JPH0719620B2 - Organic electrolyte secondary battery - Google Patents
Organic electrolyte secondary batteryInfo
- Publication number
- JPH0719620B2 JPH0719620B2 JP61133307A JP13330786A JPH0719620B2 JP H0719620 B2 JPH0719620 B2 JP H0719620B2 JP 61133307 A JP61133307 A JP 61133307A JP 13330786 A JP13330786 A JP 13330786A JP H0719620 B2 JPH0719620 B2 JP H0719620B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- organic electrolyte
- lithium
- battery
- solvent
- 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 13
- 239000002904 solvent Substances 0.000 claims description 12
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 238000007599 discharging Methods 0.000 description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910005580 NiCd Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- 238000007789 sealing Methods 0.000 description 1
- 229910052718 tin Inorganic materials 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
-
- 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二次
電池の改良に関するものであり、特に有機電解質の溶媒
を改良し、負極の充放電の電流効率を向上させるもので
ある。TECHNICAL FIELD The present invention relates to an improvement in an organic electrolyte secondary battery using lithium or the like for a negative electrode, and in particular, an improvement in the solvent of the organic electrolyte to improve the charging / discharging current of the negative electrode. It improves efficiency.
従来の技術 リチウムなどのアルカリ金属を負極に用いた有機電解質
電池は、従来の鉛やニカド蓄電池に比べ、高エネルギー
密度になることが期待され、研究が活発に行われてい
る。その代表的な例として、負極にリチウム金属、正極
に二硫化チタン（TiS2）を用い、有機電解質の溶質とし
て、過塩素酸リチウム（LiClO4）や、ヘキサフロロアル
ミネート（LiAsF6）、溶媒にプロピレンカーボネート
（PC）や２−メチルテトラヒドロフラン（２−Me−TH
F）を用いたものがある。2. Description of the Related Art Organic electrolyte batteries using an alkali metal such as lithium in the negative electrode are expected to have a higher energy density than conventional lead and NiCd storage batteries, and are being actively researched. As a typical example, lithium metal is used for the negative electrode, titanium disulfide (TiS 2 ) is used for the positive electrode, and as the solute of the organic electrolyte, lithium perchlorate (LiClO 4 ), hexafluoroaluminate (LiAsF 6 ), solvent Propylene carbonate (PC) and 2-methyltetrahydrofuran (2-Me-TH
F) is used.
発明が解決しようとする問題点 これらの電池では、負極の充放電の電流効率が60〜80％
と低いために未だに実用化されていない。Problems to be Solved by the Invention In these batteries, the current efficiency of charging / discharging the negative electrode is 60 to 80%.
Because it is low, it has not been put to practical use.
問題点を解決するための手段 本発明では、従来の有機電解質の溶媒に代えて、３の位
置の水素をアセチル基で置換したエチレンカーボネート
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 by using ethylene carbonate in which hydrogen at the 3-position is replaced with an acetyl group, instead of the solvent of the conventional organic electrolyte.
作用 従来のPCや２−Me−THFを溶媒として用いた有機電解質
中で負極リチウムを充電すると、活性なリチウムのた
め、析出したリチウムの一部が溶媒と反応して、リチウ
ムの塩が生成する。例えばPC中では、次式のように 析出したリチウムが炭酸リチウムになることが報告され
ている。２−Me−THFの場合にも、この溶媒がリチウム
と反応すると考えられる。このため負極の電流効率（充
電に用した電荷量に対する、放電可能な電荷量）は、60
〜80％と低かった。Action When negative electrode lithium is charged in an organic electrolyte using conventional PC or 2-Me-THF as a solvent, part of the deposited lithium reacts with the solvent due to active lithium, and a lithium salt is formed. . For example, in a PC, It is reported that the deposited lithium becomes lithium carbonate. Even in the case of 2-Me-THF, this solvent is considered to react with lithium. Therefore, the current efficiency of the negative electrode (the amount of charge that can be discharged with respect to the amount of charge used for charging) is 60.
It was as low as ~ 80%.
