電解質を用いた電池では、リチウム塩
のイオン解離が不十分で高率放電で電池電圧の低下が起
こった。ECは室温では固体であるが、エーテル類例えば
２−Me−THFに添加すると均一な溶液となり混合溶媒を
作るとされている。そしてこの混合溶媒にリチウム塩を
溶解するとECの作用によりリチウム塩のイオン解離が十
分となり、有機電解質のイオン電導度の上昇とともに、
電池の放電電圧も上昇することが知られている。このこ
とはECのようにたとえ室温で固体であっても、エーテル
類などのイオン解離能力の小さい溶媒に添加され均一な
溶液となる場合には、リチウム塩のイオン解離が大きく
なる場合があることを示している。Action The present invention is based on the idea of an organic electrolyte using EC. As described above, in the battery using the organic electrolyte in which the lithium salt is dissolved in the solvent containing only ethers, the ionic dissociation of the lithium salt is insufficient and the battery voltage drops due to high rate discharge. Although EC is a solid at room temperature, it is said that when it is added to ethers such as 2-Me-THF, it becomes a uniform solution to form a mixed solvent. When the lithium salt is dissolved in this mixed solvent, the ionic dissociation of the lithium salt becomes sufficient due to the action of EC, and the ionic conductivity of the organic electrolyte increases,
It is known that the discharge voltage of a battery also rises. This means that even if it is a solid at room temperature like EC, the ionic dissociation of the lithium salt may increase when it is added to a solvent with a low ionic dissociation ability such as ethers to form a uniform solution. Is shown.
無水コハク酸は、ECと同じように20℃では固体であ
る。しかし、DMEや２−Me−THFに添加すると均一な溶液
ができる。この無水コハク酸を添加したエーテル類の溶
液にLiClO4などのリチウム塩を溶解させると、リチウム
塩は十分にイオン解離した。この有機電解質を用いた電
池では、従来のPCやECとエーテル類との混合溶媒にリチ
ウム塩を溶解した有機電解質を利用した電池に比べ同等
もしくは以上の充放電特性が得られた。また、過放電を
行っても有機電解質中にPCやECを用いていないので、PC
やECの分解は起こらず、その後の充放電特性も良好であ
った。本発明はPCやECなどのカーボネート類を利用しな
い有機電解質のみに限定するものではない。無水コハク
酸を添加することにより、有機電解質中のPCやECの量を
減らすことができ、その分過放電特性を改善できるから
である。この無水コハク酸は有機電解質の中でイオン解
離という溶媒の役割を果たしているが溶媒でないことは
明らかである。有機電解質への添加剤と考えるべきであ
る。Succinic anhydride is a solid at 20 ° C, similar to EC. However, when added to DME or 2-Me-THF, a uniform solution is formed. When a lithium salt such as LiClO 4 was dissolved in this ether solution containing succinic anhydride, the lithium salt was sufficiently ion dissociated. In the battery using this organic electrolyte, the charge / discharge characteristics equivalent to or higher than those of the battery using the organic electrolyte in which the lithium salt was dissolved in the conventional mixed solvent of PC and EC and ethers were obtained. In addition, since PC and EC are not used in the organic electrolyte even after overdischarging, PC
No decomposition of EC or EC occurred, and the charge / discharge characteristics after that were also good. The present invention is not limited to only organic electrolytes that do not utilize carbonates such as PC and EC. By adding succinic anhydride, the amounts of PC and EC in the organic electrolyte can be reduced, and the overdischarge characteristics can be improved accordingly. This succinic anhydride plays a role of a solvent called ion dissociation in the organic electrolyte, but it is clear that it is not a solvent. It should be considered as an additive to the organic electrolyte.
実 施 例 以下に本発明の実施例を説明する。Examples Examples of the present invention will be described below.
