JPH0636370B2 - Electrolyte for lithium secondary battery - Google Patents
Electrolyte for lithium secondary batteryInfo
- Publication number
- JPH0636370B2 JPH0636370B2 JP59010783A JP1078384A JPH0636370B2 JP H0636370 B2 JPH0636370 B2 JP H0636370B2 JP 59010783 A JP59010783 A JP 59010783A JP 1078384 A JP1078384 A JP 1078384A JP H0636370 B2 JPH0636370 B2 JP H0636370B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic solution
- charge
- electrode
- electrolyte
- 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
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
Description
【発明の詳細な説明】 〔発明の技術分野〕 本発明はリチウム電池に用いる電解液に関するものであ
る。TECHNICAL FIELD OF THE INVENTION The present invention relates to an electrolytic solution used in a lithium battery.
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 formation has become a serious 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４，０８
９，０５２号明細書参照）等が開示されている。Examples of the positive electrode active material that can be used as a secondary material include V 2 O 5 and V 6 O 13
Metal oxides such as, and layered compounds such as TiS 2 and VS 2 ,
It is known as a compound that undergoes a topochemical reaction with Li, and up to the present, batteries using sulfides, selenides and tellurides of titanium, zirconium, hafnium, niobium, tantalum and vanadium (US Pat.
No. 9,052) are 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充分とはい
えず、リチウム二次電池実現のためには、充放電効率及
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イトにニ
トロメタン、SO２などの添加剤を加える試み〔Electoro
chimica.Acta. Vol.22，第75頁〜第83時（1977）〕等が
行われているが、必ずしも充分とは言えず、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 a lithium 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 charge / discharge efficiency of the Li electrode, an attempt to add additives such as nitromethane and SO 2 to LiClO 4 / propylene carbonate [Electoro
chimica.Acta. Vol.22, pp. 75-83 (1977)] has been conducted, but it is not always sufficient, and an electrolytic solution for lithium secondary batteries with further excellent characteristics is demanded. There is.
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、導電率が高く、かつLi極の充放電特性
の優れたリチウム二次電池用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 an electrolytic solution for a lithium secondary battery, which has high conductivity and excellent charge / discharge characteristics of a Li electrode.
したがって、本発明によるリチウム二次電池用電解液
は、リチウム塩を有機溶媒に溶解させたリチウム電池用
電解液において、前記有機溶媒として、テトラハライド
ロフラン又は１，２−ジメトキシエタンと、ジメチルス
ルホキシドの混合比１；９〜９：１の混合溶媒を用いた
ことを特徴とするものである。Therefore, the electrolytic solution for a lithium secondary battery according to the present invention is a lithium battery electrolytic solution in which a lithium salt is dissolved in an organic solvent, and the organic solvent is tetrahalidorofuran or 1,2-dimethoxyethane, and dimethyl sulfoxide. A mixed solvent having a mixing ratio of 1; 9 to 9: 1 is used.
本発明によれば、リチウム塩を有機溶媒に溶解した電解
液に、前記有機溶媒として、テトラハイドロフラン又は
１，２−ジメトキシエタンと、ジメチルスルホキシドの
混合溶媒を用いることにより、導電率が高く、Li極の充
放電特性が良好なリチウム二次電池用非水電解液を提供
することができる。According to the present invention, in an electrolytic solution in which a lithium salt is dissolved in an organic solvent, by using a mixed solvent of tetrahydrofuran or 1,2-dimethoxyethane and dimethyl sulfoxide as the organic solvent, the conductivity is high, It is possible to provide a non-aqueous electrolyte solution for a lithium secondary battery, which has excellent charge and discharge characteristics of the Li electrode.
本発明を更に詳しく説明する。 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+ イオンを可逆的な電気化学反応を行
う物質を正極活物質とする電池であるが、本発明のよれ
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、テトラハイドロフラン又は１，２−ジメトキシ
エタンと、＞S ＝0 基を有する高誘電率環状あるいは非
環状非プロトン性エステルの混合溶媒を用いる。A lithium battery is a battery in which lithium is used as a negative electrode active material, and a material that is electrochemically active and that undergoes a reversible electrochemical reaction of Li + ions is used as a positive electrode active material. As an organic solvent for an electrolytic solution in which is dissolved in an organic solvent, a mixed solvent of tetrahydrofuran or 1,2-dimethoxyethane and a high dielectric constant cyclic or acyclic aprotic ester having a> S = 0 group is used.
テトラハイドロフラン又は１，２−ジメトキシエタンお
よびジメチルスルホキシドとの混合比は、好ましくは1
：9 〜9 ：1 であるのがよい。この範囲を外れると、
すなわちエーテルが大すぎると、導電率が悪くなる虞を
生じ、またエーテルが少なすぎると、充放電効率が低下
する虞があるからである。最も好ましくは5 ：5 付近で
ある。The mixing ratio of tetrahydrofuran or 1,2-dimethoxyethane and dimethyl sulfoxide is preferably 1
: 9 to 9: 1 is preferable. Outside this range,
That is, if the amount of ether is too large, the conductivity may deteriorate, and if the amount of ether is too small, the charge / discharge efficiency may decrease. Most preferably, it is around 5: 5.
さらに、溶質であるリチウム塩は、従来この主の電解液
に用いられるものであれば、いかなるものでもよい。例
えば LiClO４、LiBF４、 LiAsF６、LiPF６、LiAlCl４、
CF３SO３Li、CF３CO２Liから選択された１種以上のよう
な、一般に非水電解液の溶質として用いられるリチウム
塩を有効に用いることができる。Further, the lithium salt as a solute may be any one as long as it is conventionally used in the main electrolytic solution. For example, LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiAlCl 4 ,
A lithium salt generally used as a solute of a non-aqueous electrolyte, such as one or more selected from CF 3 SO 3 Li and CF 3 CO 2 Li, can be effectively used.
リチウム二次電池用電解液に要求される特性は導電率が
高く、かつLiの充放電効率が高いことである。上述した
ようなエーテルは、Liと比較的反応し難く、低電流にお
けるLiの充放電効率の向上には効果的であるが、誘電率
が低く、導電率は低い。また、＞S ＝0 基を有するエス
テルは、＞S ＝0 の分極によい誘電率が高く、誘電率が
高いが、二重結合を有するため、Liとの反応性が大きく
Liの充放電効率は低い。The characteristics required for the electrolyte solution for a lithium secondary battery are high conductivity and high Li charging / discharging efficiency. The above-mentioned ether is relatively difficult to react with Li and is effective in improving the charge / discharge efficiency of Li at low current, but has a low dielectric constant and a low conductivity. Further, the ester having a> S = 0 group has a high dielectric constant which is good for the polarization of> S = 0 and has a high dielectric constant, but since it has a double bond, it has a large reactivity with Li.
The charge / discharge efficiency of Li is low.
ところが、後述の実施例に示すように、エーテルと＞S
＝0 基とを有するエステルを混合することにより、両者
の利点のみが加成され、導電率が高く、かつLiの充放電
効率も高くすることができる。However, as shown in the examples below, ether and> S
By mixing the ester having a = 0 group, only the advantages of both are added, the conductivity is high, and the charging / discharging efficiency of Li can also be increased.
次ぎに、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 Pt極を作用極、対極にLiを参照電極としてLiを用いた電
池を組み、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 battery using a Pt electrode as a working electrode and Li as a counter electrode with 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１モル／１のLiClO4をテトラハイドロフラン
とジメチルスルホキシドの１：１体積比混合溶媒に溶解
したものを用いた。この電解液の導電率は15.1×10−３
ohm -1cm-1であり、1M LiClO４−テトラハイドロフラン
単独溶媒系電解液の導電率（4.0 ×10−３ohm -1cm-1）
より高かった。The electrolyte used was 1 mol / 1 of LiClO 4 dissolved in a mixed solvent of tetrahydrofuran and dimethyl sulfoxide at a volume ratio of 1: 1. The conductivity of this electrolyte is 15.1 × 10 -3
ohm -1 cm -1, which is the conductivity of 1M LiClO 4 -tetrahydrofuran single solvent electrolyte (4.0 x 10 -3 ohm -1 cm -1 ).