本発明者は、PCの場合Ｃ−Ｏの結合がLiとの反応により
切れると考えて、このＣの位置の水素をアセチル基で置
換することにより、これらの強い電子吸引性のため、Ｃ
−Ｏの結合は切れにくくなり、これにより電流効率は向
上すると考えた。さらに、カーボネートの骨格をエチレ
ンカーボネートとすることにより、CH3基の電子供与性
はなくなり、充放電の電流効率は増加すると考えた。例
えば、３の位置をアセチル基で置換した３−アセチルエ
チレンカーボネートは次式のような構造となる。The present inventors believe that in the case of PC, the C—O bond is broken by the reaction with Li, and by substituting the hydrogen at the C position with an acetyl group, these strong electron-withdrawing properties cause C.
It was thought that the bond of -O was hard to be broken, and thereby the current efficiency was improved. Furthermore, by using ethylene carbonate as the skeleton of the carbonate, it was considered that the electron donating property of the CH 3 group disappears and the current efficiency of charge / discharge increases. For example, 3-acetylethylene carbonate in which the 3-position is substituted with an acetyl group has a structure represented by the following formula.
実施例 以下、本発明の実施例を説明する。 Examples Hereinafter, examples of the present invention will be described.
実施例１ ビーカー形セル中で負極リチウムの電流効率を検討し
た。大きさ2cm×2cmのニッケル板を負極の集電体とし、
これにリードとしてニッケルリボンを付けた。対極には
白金を用い、照合電極にはリチウムを用いた。このセル
中に各種有機電解質を入れ、4mAで２時間充電したの
ち、4mAで負極の電位が照合電極に対して1.0Vになるま
で放電した。この充電放電をくり返した。電流効率は、
充電した電荷量に対する放電できた電荷量で計算した。
例えば、放電が1.5時間であるならば、（1.5hr×4mA）
／（2hr×4mA）×100＝75％ となる。この充放電を50サイクルくり返して、平均の電
流効率を求めた。この値が大きい程、析出したリチウム
は溶媒と反応していないことになる。溶質は全て濃度１
モル／のLiClO4を用いた。結果を表に示す。Example 1 The current efficiency of negative electrode lithium was examined in a beaker cell. A nickel plate with a size of 2 cm x 2 cm was used as the negative electrode current collector,
A nickel ribbon was attached to this as a lead. Platinum was used for the counter electrode and lithium was used for the reference electrode. Various organic electrolytes were placed in this cell, charged at 4 mA for 2 hours, and then discharged at 4 mA until the potential of the negative electrode became 1.0 V with respect to the reference electrode. This charging / discharging was repeated. The current efficiency is
It was calculated by the amount of charge that could be discharged relative to the amount of charge that was charged.
For example, if the discharge is 1.5 hours, (1.5hr x 4mA)
/ (2hr x 4mA) x 100 = 75%. This charging / discharging was repeated 50 cycles to obtain the average current efficiency. The larger this value is, the less the precipitated lithium reacts with the solvent. Concentration of all solutes is 1
Mol / LiClO 4 was used. The results are shown in the table.
これより、３の位置の水素をアセチル基で置換すること
により、充放電の電流効率は増大することがわかる。From this, it is understood that the charge / discharge current efficiency is increased by substituting the hydrogen at the 3 position with an acetyl group.
実施例２ 負極に直径17.5mm、厚さ0.5mmの円板状リチウムを用い
た。この時の理論充填容量は247mAhである。正極には、
TiS2100重量部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４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の円板状に圧縮成形
したものを用いた。この時の理論充填容量は80mAhであ
った。これらの正極，負極により扁平形電池を試作し
た。この電池の構造を第１図に示す。 Example 2 Discotic lithium having a diameter of 17.5 mm and a thickness of 0.5 mm was used as the negative electrode. The theoretical filling capacity at this time is 247 mAh. For the positive electrode,
Acetylene black 10 as a conductive agent in 100 parts by weight of TiS 2
0.4 g of a mixture containing 10 parts by weight of polytetrafluoroethylene resin as a binder was compression-molded into a disk having a diameter of 17.5 mm. The theoretical filling capacity at this time was 80 mAh. A flat battery was prototyped using these positive and negative electrodes. The structure of this battery is shown in FIG.
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.
この電池を2mAの定電流で充放電をくり返した。放電は
電池電圧が1.2Vになる時点で、充電は2.8Vになる時点で
それぞれ止めた。有機電解質の溶質には１モル／のLi
AsF6を用いた。各電池の有機電解質量は全て200μと
した。有機電解質の溶媒に本発明の３−アセチルエチレ
ンカーボネートを用いた電池をＡとし、従来のPC,2−Me
−THFを用いた電池を各々B,Cとする。第２図にはこれら
電池の各サイクルにおける放電電気量をプロットした。
これより本発明の３の位置の水素をアセチル基で置換し
たエチレンカーボネートを用いることにより、電池のサ
イクル特性が向上することがわかる。これは、実施例１
に示したように負極の充放電の電流効率が向上したため
である。This battery was repeatedly charged and discharged at a constant current of 2 mA. Discharging was stopped when the battery voltage reached 1.2V and charging was stopped at 2.8V. 1 mol / Li for solute of organic electrolyte
AsF 6 was used. The organic electrolytic mass of each battery was 200 μm. A battery using the 3-acetylethylene carbonate of the present invention as the solvent of the organic electrolyte is designated as A, and the conventional PC, 2-Me
-The batteries using THF are B and C, respectively. In FIG. 2, the amount of electricity discharged in each cycle of these batteries is plotted.
From this, it is understood that the cycle characteristics of the battery are improved by using ethylene carbonate in which hydrogen at the 3-position of the present invention is substituted with an acetyl group. This is Example 1
This is because the current efficiency of charging / discharging the negative electrode is improved as shown in FIG.
以上は、リチウムを負極として用いた実施例について述
べたが、負極にリチウム−アルミニウム合金や、負極に
鉛，スズ，ビスマス，カドミウムなどの合金を用いて、
充電により負極中にリチウムを吸蔵させ、放電で吸蔵し
たリチウムを放出させる電極に対しても、本発明の溶媒
は大きな効果を有した。In the above, the embodiment using lithium as the negative electrode was described, but using a lithium-aluminum alloy for the negative electrode or an alloy such as lead, tin, bismuth, or cadmium for the negative electrode,
The solvent of the present invention also had a great effect on an electrode that occludes lithium in the negative electrode by charging and releases lithium occluded by discharging.
また正極については、TiS2の場合のみを示したが、本発
明の溶媒が負極に対して大きな効果を有するのであり、
他の活物質を正極に用いても、電池の負極の充放電効率
は向上し、それに伴い電池のサイクル特性は向上する。Further, for the positive electrode, only the case of TiS 2 is shown, but since the solvent of the present invention has a great effect on the negative electrode,
Even if another active material is used for the positive electrode, the charge and discharge efficiency of the negative electrode of the battery is improved, and the cycle characteristics of the battery are improved accordingly.
発明の効果 以上のように、本発明により、負極の充放電の電流効率
が向上し、電池のサイクル特性が向上する。Effects of the Invention As described above, according to the present invention, the current efficiency of charging / discharging the negative electrode is improved, and the cycle characteristics of the battery are improved.
第１図は実施例に用いた電池の縦断面図、第２図は各種
溶媒を用いた電池のサイクル特性を示す図である。Ａが
本発明のもの、B,Cが従来例である。 ３……負極、４……セパレータ、５……正極。FIG. 1 is a longitudinal sectional view of a battery used in Examples, and FIG. 2 is a diagram showing cycle characteristics of batteries using various solvents. A is the present invention, and B and C are conventional examples. 3 ... Negative electrode, 4 ... Separator, 5 ... Positive electrode.
Claims (1)
電解質の溶媒に、３の位置の水素をアセチル基で置換し
たエチレンカーボネートを用いた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, wherein ethylene carbonate in which hydrogen at the 3-position is replaced by an acetyl group is used as a solvent of the organic electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61133307A JPH0719620B2 (en) | 1986-06-09 | 1986-06-09 | Organic electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61133307A JPH0719620B2 (en) | 1986-06-09 | 1986-06-09 | Organic electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62290074A JPS62290074A (en) | 1987-12-16 |
| JPH0719620B2 true JPH0719620B2 (en) | 1995-03-06 |
Family
ID=15101607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61133307A Expired - Fee Related JPH0719620B2 (en) | 1986-06-09 | 1986-06-09 | Organic electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0719620B2 (en) |
-
1986
- 1986-06-09 JP JP61133307A patent/JPH0719620B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62290074A (en) | 1987-12-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |