JPH0760701B2 - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH0760701B2 JPH0760701B2 JP61174208A JP17420886A JPH0760701B2 JP H0760701 B2 JPH0760701 B2 JP H0760701B2 JP 61174208 A JP61174208 A JP 61174208A JP 17420886 A JP17420886 A JP 17420886A JP H0760701 B2 JPH0760701 B2 JP H0760701B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- organic electrolyte
- diox
- solvent
- positive electrode
- 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 - Lifetime
Links
- 239000005486 organic electrolyte Substances 0.000 title claims description 19
- 239000002904 solvent Substances 0.000 claims description 12
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 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 5
- 239000012046 mixed solvent Substances 0.000 description 4
- XEEVZYJHSSNNDI-UHFFFAOYSA-N 1-(1,3-dioxolan-2-yl)ethanone Chemical compound CC(=O)C1OCCO1 XEEVZYJHSSNNDI-UHFFFAOYSA-N 0.000 description 2
- YGZLYOZDDNGRSZ-UHFFFAOYSA-N 1-(1,3-dioxolan-4-yl)ethanone Chemical compound CC(=O)C1COCO1 YGZLYOZDDNGRSZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 2
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-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
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 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
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 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
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (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。Description: TECHNICAL FIELD The present invention relates to an improvement in an organic electrolyte battery using lithium or the like for a negative electrode, and more particularly to an improvement in an organic solvent constituting an 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。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。2. Description of the Related Art As an organic electrolyte battery, a battery using an alkali metal such as lithium or magnesium or an alkaline earth metal for a negative electrode and fluorinated graphite or manganese dioxide for a positive electrode has been studied and partially put into practical use. Recently, research on a lithium organic electrolyte secondary battery using lithium for the negative electrode and titanium disulfide for the positive electrode has also been actively conducted.
これら電池の電解質には、溶媒にプロピレンカーボネイ
ト（PC）や1,3−ジオキソラン（1,3−Diox）,4−メチル
−1,3−ジオキソラン（４−Me−1,3−Diox）を用い、こ
れら溶媒に過塩素酸リチウム（LiClO4）やリチウムヘキ
サフロロアルシネート（LiAsF6）を溶質として溶解した
有機電解質が用いられて来た。Propylene carbonate (PC), 1,3-dioxolane (1,3-Diox), and 4-methyl-1,3-dioxolane (4-Me-1,3-Diox) were used as the solvent for the electrolyte of these batteries. , Organic solvents obtained by dissolving lithium perchlorate (LiClO 4 ) and lithium hexafluoroarsinate (LiAsF 6 ) as solutes in these solvents 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 In batteries using these organic electrolytes, there is a problem 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、２また
は４の位置にアセチル基を有する1,3−ジオキソランを
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 1,3-dioxolane having an acetyl group at the 2 or 4 position is used as a solvent used for a conventional organic electrolyte.
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
利用率の低下が起った。一方、1,3−Dioxや４−Me−1,3
−Dioxでは、粘度は小さいが、誘電率が小のため、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
起り、したがって、1,3−Dioxや４−Me−1,3−Dioxの類
で誘電率を大にすることにより、電池に使用した場合、
良好な特性が得られる。Function Conventional PC has a large dielectric constant but a large viscosity. Therefore, when it is used in a battery, the voltage and the utilization factor of the positive electrode are decreased during high-rate discharge. On the other hand, 1,3-Diox and 4-Me-1,3
-Diox has a low viscosity but a low dielectric constant, so the utilization factor of the positive electrode is high at high rate discharge, but the battery voltage drops, and therefore 1,3-Diox or 4-Me-1, When used in batteries by increasing the dielectric constant with 3-Diox type,
Good characteristics are obtained.
実施例 本発明は1,3−Dioxを改良し、下に示すように1,3−Diox
の ２または４の位置にアセチル基を持たせることにより、
誘電率が増大し、電池特性を向上させたものである。EXAMPLE The present invention improves on 1,3-Diox, as shown below, 1,3-Diox
of By having an acetyl group at the 2 or 4 position,
The dielectric constant is increased and the battery characteristics are improved.
〔実施例１〕 負極に直径17.5mm,厚さ0.5mmのリチウムを用いた。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
部よりなる合剤0.4gを、直径17μ5mmの円盤状に圧縮成
型したものを用いた。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２図に示したコイ
ン形電池を構成し、有機電解質の違いによる特性差を検
討した。なお、第２図において１は正極、２は負極、３
はセパレータである。有機電解質の溶質として、全て１
モル/lのLiClO4を用いた。有機電解質の溶媒として、本
発明の４−アセチル−1,3−ジオキソランを用いた電池
をA,従来のPC,1,3−Dioc,4−Me−1,3−Dioxを用いた電
池各々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PCと1,3−Dioxの混合溶媒を用いた
電池をＥとする。Ａ〜Ｅの電池の有機電解質の量は全て
200μｌとした。これらの電池を100Ωの負荷で放電させ
た時の放電特性を第１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1,3−Dioxや４−Me−1,3−Diox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。そこで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1,3−Diox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４−アセチル−1,3−ジオキソランを
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。Example 1 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 consisting 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 compression molded into a disk shape having a diameter of 17 μ5 mm. I used one. The theoretical filling capacity of this positive electrode is 103mAh
Met. The positive and negative electrodes were used to construct the coin battery shown in FIG. 2, and the difference in characteristics due to the difference in organic electrolyte was examined. In FIG. 2, 1 is a positive electrode, 2 is a negative electrode, 3
Is a separator. All 1 as solute of organic electrolyte
Mol / l LiClO 4 was used. As a solvent for the organic electrolyte, the battery using 4-acetyl-1,3-dioxolane of the present invention is A, and the battery using conventional PC, 1,3-Dioc, 4-Me-1,3-Diox is B, respectively. , C, D. Also, as an example of a conventional mixed solvent,
Let E be a battery using a mixed solvent of 1: 1 PC and 1,3-Diox in a volume ratio. The amount of organic electrolyte in the batteries A to E is all
The volume was 200 μl. Fig. 1 shows the discharge characteristics when these batteries were discharged under a load of 100Ω. In the battery B using the conventional PC, the voltage at the initial stage of discharge is large, but the utilization rate is low.
Also, in the C and D batteries using low-viscosity solvents such as 1,3-Diox and 4-Me-1,3-Diox, the utilization rate is improved but the voltage is low. Therefore, in the battery E using the conventional mixed solvent of PC and 1,3-Diox in which the solvent having a high dielectric constant and the solvent having a low viscosity are combined, the battery characteristics are improved as compared with B, C and D.
However, in the organic electrolyte battery A using 4-acetyl-1,3-dioxolane of the present invention as a solvent, both voltage and utilization are improved as compared with B to E.
〔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。
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と同じである。
したがって正極の理論充填量は80mAhであった。有機電
解質の溶質は、LiClO4の代りに１モル/lのLiAsF6を用い
た。本発明の２−アセチル−1,3−ジオキソランを溶媒
に用いた電池をF,PC,1,3−Diox,4−Me−1,3−Diox体積
比で1:1とPCと1,3−Dioxの混合溶媒を用いた電池を各々
G,H,I,Jとする。この電池を10mA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になる時点で止めるようにした。第３図には、
第３サイクルでの放電曲線を示す。これにより本発明の
２−アセチル−1,3−ジオキソランを用いた電池は、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。[Embodiment 2] In this embodiment, the case of application to a secondary battery will be described.
A battery was constructed in the same manner as in Example 1. However, titanium disulfide was used as the active material of the positive electrode instead of manganese dioxide, and the mixture mixture amount and mixture mixture amount were the same as in Example 1.
Therefore, the theoretical filling amount of the positive electrode was 80 mAh. As the solute of the organic electrolyte, 1 mol / l LiAsF 6 was used instead of LiClO 4 . A battery using 2-acetyl-1,3-dioxolane of the present invention as a solvent was used as F, PC, 1,3-Diox, 4-Me-1,3-Diox volume ratio of 1: 1 and PC and 1,3. − Each battery using Diox mixed solvent
G, H, I, J. This battery was repeatedly charged and discharged at a constant current of 10 mA. Discharging was stopped when the battery voltage reached 1.2V, and charging was stopped when the battery voltage reached 2.8V. In Figure 3,
The discharge curve in the 3rd cycle is shown. From this, it can be seen that the battery using 2-acetyl-1,3-dioxolane of the present invention has improved voltage and utilization rate as compared with the battery using the conventional solvent.
発明の効果 以上示したように本発明の２または４の位置にアセチル
基を有する1,3−ジオキソランを有機電解質の溶媒に用
いた電池では、高率放電特性に優れている。EFFECTS OF THE INVENTION As described above, the battery of the present invention in which 1,3-dioxolane having an acetyl group at the 2 or 4 position is used as the solvent of the organic electrolyte is excellent in high rate discharge characteristics.
第１図は本発明の一実施例の有機電解質電池の放電曲線
図、第２図は特性測定に用いたコイン形電池の断面図、
第３図は二次電池の第３サイクル目の放電曲線図であ
る。 A,F……本発明の一実施例の有機電解質電池、Ｂ〜E,G〜
Ｊ……従来例の電池。FIG. 1 is a discharge curve diagram of an organic electrolyte battery of one embodiment of the present invention, FIG. 2 is a sectional view of a coin-shaped battery used for characteristic measurement,
FIG. 3 is a discharge curve diagram of the secondary battery in the third cycle. A, F ... Organic electrolyte battery of one embodiment of the present invention, B to E, G to
J: Conventional battery.
Claims (1)
該有機電解質の溶媒に、２または４の位置にアセチル基
を有する1,3−ジオキソランを用いることを特徴とする
有機電解質電池。1. A negative electrode, a positive electrode, and an organic electrolyte,
An organic electrolyte battery, wherein 1,3-dioxolane having an acetyl group at the 2 or 4 position is used as a solvent for the organic electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174208A JPH0760701B2 (en) | 1986-07-24 | 1986-07-24 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174208A JPH0760701B2 (en) | 1986-07-24 | 1986-07-24 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6332869A JPS6332869A (en) | 1988-02-12 |
| JPH0760701B2 true JPH0760701B2 (en) | 1995-06-28 |
Family
ID=15974613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61174208A Expired - Lifetime JPH0760701B2 (en) | 1986-07-24 | 1986-07-24 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0760701B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017060151A1 (en) * | 2015-10-09 | 2017-04-13 | Basf Se | Electrolyte composition containing methyl 2-methyl-1,3-dioxolane-2-carboxylate, and electrochemical cells comprising the same |
-
1986
- 1986-07-24 JP JP61174208A patent/JPH0760701B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6332869A (en) | 1988-02-12 |
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