（実施例１） 負極に直径17.5mm,厚さ0.5mmの円板状リチウムを用い
た。この時の理論充填量は247mAhである。正極には、二
酸化マンガン100重量に導電剤としてのアセチレンブラ
ック10重量部、結着剤としてのポリ四フッ化エチレン樹
脂10重量部を加えた合剤0.4gを、直径17.5mmの円盤状に
圧縮成形したものを用いた。この正極の理論充填容量は
103mAhであった。この正極，負極を用いて第１図に示し
た扁平形電池を構成し、有機電解質の違いによる特性差
を検討した。(Example 1) Disc-shaped lithium having a diameter of 17.5 mm and a thickness of 0.5 mm was used as the negative electrode. The theoretical filling amount at this time is 247 mAh. For the positive electrode, 0.4 g of a mixture of 100 parts by weight of manganese dioxide, 10 parts by weight of acetylene black as a conductive agent, and 10 parts by weight of polytetrafluoroethylene resin as a binder was compressed into a disk shape with a diameter of 17.5 mm. A molded product was used. The theoretical filling capacity of this positive electrode is
It was 103 mAh. The positive and negative electrodes were used to construct the flat battery shown in FIG. 1, and the difference in characteristics due to the difference in organic electrolyte was examined.
第１図において、１は電池ケース、２は封口板、３は
負極、４はセパレータ、５は正極、６はガスケットであ
る。In FIG. 1, 1 is a battery case, 2 is a sealing plate, 3 is a negative electrode, 4 is a separator, 5 is a positive electrode, and 6 is a gasket.
有機電解質のリチウム塩にはLiClO4を用いて、その濃
度はすべて１モル/lとした。DME10モルに対して無水コ
ハク酸５モルを添加して均一溶液を作り、これにリチウ
ム塩を溶解して有機電解質とした。この電解質を用いた
電池をＡとする。同じく２−Me−THF10モルに対して５
モルの無水コハク酸を添加して、これにリチウム塩を溶
解した有機電解質を用いた電池をＢとする。また従来例
として、モル比で5:10のPCとDMEの混合溶媒を用い、こ
れにリチウム塩を溶解した有機電解質を用いた電池を
Ｃ、同じく5:10のPCと２−Me−THFを用いた電池をＤ、
２−Me−THF単独溶媒を用いた電池をＥとする。LiClO 4 was used as the lithium salt of the organic electrolyte, and the concentration thereof was all 1 mol / l. 5 mol of succinic anhydride was added to 10 mol of DME to prepare a uniform solution, and a lithium salt was dissolved in this to prepare an organic electrolyte. A battery using this electrolyte is designated as A. Similarly, for every 10 moles of 2-Me-THF, 5
Let B be a battery using an organic electrolyte obtained by adding a molar amount of succinic anhydride and dissolving a lithium salt therein. Also, as a conventional example, a battery using a mixed solvent of PC and DME at a molar ratio of 5:10 and an organic electrolyte in which a lithium salt was dissolved was used as C, and PC at the same ratio of 5:10 and 2-Me-THF were also used. The battery used is D,
A battery using a single solvent of 2-Me-THF is designated as E.
各電池を2mAで2Vまで放電し、3.9Vまで充電するサイ
クルを10サイクルまで行い、11サイクル目以降は放電を
電池端子電圧が0Vになるまで行った。第２図には、各電
池の15サイクル目の放電曲線を示す。これより、過放電
を行った場合でも、本発明の無水コハク酸を添加した有
機電解質を用いた二次電池では、良好な充放電サイクル
が可能であることがわかる。また、過放電を行う前の８
サイクル目の電池の放電曲線を第３図に示す。２−Me−
THFに無水コハク酸を添加した有機電解質を用いたＢの
電池は、リチウム塩を溶解するのに２−Me−THF単独溶
媒を使った電池Ｅ、従来のPCと２−Me−THFとの混合溶
媒を有機電解質に用いた電池Ｄと同等もしくは、それ以
上の性能を示すことがわかる。Each battery was discharged to 2 V at 2 mA and charged to 3.9 V up to 10 cycles, and after the 11th cycle, discharge was performed until the battery terminal voltage reached 0 V. FIG. 2 shows the 15th cycle discharge curve of each battery. From this, it can be seen that even when overdischarge is performed, a good charge / discharge cycle is possible in the secondary battery using the organic electrolyte to which the succinic anhydride of the present invention is added. In addition, 8 before the over discharge
The discharge curve of the battery at the cycle is shown in FIG. 2-Me-
Battery B, which uses an organic electrolyte in which succinic anhydride is added to THF, is battery E, which uses a single solvent of 2-Me-THF to dissolve the lithium salt, and is a mixture of conventional PC and 2-Me-THF. It can be seen that the performance is equal to or higher than that of the battery D using the solvent as the organic electrolyte.
