JPH0652670B2 - Lithium secondary battery electrolyte - Google Patents
Lithium secondary battery electrolyteInfo
- Publication number
- JPH0652670B2 JPH0652670B2 JP58093460A JP9346083A JPH0652670B2 JP H0652670 B2 JPH0652670 B2 JP H0652670B2 JP 58093460 A JP58093460 A JP 58093460A JP 9346083 A JP9346083 A JP 9346083A JP H0652670 B2 JPH0652670 B2 JP H0652670B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- secondary battery
- electrode
- charge
- lithium secondary
- 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
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】 本発明はリチウム一次および二次電池に用いる電解液に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrolytic solution used in lithium primary and secondary batteries.
リチウムを負極活物質として用いる電池は、小型・高エ
ネルギー密度を有する電池として研究されているが、そ
の二次化が大きな問題となっている。A battery using lithium as a negative electrode active material has been studied as a battery having a small size and a high energy density, but its secondary conversion has become a big problem.
二次化が可能な正極活物質として、V2O5、V6O13等の金
属酸化物、TiS2、VS2等の層状化合物が、Ｌｉとの間で
トポケミカルな反応をする化合物として知られており、
現在までチタン、ジルコニウム、ハフニウム、ニオビウ
ム、タンタル、バナジウムの硫化物、セレン化物、テル
ル化物を用いた電池（米国特許第４０８９０５２号明細
書参照）等が開示されている。As a positive electrode active material that can be secondaryized, metal oxides such as V 2 O 5 and V 6 O 13 and layered compounds such as TiS 2 and VS 2 are known as compounds that undergo a topochemical reaction with Li. Has been
Until now, batteries using sulfides, selenides and tellurides of titanium, zirconium, hafnium, niobium, tantalum and vanadium (see US Pat. No. 4,890,052) and the like have been disclosed.
しかしながら、このような二次電池用正極活物質の研究
に比して、Ｌｉ極の充放電特性に関する研究は十分とは
いえず、Ｌｉ二次電池実現のためには、充放電効率およ
びサイクル寿命等の充放電特性の良好な電解液の探査が
重大な問題となっている。Ｌｉ極の充放電効率を向上さ
せる試みとしてはLiClO4／プロピレンカーボネートにニ
トロメタン、SO2等の添加剤を加える試み（Electrochim
ica.Acta.vol.22,第７５頁〜８３頁（１９７７））等が
行なわれているが必ずしも十分とはいえず、さらに特性
の優れたリチウム二次電池用電解液が求められている。However, research on the charge and discharge characteristics of the Li electrode is not sufficient compared to research on such positive electrode active materials for secondary batteries, and in order to realize the Li secondary battery, charge and discharge efficiency and cycle life are required. The search for an electrolytic solution having a good charge / discharge characteristic such as is a serious problem. As an attempt to improve the charging and discharging efficiency of the Li electrode, an attempt to add additives such as nitromethane and SO 2 to LiClO 4 / propylene carbonate (Electrochim
ica.Acta.vol.22, pp. 75-83 (1977)) has been carried out, but this is not always sufficient, and there is a demand for an electrolyte solution for lithium secondary batteries having further excellent characteristics.
本発明は、このような現状に鑑みてなされたものであ
り、その目的はＬｉ極の充放電特性の優れたリチウム電
池用非水電解液を提供することにある。The present invention has been made in view of such a current situation, and an object thereof is to provide a non-aqueous electrolyte solution for a lithium battery, which has excellent charge and discharge characteristics of a Li electrode.
したがって、本発明によるリチウム電池用電解液は、リ
チウム塩を有機溶媒に溶解させたリチウム二次電池用電
解液において、有機溶媒として、１，２−ジブトキシエ
タンとγ−ブチロラクトンの体積混合比１：１の混合溶
媒を用い、かつ前記リチウム塩として過塩素酸リチウム
を用いることを特徴とするものである。Therefore, the electrolyte solution for a lithium battery according to the present invention is a lithium secondary battery electrolyte solution in which a lithium salt is dissolved in an organic solvent, and the volume ratio of 1,2-dibutoxyethane and γ-butyrolactone is 1 as an organic solvent. A mixed solvent of 1: 1 is used, and lithium perchlorate is used as the lithium salt.
本発明によれば、上記非水電解液において、有機溶媒と
して、１，２−ジブトキシエタンとγ−ブチロラクトン
の体積混合比１：１の混合溶媒を用い、かつ前記リチウ
ム塩として過塩素酸リチウムを用いることにより、Ｌｉ
極の充放電特性の優秀なリチウム電池を実現し得る。According to the present invention, in the above non-aqueous electrolyte, a mixed solvent of 1,2-dibutoxyethane and γ-butyrolactone in a volume mixing ratio of 1: 1 is used as an organic solvent, and lithium perchlorate is used as the lithium salt. By using Li
It is possible to realize a lithium battery having excellent charge and discharge characteristics of the electrodes.
本発明をさらに詳しく説明する。The present invention will be described in more detail.
リチウム電池はリチウムを負極活物質とし、電気化学的
に活性で、かつＬｉ+イオンと可逆的な電気化学反応を
行なう物質を正極活物質とする電池であるが、本発明に
よれば、リチウム塩を有機溶媒に溶解した電解液の有機
溶媒として、１，２−ジブトキシエタンとγ−ブチロラ
クトンとの混合溶媒を用いる。A lithium battery uses lithium as a negative electrode active material, and uses as a positive electrode active material a material that is electrochemically active and undergoes a reversible electrochemical reaction with Li + ions. According to the present invention, a lithium salt is used. A mixed solvent of 1,2-dibutoxyethane and γ-butyrolactone is used as an organic solvent of an electrolytic solution in which is dissolved in an organic solvent.
前記１，２−ジブトキシエタンとγ−ブチロラクトンの
混合比は１：１である。このような混合比範囲から逸脱
すると、充放電特性が悪化するからである。The mixing ratio of 1,2-dibutoxyethane and γ-butyrolactone is 1: 1. This is because the charge / discharge characteristics deteriorate if the mixture ratio deviates from this range.
これに溶解される溶質は過塩素酸リチウム（LiClO4）用
いることができる。これらの溶質は前記有機溶媒に、好
ましくは０．５〜２．５Ｎ溶解される。溶解する溶質が
０．５Ｎ未満であると充放電特性が著しく低下し、一方
２．５Ｎを越えると、溶質は溶媒に溶解困難となるから
である。Lithium perchlorate (LiClO 4 ) can be used as the solute dissolved in this. These solutes are preferably dissolved in the organic solvent by 0.5 to 2.5N. This is because if the solute to be dissolved is less than 0.5 N, the charge / discharge characteristics are significantly deteriorated, while if it exceeds 2.5 N, the solute becomes difficult to dissolve in the solvent.
次に、本発明の実施例を説明する。Next, examples of the present invention will be described.
実施例１ 作用極としてＰｔ極を、対極としてＬｉを、さらに参照
電極としてＬｉを用いたセルを組み、Ｐｔ極上にＬｉを
析出させることにより、Ｌｉ極の充放電特性を測定し
た。Example 1 A cell using a Pt electrode as a working electrode, Li as a counter electrode, and Li as a reference electrode was assembled, and Li was deposited on the Pt electrode to measure the charge / discharge characteristics of the Li electrode.
電解液には、１Ｎ LiClO4をγ−ブチロラクトンと１，
２−ジブトキシエタンの５：５体積比混合溶媒に溶解さ
せたものを用いた。For the electrolyte, 1N LiClO 4 was added to γ-butyrolactone and 1,
What was melt | dissolved in the 5: 5 volume ratio mixed solvent of 2-dibutoxyethane was used.
測定はまず、０．５mA/cm2の定電流で１分間、Ｐｔ極上
にＬｉを析出させ充電した後、５mA/cm2の定電流で１分
間Ｐｔ極上に析出したＬｉをＬｉ+イオンとして充放電
するサイクル試験を行なった。The measurement was carried out by first depositing Li on the Pt electrode at a constant current of 0.5 mA / cm 2 for 1 minute and charging it, and then charging Li deposited on the Pt electrode as a Li + ion at a constant current of 5 mA / cm 2 for 1 minute. A cycle test of discharging was performed.
第１図はＬｉ極の充放電効率とサイクル数の関係を示す
図であり、図中、（ａ）は本発明の１Ｎ LiClO4／１，
２−ジブトキシエタン／γ−ブチロラクトン（体積混合
比５：５）を電解液として用いた場合であり、図中
（ｂ）は参考例として０．７５Ｎ LiClO4／γ−ブチロ
ラクトン単独溶媒系電解液を用いた場合のＬｉ極の充放
電特性を示したものである。FIG. 1 is a diagram showing a charge-discharge efficiency and cycle number relationship Li electrode, in FIG., (A) represents 1N LiClO 4/1 of the present invention,
This is a case where 2-dibutoxyethane / γ-butyrolactone (volume mixing ratio 5: 5) was used as an electrolytic solution, and in the figure, (b) is a 0.75N LiClO 4 / γ-butyrolactone single solvent type electrolytic solution as a reference example. 3 shows the charge / discharge characteristics of the Li electrode in the case of using.
第１図からわかるように、単独系（ｂ）に比べて、混合
系（ａ）は明かに充放電特性が向上している。As can be seen from FIG. 1, the charge / discharge characteristics of the mixed system (a) are clearly improved as compared with the single system (b).
以上の説明から明らかなように、本発明によればリチウ
ム塩を溶質として溶媒に溶解させた非水電解液におい
て、前記有機溶媒として１，２−ジブトキシエタンとγ
−ブチロラクトンの体積混合比１：１の混合溶媒を用
い、かつ前記リチウム塩として過塩素酸リチウムを用い
ることにより、Ｌｉの充放電特性が優れたリチウム電池
用非水電解液を提供することができる。As is clear from the above description, according to the present invention, in a nonaqueous electrolytic solution in which a lithium salt is dissolved as a solute in a solvent, 1,2-dibutoxyethane and γ are used as the organic solvent.
-By using a mixed solvent of butyrolactone in a volume mixing ratio of 1: 1 and using lithium perchlorate as the lithium salt, it is possible to provide a non-aqueous electrolyte for a lithium battery having excellent Li charge / discharge characteristics. .
第１図は本発明による電解液を用いた場合のＬｉ極の充
放電効率とサイクル数の関係を示す図である。FIG. 1 is a diagram showing the relationship between the charge and discharge efficiency of the Li electrode and the number of cycles when the electrolytic solution according to the present invention is used.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡田 武司 茨城県那珂郡東海村大字白方字白根162番 地 日本電信電話公社茨城電気通信研究所 内 (56)参考文献 特開 昭58−64768（ＪＰ，Ａ) 特開 昭58−163177（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Okada 162 Shirahane, Shirahoji, Tokai-mura, Naka-gun, Ibaraki Pref., Ibaraki Telecommunications Research Institute, Nippon Telegraph and Telephone Corporation (56) Reference JP-A-58-64768 ( JP, A) JP-A-58-163177 (JP, A)
Claims (1)
ム二次電池用電解液において、前記有機溶媒として、
１，２−ジブトキシエタンとγ−ブチロラクトンの体積
混合比１：１の混合溶媒を用い、かつ前記リチウム塩と
して過塩素酸リチウムを用いることを特徴とするリチウ
ム二次電池用電解液。1. An electrolytic solution for a lithium secondary battery in which a lithium salt is dissolved in an organic solvent, wherein the organic solvent is:
An electrolytic solution for a lithium secondary battery, which comprises using a mixed solvent of 1,2-dibutoxyethane and γ-butyrolactone in a volume mixing ratio of 1: 1 and using lithium perchlorate as the lithium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58093460A JPH0652670B2 (en) | 1983-05-27 | 1983-05-27 | Lithium secondary battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58093460A JPH0652670B2 (en) | 1983-05-27 | 1983-05-27 | Lithium secondary battery electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59219869A JPS59219869A (en) | 1984-12-11 |
| JPH0652670B2 true JPH0652670B2 (en) | 1994-07-06 |
Family
ID=14082940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58093460A Expired - Lifetime JPH0652670B2 (en) | 1983-05-27 | 1983-05-27 | Lithium secondary battery electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0652670B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3425493B2 (en) * | 1994-07-28 | 2003-07-14 | 日立マクセル株式会社 | Non-aqueous secondary battery and method of manufacturing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5864768A (en) * | 1981-10-14 | 1983-04-18 | Sanyo Electric Co Ltd | non-aqueous electrolyte battery |
| JPS58163177A (en) * | 1982-03-20 | 1983-09-27 | Hitachi Maxell Ltd | Organic electrolytic battery |
-
1983
- 1983-05-27 JP JP58093460A patent/JPH0652670B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59219869A (en) | 1984-12-11 |
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