JPH01132059A - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH01132059A JPH01132059A JP62291103A JP29110387A JPH01132059A JP H01132059 A JPH01132059 A JP H01132059A JP 62291103 A JP62291103 A JP 62291103A JP 29110387 A JP29110387 A JP 29110387A JP H01132059 A JPH01132059 A JP H01132059A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- organic electrolyte
- solvent
- batteries
- tetrahydrofuran
- 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
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 16
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 208000028659 discharge Diseases 0.000 description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
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電池
の改良に関するものであり、特に有機電解質を構成する
有機溶媒の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to improvements in organic electrolyte batteries using lithium or the like as a negative electrode, and particularly to improvements in organic solvents constituting the organic electrolyte.
従来の技術
有機電解質電池として、負極にリチウムやマグネシウム
などのアルカリ金属、アルカリ土類金属を用い、正極に
フッ化黒鉛や、二酸化マンガンを用いた電池が研究され
、一部実用化されている。Conventional technology Organic electrolyte batteries using alkali metals or alkaline earth metals such as lithium or magnesium for the negative electrode and graphite fluoride or manganese dioxide for the positive electrode have been researched and some have been put into practical use.
また最近では、負極にリチウム、正極に二硫化チタンを
用いたリチウム有機電解質二次電池の研究も活発に行わ
れている。Recently, research has also been actively conducted on lithium organic electrolyte secondary batteries that use lithium for the negative electrode and titanium disulfide for the positive electrode.
これら電池の電解質には、溶媒にプロピレンカーボネー
ト（ＰＣ）やテトラヒドロフラン（’Ｉ’ＨＦ）、２−
メチルテトラヒトｏ７ラン（２−Ｍｅ −ＴＨＦ） 。The electrolytes for these batteries include solvents such as propylene carbonate (PC), tetrahydrofuran ('I'HF), and 2-
Methyltetrahydro7ran (2-Me-THF).
を用い、これら溶媒に、過塩素酸リチウム（Ｌ Ｉ Ｃ
ＺＯ４）やリチウムへキサフロロアルシネート（ＬｉＡ
ｓＦ６）を溶質として溶款した有機電解質が用いられて
来た。using lithium perchlorate (L I C
ZO4) and lithium hexafluoroarsinate (LiA
Organic electrolytes in which sF6) is dissolved as a solute have been used.
発明が解決しようとする問題点
これらの有機電解質を用いた電池では、高率放電を行っ
た場合、電池の電圧が低下するという問題点があった。Problems to be Solved by the Invention Batteries using these organic electrolytes have a problem in that the voltage of the battery decreases when high rate discharge is performed.
問題点を解決するための手段
本発明では、従来の有機電解質に用いる溶媒に、少なく
ともテトラヒドロフラン−３、５−ジオンを使用するこ
とを特徴としている。Means for Solving the Problems The present invention is characterized in that at least tetrahydrofuran-3,5-dione is used as a solvent for conventional organic electrolytes.
作 用
従来のｐｃは、誘電率は大であるが粘度が大であり、こ
のため、電池に使用すると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ＴＨＦや２− Ｍｅ
−Ｔ ＨＦでは、粘度は小さいが、誘電率が小さいため
、高率放電時には、正極の利用率は大となるが電池電圧
の低下が起こる。したがって、ＴＨＦや２− Ｍｅ −
Ｔ ＨＦＯ類で誘電率を大にすることによシ、電池に使
用した場合、良好な特性が得られることが予想できる。Function Conventional PC has a high dielectric constant but a high viscosity, and for this reason, when used in a battery, a drop in voltage and a drop in the utilization rate of the positive electrode occur during high rate discharge. On the other hand, THF and 2-Me
-TH HF has a low viscosity but a low dielectric constant, so during high rate discharge, the utilization rate of the positive electrode is high, but the battery voltage decreases. Therefore, THF and 2-Me-
By increasing the dielectric constant with T HFOs, it can be expected that good characteristics will be obtained when used in batteries.
本発明は、Ｔ！（Ｆを改良し、下に示すようにＴＨＦの
３および５の位置が、カルボニルおよびカルボキシル基
とすることにより誘電率が増大し、電池特性を向上させ
たものである。The present invention is based on T! (By improving F and replacing the 3 and 5 positions of THF with carbonyl and carboxyl groups as shown below, the dielectric constant is increased and the battery characteristics are improved.