（実施例２） 無水コハク酸は室温で固体であるため、有機電解質を
構成するには、溶媒へ添加して溶解させることが必要で
ある。添加量を検討するために実施例１と同じ構成の電
池を作り、充放電特性を調べた。DME10モルに対して無
水コハク酸の添加量を変えて溶液を作り、これに１モル
/lとなるようにリチウムヘキサフルオロフォスフェート
（LiPF6）を溶解して有機電解質とした。充放電条件
は、実施例１と同様に行った。第４図には、DME10モル
に対して添加する無水コハク酸のモル数を変えた有機電
解質を用いた電池において過放電を行った時の第15サイ
クル目の放電容量をプロットした。DME10モルに対し
て、無水コハク酸が１モル未満では、LiPF6のイオン解
離が不十分であると思われる放電容量の低下が見られ、
また30モルを超えると粘度が増し全ての無水コハク酸が
DMEに溶解しなくなる。このため、無水コハク酸とDMEの
比率は、1:10から30:10が良い。(Example 2) Since succinic anhydride is a solid at room temperature, it is necessary to add it to a solvent to dissolve it in order to form an organic electrolyte. In order to study the amount of addition, a battery having the same configuration as in Example 1 was made and the charge / discharge characteristics were investigated. Make a solution by changing the addition amount of succinic anhydride to 10 mol of DME, and add 1 mol to this solution.
Lithium hexafluorophosphate (LiPF 6 ) was dissolved to give an organic electrolyte of / l. The charge and discharge conditions were the same as in Example 1. In FIG. 4, the discharge capacity at the 15th cycle when overdischarging was performed in a battery using an organic electrolyte in which the number of moles of succinic anhydride added was changed with respect to 10 moles of DME was plotted. If the amount of succinic anhydride is less than 1 mol with respect to 10 mol of DME, a decrease in discharge capacity, which is considered to be insufficient for ion dissociation of LiPF 6 , is observed.
If it exceeds 30 mol, the viscosity will increase and all succinic anhydride will be
It no longer dissolves in DME. Therefore, the ratio of succinic anhydride to DME is preferably 1:10 to 30:10.
（実施例３） 過放電を行うと分解するPCやEC存在下での無水コハク
酸添加の効果を調べた。実施例１と同様の電池を用い、
有機電解質に使うリチウム塩の種類濃度も同じにした。
モル比でPCとDMEが5:10の混合溶媒に無水コハク酸を５
の割合で添加し、これにリチウム塩を溶解して有機電解
質とした。この有機電解質を用いた電池をＦとする。従
来例として、PC:DMEが5:10の混合溶媒にリチウム塩を溶
解した有機電解質を用いた電池をＧとする。実施例１と
同じ条件で充放電を行った。(Example 3) The effect of adding succinic anhydride in the presence of PC or EC, which decomposes when over-discharged, was investigated. Using the same battery as in Example 1,
The concentration of the lithium salt used for the organic electrolyte was also the same.
5% succinic anhydride in a mixed solvent of PC and DME in a molar ratio of 5:10
Was added at a rate of 1, and a lithium salt was dissolved in this to obtain an organic electrolyte. A battery using this organic electrolyte is designated as F. As a conventional example, a battery using an organic electrolyte in which a lithium salt is dissolved in a mixed solvent of PC: DME of 5:10 is designated as G. Charging and discharging were performed under the same conditions as in Example 1.