It was higher.
測定は、まず０．５mA/cm2の定電流で２０分間、Pt極上
にLiを析出させて充電した後、０．５mA/cm2の定電流で
Pt極上に析出したLiをLi+イオンとして放電するサイク
ル試験を行なった。充放電効率はPt極の電位の変化より
求め、Pt極上に析出したLiをLi+イオンとして放電させ
るのに要した電気量との比から算出した。The measurement was performed by first depositing Li on the Pt electrode for 20 minutes at a constant current of 0.5 mA / cm 2 and charging it, and then at a constant current of 0.5 mA / cm 2.
A cycle test was performed in which Li deposited on the Pt electrode was discharged as Li + ions. The charging / discharging efficiency was obtained from the change in the potential of the Pt electrode, and was calculated from the ratio with the amount of electricity required to discharge Li deposited on the Pt electrode as Li + ions.
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、蒸気電解液を用いた
場合であり、（ｂ）は本発明の効果を示す参考例として
１M LiClO４／テトラハイドロフランを用いた場合のLi
の充放電特性を示したものである。FIG. 1 is a diagram showing the relationship between the charge and discharge efficiency of the Li electrode and the number of cycles. In the figure, (a) is the case of using the vapor electrolyte of the present invention, and (b) is the effect of the present invention. In the case of using 1M LiClO 4 / tetrahydrofuran as a reference example showing
3 shows the charge / discharge characteristics of
第１図から判る様に、単独系（b ）に比べて、本発明に
よる混合系（a ）は明らかに充放電特性が向上してい
る。As can be seen from FIG. 1, the mixed system (a) according to the present invention has clearly improved charge / discharge characteristics as compared with the single system (b).
実施例２ 電解液として、1.モル／の LiClO４を１，２−ジメト
キシエタンとジメチルスルホキシドの1 ：1 体積比混合
溶媒に溶解したものを用いた以外は実施例1 と同様にし
てLiの充放電特性を測定した。Example 2 The same procedure as in Example 1 was repeated except that 1 mol / mol of LiClO 4 was dissolved in a 1: 1 volume ratio mixed solvent of 1,2-dimethoxyethane and dimethylsulfoxide as an electrolytic solution. The charge / discharge characteristics were measured.
第２図は上記電解液を用いた場合のLiの充放電効率とサ
イクル数の関係を示す図である。第２図より明らかなよ
うに、本発明による電解液を用いることにより、良好な
充放電特性をえることができる。FIG. 2 is a diagram showing the relationship between the charge / discharge efficiency of Li and the number of cycles when the above electrolytic solution is used. As is apparent from FIG. 2, good charge / discharge characteristics can be obtained by using the electrolytic solution of the present invention.
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有機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、テトラハイドロフラン又
は１，２ジメトキシエタンと、ジメチルスルホキシドと
＞S ＝0 基を有するエステルを混合したものを用いるこ
とにより、導電率が高く、かつLiの充放電特性の優れた
リチウム二次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 the non-aqueous electrolytic solution obtained by dissolving a lithium salt as a solute in an organic solvent, the organic solvent is tetrahydrofuran or 1,2-dimethoxyethane, and dimethyl sulfoxide. By using a mixture of and an ester having> S = 0 group, it is possible to provide a non-aqueous electrolytic solution for a lithium secondary battery, which has high conductivity and excellent Li charge / discharge characteristics.
第１図から第２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。1 to 2 show the case where the electrolytic solution according to the present invention is used.
It is a figure which shows the relationship between the charging / discharging efficiency of a Li electrode, and the number of cycles.