実施例 以下、本発明の詳細な説明する。Example The present invention will be explained in detail below.
実施例１
負極に直径１７．５ｍｍ、厚さ０．５ ｍｍの円柱体リ
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１ｏｏ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１．
４ｇを、直径１７．６ｍｍ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１０３ ｍＡｈ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 A lithium cylinder having a diameter of 17.5 mm and a thickness of 0.5 mm was used as a negative electrode. The theoretical charging amount at this time is 247mAh. For the positive electrode, a mixture of 1.0 g 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 used.
4 g was compression-molded into a disk shape with a diameter of 17.6 mm. The theoretical filling capacity of this positive electrode was 103 mAh. A flat battery shown in FIG. 1 was constructed using these positive and negative electrodes, and differences in characteristics due to differences in organic electrolytes were investigated.
第１図において、１は電池ケース、２は封目板、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.
有機電解質の溶質として、全て濃度１モ／Ｉ／／ｌのＬ
ｉＣＩＯ４を用いた。有機電解質の溶媒として、テトラ
ヒドロフラン−３、５−ジオンを用いり電池をＡ、従来
のＰＣ、ＴＨＦ 、 ２− Ｍｅ−ＴＨＦを用いた電池
を各々Ｂ、Ｃ，Ｄとする。また従来の混合溶媒の例とし
て、溶媒に体積比で１＝１の割合でＰＣとＴＨＦとを混
合した溶媒を用いた電池をＥとする。また、これらの電
池の有機電解質の量は、全て２００μｔとした。As a solute in an organic electrolyte, all L at a concentration of 1 mo/I//l
iCIO4 was used. A battery using tetrahydrofuran-3,5-dione as the organic electrolyte solvent is designated as A, and batteries B, C, and D are designated as batteries using conventional PC, THF, and 2-Me-THF, respectively. Further, as an example of a conventional mixed solvent, a battery E uses a solvent in which PC and THF are mixed at a volume ratio of 1=1. Further, the amount of organic electrolyte in these batteries was all 200 μt.
これらの電池を１０ｏΩの負荷で放電させた時の放電特
性を第２図に示す。従来のＰＣを用いた電池Ｂでは、放
電初期の電圧は大であるが、利用率が低い。またＴＨＦ
や２− Ｍｅ −Ｔ ＨＦなどの低粘度溶媒を用いたＣ
、Ｄの電池では、利用率は向上しているが、電圧が低い
ことがわかる。また、従来の高誘電率の溶媒と低粘度の
溶媒を組み合せたｐｃとＴＨＦの混合溶媒を用いた電池
Ｅでは、Ｂ、Ｃ，Ｄに比べ電池特性は向上している。し
かし、本発明のテトラヒドロフラン−３、５−ジオンを
溶媒に用いた有機電解質電池Ａでは、Ｂ−Ｅに比べ、電
圧、利用率ともに向上していることがわかる。FIG. 2 shows the discharge characteristics when these batteries were discharged under a load of 10 ohms. In battery B using a conventional PC, the voltage at the initial stage of discharge is high, but the utilization rate is low. Also THF
C using a low viscosity solvent such as or 2-Me-THF
It can be seen that in the batteries of , D, the utilization rate is improved, but the voltage is low. Further, in battery E using a mixed solvent of PC and THF, which is a combination of a conventional high dielectric constant solvent and a low viscosity solvent, the battery characteristics are improved compared to B, C, and D. However, it can be seen that in organic electrolyte battery A using tetrahydrofuran-3,5-dione of the present invention as a solvent, both the voltage and the utilization rate are improved compared to BE.
実施例２ 本実施例では、二次電池に応用した場合について示す。Example 2 In this example, a case where the present invention is applied to a secondary battery will be described.
実施例１と同様に電池を構成した。ただし、正極の活物
質には、二酸化マンガンの代わりに、二硫化チタンを用
い、合剤配合量、合剤充填量は実施例１と同様である。A battery was constructed in the same manner as in Example 1. However, as the active material of the positive electrode, titanium disulfide was used instead of manganese dioxide, and the amount of the mixture blended and the amount of the mixture filled were the same as in Example 1.
したがって正極の理論充填量は８０ ｍＡｈであった。Therefore, the theoretical filling amount of the positive electrode was 80 mAh.