第５図には、過放電を行った第15サイクル目の放電曲
線を示す。これより、従来のPCとDMEの混合溶媒に、さ
らに無水コハク酸を添加した時にも、過放電特性が向上
していることがわかる。FIG. 5 shows a discharge curve at the 15th cycle after overdischarging. From this, it can be seen that the overdischarge characteristics are improved even when succinic anhydride is further added to the conventional mixed solvent of PC and DME.
以上の実施例は、正極活物質にMnO2を用いた場合を示
したが、TiS2やCr2O5や八三酸化クロム（Cr3O8）を用い
た場合にも同様な効果が見られた。Although the above examples show the case where MnO 2 is used as the positive electrode active material, the same effect is observed when using TiS 2 , Cr 2 O 5 or chromium trioxide (Cr 3 O 8 ). Was given.
発明の効果 以上のように、本発明により、過放電特性に優れた電
池が得られる。Effects of the Invention As described above, according to the present invention, a battery having excellent overdischarge characteristics can be obtained.
第１図は本発明の一実施例の有機電解質電池の縦断面
図、第２図は各種有機電解質を用いた電池の過放電を行
った後の充放電での放電特性図、第３図は過放電を行う
前の充放電での放電特性図、第４図はモル比で10のDME
に添加する無水コハク酸のモル数を変えた時の電池の放
電容量特性図、第５図は各種有機電解質を用いた電池の
過放電を行った後の充放電での放電特性図である。 A,B,F……本発明の実施例電池、C,D,E,G……従来電池。FIG. 1 is a vertical cross-sectional view of an organic electrolyte battery according to an embodiment of the present invention, FIG. 2 is a discharge characteristic diagram in charging and discharging after overdischarging a battery using various organic electrolytes, and FIG. Discharge characteristics before charge and discharge before over-discharge, Fig. 4 shows DME with molar ratio of 10
FIG. 5 is a discharge capacity characteristic diagram of the battery when the number of moles of succinic anhydride added to is changed, and FIG. 5 is a discharge characteristic diagram in charge and discharge after overdischarging the battery using various organic electrolytes. A, B, F ... Example batteries of the present invention, C, D, E, G ... Conventional batteries.
Claims (2)
機電解質を有し、前記有機電解質中に無水コハク酸が添
加されていることを特徴とする有機電解質二次電池。1. An organic electrolyte secondary battery comprising a negative electrode, a positive electrode, and an organic electrolyte in which a lithium salt is dissolved, and succinic anhydride is added to the organic electrolyte.
成する有機溶媒に対して、モル比で1:10から30:10であ
ることを特徴とする特許請求の範囲第１項記載の有機電
解質二次電池。2. The succinic anhydride is added in a molar ratio of 1:10 to 30:10 with respect to the organic solvent that constitutes the organic electrolyte. Organic electrolyte secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291104A JPH084015B2 (en) | 1987-11-18 | 1987-11-18 | Organic electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291104A JPH084015B2 (en) | 1987-11-18 | 1987-11-18 | Organic electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01134872A JPH01134872A (en) | 1989-05-26 |
| JPH084015B2 true JPH084015B2 (en) | 1996-01-17 |
Family
ID=17764501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62291104A Expired - Fee Related JPH084015B2 (en) | 1987-11-18 | 1987-11-18 | Organic electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH084015B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2697365B2 (en) * | 1991-05-30 | 1998-01-14 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
| KR100801592B1 (en) * | 2006-01-05 | 2008-02-11 | 제일모직주식회사 | Non-aqueous electrolyte containing succinic acid and trimethylsilyl borate and lithium secondary battery comprising same |
| JP5229527B2 (en) | 2006-08-25 | 2013-07-03 | ソニー株式会社 | Secondary battery electrolyte and secondary battery |
-
1987
- 1987-11-18 JP JP62291104A patent/JPH084015B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01134872A (en) | 1989-05-26 |
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