JPH0760702B2 - Organic electrolyte secondary battery - Google Patents
Organic electrolyte secondary batteryInfo
- Publication number
- JPH0760702B2 JPH0760702B2 JP61174209A JP17420986A JPH0760702B2 JP H0760702 B2 JPH0760702 B2 JP H0760702B2 JP 61174209 A JP61174209 A JP 61174209A JP 17420986 A JP17420986 A JP 17420986A JP H0760702 B2 JPH0760702 B2 JP H0760702B2
- Authority
- JP
- Japan
- Prior art keywords
- organic electrolyte
- negative electrode
- lithium
- solvent
- secondary battery
- 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 15
- 239000002904 solvent Substances 0.000 claims description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 10
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 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 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- -1 3-acetylpropylene carbonate Chemical compound 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 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
- 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
- 229910013684 LiClO 4 Inorganic materials 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
- CBPYEEVDXLVKCU-UHFFFAOYSA-N carbonic acid;pent-4-en-2-one Chemical compound OC(O)=O.CC(=O)CC=C CBPYEEVDXLVKCU-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
- 125000004435 hydrogen atom Chemical group [H]* 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
- 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
- 239000004071 soot Substances 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、従来の鉛蓄電池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。そして代表的な例として、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
ロロアルシネート（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
−THF）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 as a negative electrode are expected to have higher energy density than conventional lead storage batteries and nicad storage batteries, and research is being actively conducted. As a typical example, lithium metal is used for the negative electrode, titanium disulfide (TiS 2 ) is used for the positive electrode, and lithium perchlorate (LiClO 4 ) or hexafluoroarsinate (LiAsF 6 ) or solvent is used as the solute of the organic electrolyte. Propylene carbonate (PC) and 2-methyltetrahydrofuran (2-Me
-THF) 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また
は４の少くとも一方の位置の水素をアセチル基で置換し
たプロピ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 propylene carbonate in which hydrogen in at least one position of 3 or 4 is substituted with an acetyl group in place of the solvent of the conventional organic electrolyte.
作用 PCの３または４の位置にアセチル基を導入することによ
り、Ｃ−Ｏの結合が切れ難くなり電流効率が向上する。By introducing an acetyl group at the 3 or 4 position of PC, the bond of C—O becomes difficult to break and the current efficiency is improved.
実施例 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
ムの塩が生成した。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。Example When negative electrode lithium is charged in an organic electrolyte using conventional PC or 2-Me-THF as a solvent, a part of the deposited lithium reacts with the solvent due to active lithium, and a lithium salt is formed. did. 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３または４のＣの位置にアセチル
基を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。例えば、３の位置をアセチル基
で置換した３−アセチルプロピレンカーボネートは
（１）式のような構造となる。In the case of PC, the present inventor believes that the C—O bond is broken by the reaction with Li, and by substituting the acetyl group at the C position of 3 or 4, the strong electron-withdrawing property causes It was thought that the C—O bond would be less likely to break, which would improve the current efficiency. For example, 3-acetylpropylene carbonate in which the 3-position is substituted with an acetyl group has a structure represented by the formula (1).
同様に４−アセチルプロピレンカーボネートの構造を
（２）式に示す。 Similarly, the structure of 4-acetylpropylene carbonate is shown in formula (2).
〔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。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
用いた。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、4
mA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、1.5hr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。この値が大である
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１モル/l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 2 cm x 2 cm nickel plate was used as a negative electrode current collector, and a nickel ribbon was attached to this as a lead. Platinum was used as the counter electrode. Lithium was used for the reference electrode. Put various organic electrolytes in this cell and charge at 4mA for 2 hours.
It was discharged with 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 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 1.5hr, then (1.5hr × 4mA) / (2hr ×
4mA) x 100 = 75%. This charging / discharging was repeated 50 cycles to obtain the average current efficiency. The larger this value is, the less precipitated lithium has reacted with the solvent. All solutes used were 1 mol / l LiClO 4 . The results are shown in the table.
これより、３および４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 hydrogen at the 3 and 4 positions with an acetyl group.
〔実施例２〕 負極に直径17.5mm、厚さ0.5mmのリチウムを用いた。こ
の時の理論充填容量は、247mAhである。正極には、TiS2
100重量部に導電剤としてのアセチレンブラック10重量
部、結着剤としてポリ４フッ化エチレン樹脂10重量部よ
りなる合剤0.4gを直径17.5mmに圧縮成型したものを用い
た。この時の理論充填容量は80mAhであった。これらの
正極，負極よりコイン型電池を試作した。この電池の断
面を第２図に示す。図において、１は正極、２は負極、
３はセパレータである。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になる時点で止めた。有機電解質の溶
質には１モル/lのLiAsF6を用いた。各電池の有機電解質
量は全て200μｌとした。有機電解質の溶媒に本発明の
３−アセチルプロビレンカーボネート、４−アセチルプ
ロピレンカーボネートを用いた電池を各々A,Bとし、従
来のPC,2−Me−THFを用いた電池を各々C,Dとする。第１
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または４の位置の水素
を、アセチル基で置換したプロピ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。Example 2 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, TiS 2
A mixture of 0.4 parts by weight of 100 parts by weight of acetylene black as a conductive agent and 10 parts by weight of polytetrafluoroethylene resin as a binder was compression-molded to a diameter of 17.5 mm. The theoretical filling capacity at this time was 80 mAh. A coin-type battery was prototyped from these positive and negative electrodes. The cross section of this battery is shown in FIG. In the figure, 1 is a positive electrode, 2 is a negative electrode,
3 is a separator. 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 when the battery voltage reached 2.8V. As the solute of the organic electrolyte, 1 mol / l LiAsF 6 was used. The organic electrolytic mass of each battery was 200 μl. Batteries using the 3-acetyl propylene carbonate of the present invention and 4-acetyl propylene carbonate of the present invention as the solvent of the organic electrolyte are referred to as A and B, respectively, and batteries using conventional PC, 2-Me-THF are referred to as C and D, respectively. To do. First
The amount of electricity discharged in each cycle of these batteries is plotted in the figure. From this, it is understood that the cycle characteristics of the battery are improved by using propylene carbonate in which hydrogen at the 3 or 4 position of the present invention is substituted with an acetyl group. This is because the current efficiency of charging / discharging the negative electrode was improved as shown in Example 1.
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，スス，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 and an alloy such as lead, soot, bismuth, and 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ものであ
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。Also, for the positive electrode, only the case of TiS 2 is shown, but the solvent of the present invention has a great effect on the negative electrode, and even if other active materials are used for the positive electrode, the charging and discharging 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 以上示したように、本発明の溶媒を有機電解質に用いる
ことにより、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した。Effect of the Invention As described above, by using the solvent of the present invention in the organic electrolyte, the current efficiency of charging / discharging the negative electrode was improved, and the cycle characteristics of the battery were improved.
第１図は本発明の一実施例の有機電解質二次電池のサイ
クル特性図、第２図はコイン型電池の断面図である。 A,B……本発明の実施例、C,D……従来例。FIG. 1 is a cycle characteristic diagram of an organic electrolyte secondary battery of one embodiment of the present invention, and FIG. 2 is a sectional view of a coin-type battery. A, B ... Examples of the present invention, C, D ... Conventional examples.
Claims (1)
機電解質の溶媒に、３または４の位置の水素をアセチル
基で置換したプロピレンカーボネートを用いることを特
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, wherein propylene carbonate in which hydrogen at the 3 or 4 position is replaced with an acetyl group is used as a solvent of the organic electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174209A JPH0760702B2 (en) | 1986-07-24 | 1986-07-24 | Organic electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174209A JPH0760702B2 (en) | 1986-07-24 | 1986-07-24 | Organic electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6332870A JPS6332870A (en) | 1988-02-12 |
| JPH0760702B2 true JPH0760702B2 (en) | 1995-06-28 |
Family
ID=15974631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61174209A Expired - Lifetime JPH0760702B2 (en) | 1986-07-24 | 1986-07-24 | Organic electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0760702B2 (en) |
-
1986
- 1986-07-24 JP JP61174209A patent/JPH0760702B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6332870A (en) | 1988-02-12 |
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