有機電解質の溶質は、Ｌｉ（ＪＯ４Ｏ代わりＫ １ ％
／’ ／ ｌ ＯＬ Ｉ Ａ ｓ Ｆ ｅ ヲ用いた
。本発明のテトラヒドロフラン−３、５−ジオンを溶媒
に用いた電池をＦ 、 ＰＣ、ＴＨＦ 。The solute of the organic electrolyte is Li (K1% instead of JO4O).
/' / l OL I A s Fe wo was used. Batteries using the tetrahydrofuran-3,5-dione of the present invention as a solvent were F, PC, and THF.
２−Ｍｅ−ＴＨＦ、体積比で１：１の割合でＰＣとＴＨ
Ｆとを混合した溶液を用いた電池を各々Ｇ。2-Me-THF, PC and TH in a 1:1 volume ratio
Each battery using a solution mixed with F is labeled G.
Ｈ，Ｉ 、Ｊとする。Let them be H, I, and J.
これらの電池を１０ ｍＡの定電流で充放電をくり返し
た。放電は電池電圧が１．２ｖになる時点、充電は２．
８ｖになる時点でそれぞれ止めるようにした。These batteries were repeatedly charged and discharged at a constant current of 10 mA. Discharging occurs when the battery voltage reaches 1.2V, and charging occurs when the battery voltage reaches 2.2V.
I tried to stop each when it reached 8v.
第３図には、第３サイクルでの放電曲線を示す。FIG. 3 shows the discharge curve in the third cycle.
これより本発明の溶媒を用いた電池は、従来の溶媒を用
いたものに比べ、電圧、利用率ともに向上していること
がわかる。From this, it can be seen that the battery using the solvent of the present invention has improved both voltage and utilization rate compared to the battery using the conventional solvent.
発明の効果
以上のように、本発明により高率放電特性に優れた電池
が得られる。Effects of the Invention As described above, the present invention provides a battery with excellent high rate discharge characteristics.
第１図は実施例に用いた電池の縦断面図、第２図は各種
溶媒を用いた一次電池の放電曲線を示す図、第３図は二
次電池の第３サイクル日の放電曲線を示す図である。
代理人の氏名 弁理士 中 尾 敏 男 はφ１１名３
− 負 極
４−’ｔ＝パレータ
５−正 板
第１図Figure 1 is a longitudinal cross-sectional view of the battery used in the examples, Figure 2 is a diagram showing the discharge curve of the primary battery using various solvents, and Figure 3 is the discharge curve of the secondary battery on the third cycle day. It is a diagram. Name of agent: Patent attorney Toshio Nakao, φ11 people 3
- Negative electrode 4-'t=Parameter 5-Positive plate Fig. 1
Claims (1)
媒に、少なくともテトラヒドロフラン−３、５−ジオン
を用いたことを特徴とする有機電解質電池。An organic electrolyte battery comprising a negative electrode, a positive electrode, and an organic electrolyte, the battery comprising at least tetrahydrofuran-3,5-dione as a solvent for the organic electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291103A JPH0763015B2 (en) | 1987-11-18 | 1987-11-18 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291103A JPH0763015B2 (en) | 1987-11-18 | 1987-11-18 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01132059A true JPH01132059A (en) | 1989-05-24 |
| JPH0763015B2 JPH0763015B2 (en) | 1995-07-05 |
Family
ID=17764488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62291103A Expired - Lifetime JPH0763015B2 (en) | 1987-11-18 | 1987-11-18 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0763015B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1807899A1 (en) * | 2004-10-27 | 2007-07-18 | Cheil Industries Inc. | Nonaqueous electrolyte for battery |
| US10135048B2 (en) | 2015-02-27 | 2018-11-20 | GS Yuasa Internationl Ltd. | Lead-acid battery |
-
1987
- 1987-11-18 JP JP62291103A patent/JPH0763015B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1807899A1 (en) * | 2004-10-27 | 2007-07-18 | Cheil Industries Inc. | Nonaqueous electrolyte for battery |
| JP2008518392A (en) * | 2004-10-27 | 2008-05-29 | チェイル インダストリーズ インコーポレイテッド | Non-aqueous electrolyte for batteries |
| EP1807899A4 (en) * | 2004-10-27 | 2009-11-11 | Cheil Ind Inc | Nonaqueous electrolyte for battery |
| US10135048B2 (en) | 2015-02-27 | 2018-11-20 | GS Yuasa Internationl Ltd. | Lead-acid battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0763015B2 (en) | 1995-07-05 |
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