───────────────────────────────────────────────────── 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58−87777（ＪＰ，Ａ) 特開 昭57−187878（ＪＰ，Ａ) 特開 昭56−7362（ＪＰ，Ａ) 特開 昭57−80679（ＪＰ，Ａ) 特開 昭57−152684（ＪＰ，Ａ) 特公 昭54−17933（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Okada 162 Shirahone, Shirahoji, Tokai-mura, Naka-gun, Ibaraki Pref. JP, A) JP 57-187878 (JP, A) JP 56-7362 (JP, A) JP 57-80679 (JP, A) JP 57-152684 (JP, A) JP Showa 54-17933 (JP, B2)
Claims (1)
ム電池用電解液において、前記有機溶媒として、テトラ
ハイドロフラン又は１，２−ジメトキシエタンと、ジメ
チルスルホキシドの混合比１；９〜９：１の混合溶媒を
用いた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 battery in which a lithium salt is dissolved in an organic solvent, wherein the organic solvent is tetrahydrofuran or 1,2-dimethoxyethane and dimethyl sulfoxide in a mixing ratio of 1; 9 to 9: 1. An electrolytic solution for a lithium secondary battery, characterized by using a mixed solvent of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59010783A JPH0636370B2 (en) | 1984-01-24 | 1984-01-24 | Electrolyte for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59010783A JPH0636370B2 (en) | 1984-01-24 | 1984-01-24 | Electrolyte for lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60154478A JPS60154478A (en) | 1985-08-14 |
| JPH0636370B2 true JPH0636370B2 (en) | 1994-05-11 |
Family
ID=11759932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59010783A Expired - Lifetime JPH0636370B2 (en) | 1984-01-24 | 1984-01-24 | Electrolyte for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0636370B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3637146A1 (en) * | 1985-11-01 | 1987-05-07 | Nippon Telegraph & Telephone | LITHIUM SECONDARY BATTERY |
| JPH0616420B2 (en) * | 1986-03-20 | 1994-03-02 | 日本電信電話株式会社 | Lithium secondary battery |
| JPH0821429B2 (en) * | 1986-10-31 | 1996-03-04 | 日本電信電話株式会社 | Electrolyte for lithium secondary battery |
| JPH0665075B2 (en) * | 1987-07-08 | 1994-08-22 | 富士電気化学株式会社 | Non-aqueous electrolyte battery |
| JP4706807B2 (en) * | 1999-04-02 | 2011-06-22 | 富山薬品工業株式会社 | Non-aqueous electrolytic secondary battery |
| WO2001063686A1 (en) * | 2000-02-22 | 2001-08-30 | Sumitomo Seika Chemicals Co., Ltd. | Electrolytic solution composition for lithium secondary battery |
| JP4618399B2 (en) | 2002-06-11 | 2011-01-26 | 日本電気株式会社 | Secondary battery electrolyte and secondary battery using the same |
| CN1993856B (en) | 2004-11-04 | 2010-05-26 | 松下电器产业株式会社 | Secondary battery with terminal for surface mounting |
| JP5169400B2 (en) | 2008-04-07 | 2013-03-27 | Ｎｅｃエナジーデバイス株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2730644A1 (en) * | 1977-07-07 | 1979-01-25 | Bayer Ag | FLUORESCENT DYES |
| CA1143002A (en) * | 1979-06-28 | 1983-03-15 | George E. Blomgren | Organic electrolyte for rechargeable lithium cells |
| JPS57187878A (en) * | 1981-05-14 | 1982-11-18 | Nippon Telegr & Teleph Corp <Ntt> | Nonaqueous electrolyte solution for secondary lithium battery |
| JPS5887777A (en) * | 1981-11-20 | 1983-05-25 | Nippon Telegr & Teleph Corp <Ntt> | Nonaqueous electrolytic solution for lithium secondary battery |
-
1984
- 1984-01-24 JP JP59010783A patent/JPH0636370B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60154478A (en) | 1985-08-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |