JPH0410364A - Nonaqueous electrolyte cell - Google Patents

Nonaqueous electrolyte cell

Info

Publication number
JPH0410364A
JPH0410364A JP2110340A JP11034090A JPH0410364A JP H0410364 A JPH0410364 A JP H0410364A JP 2110340 A JP2110340 A JP 2110340A JP 11034090 A JP11034090 A JP 11034090A JP H0410364 A JPH0410364 A JP H0410364A
Authority
JP
Japan
Prior art keywords
solvent
boiling point
battery
nonaqueous electrolyte
electrolyte
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.)
Pending
Application number
JP2110340A
Other languages
Japanese (ja)
Inventor
Sakae Sadakuni
定国　栄
Yukimasa Niwa
幸正 丹羽
Hiromi Sato
裕美 佐藤
Fumio Oo
大尾　文夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP2110340A priority Critical patent/JPH0410364A/en
Publication of JPH0410364A publication Critical patent/JPH0410364A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

  • Secondary Cells (AREA)

Abstract

PURPOSE:To improve an electrolyte to get a nonaqueous electrolyte cell good in a cold discharge characteristic and also a hot preservation characteristic by using a mixed solvent of ethylene carbonate, 1,2-butylene carbonate and tetra-hydrofuran. CONSTITUTION:Heat-treated manganese dioxide is used as active material, and a pressure-molded and heat-treated mixture made up by mixing the active material, carbon powder as conductive material and fluorocarbon resin powder as a bonding agent is used as a positive electrode. Lithium metal punched in prescribed dimensions is used as a negative electrode. A 3-component solvent made up by adding a low boiling point solvent of tetrahydrofuran to a high boiling point solvent of ethylene carbonate and 1,2 butylene carbonate is used. It is thereby possible to improve an electrolyte to get nonaqueous electrolyte cell good in a cold discharge characteristic and a hot preservation characteristic.

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は非水電解液電池に係り、特に電解液の改良に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to non-aqueous electrolyte batteries, and particularly to improvements in electrolytes.

（従来の技術及び発明が解決しようとする課題）リチウ
ム又はリチウム合金を活物質とする負極を用いた非水電
解液電池は高エネルギー密度を有し且つ自己放電が少な
いという特徴がある。(Prior Art and Problems to be Solved by the Invention) A non-aqueous electrolyte battery using a negative electrode containing lithium or a lithium alloy as an active material is characterized by having high energy density and little self-discharge.

さて、近年においてこの種電池の適用分野の拡大に伴い
電池特性の改善が要望されており、特に低温放電特性及
び高温保存特性の向上が望まれている。そのため低温特
性の優れた溶質としてトリフルオロメタンスルホン酸リ
チウム （ＬｉＣＦ３ＳＯ，）が提案されているが、この溶質を
用いた電解液は電導度が低いため高率放電における放電
電圧が低くなるという問題があった。また、この溶質を
用いると溶媒によっては（例えば、エチレンカーボネー
ト、ブチレンカーボネート。Now, in recent years, as the field of application of this type of battery has expanded, there has been a demand for improvements in battery characteristics, and in particular, improvements in low-temperature discharge characteristics and high-temperature storage characteristics are desired. For this reason, lithium trifluoromethanesulfonate (LiCF3SO,) has been proposed as a solute with excellent low-temperature properties, but electrolytes using this solute have low conductivity, resulting in a low discharge voltage during high-rate discharge. Ta. Also, depending on the solvent used with this solute (e.g., ethylene carbonate, butylene carbonate.

１．２−ジメトキシエタン）高温保存時にガスが発生し
、保存劣化が起きるという問題があった。1.2-dimethoxyethane) There was a problem in that gas was generated during high temperature storage and storage deterioration occurred.

溶質としてトリフルオロメタンスルホン酸リチウム（Ｌ
ｉＣＦ３ＳＯ，）を用いると、この溶質は有機溶媒に対
する溶解度が高いので、低温時においても溶質が析呂す
ることがないため低温放電特性に優れている。一方、溶
媒について言えば、溶媒には高沸点溶媒と低沸点溶媒が
あり、高沸点溶媒は、一般に電解液として用いた場合、
電導度が高いが粘度も高く、これに対して低沸点溶媒は
、−般に粘度が低いが、電解液として用いた場合、電導
度も低い。Lithium trifluoromethanesulfonate (L
When iCF3SO,) is used, since this solute has high solubility in organic solvents, the solute does not precipitate even at low temperatures, resulting in excellent low-temperature discharge characteristics. On the other hand, when it comes to solvents, there are high boiling point solvents and low boiling point solvents, and when high boiling point solvents are generally used as an electrolyte,
Although they have high conductivity, they also have high viscosity, whereas low boiling point solvents generally have low viscosity but also have low conductivity when used as electrolytes.

ところで、高率放電特性の向上のための条件としては、
電導度が高く、粘度が低いことが必要であるため、−射
的には、高沸点溶媒に低沸点溶媒とを組み合わせて用い
られている。By the way, the conditions for improving high rate discharge characteristics are as follows:
Since it is necessary to have high conductivity and low viscosity, a combination of a high boiling point solvent and a low boiling point solvent is used strategically.

高沸点溶媒の中においても、電導度、粘度に差があり、
エチレンカーボネート（Ｅ　Ｃ）は、電解液として用い
た場合、電導度は高いものの粘度は比較的高＜、１．２
−ブチレンカーボネート（Ｂ　Ｃ）は、電解液として用
いた場合、電導度は比較的小さいが粘度は低い。従って
一般的に、高率放電特性の向上をはかるためにこれら溶
媒のそれぞれの特徴を活かし、混合溶媒として用いられ
ている。Even among high boiling point solvents, there are differences in conductivity and viscosity.
When used as an electrolyte, ethylene carbonate (EC) has high conductivity but relatively high viscosity <1.2
-Butylene carbonate (B C) has relatively low conductivity but low viscosity when used as an electrolyte. Therefore, in order to improve high rate discharge characteristics, these solvents are generally used as a mixed solvent by taking advantage of their respective characteristics.

また、低温特性の向上をはかるために、これらの高沸点
溶媒に低沸点溶媒を混合して用いられている。これらの
高沸点溶媒（環状エーテル）を用いた場合低沸点溶媒と
して、ジメトキシエタン（ＤＭＥ）などの直鎖状エーテ
ルを用いると高温保存した場合、ＥＣあるいはＢＣの分
解が生じ保存劣化が起こる。Furthermore, in order to improve low-temperature properties, these high-boiling point solvents are mixed with low-boiling point solvents. When these high boiling point solvents (cyclic ethers) are used, and when a linear ether such as dimethoxyethane (DME) is used as a low boiling point solvent, when stored at high temperatures, EC or BC decomposes and storage deterioration occurs.

本発明は電解液を改良し、低温放電特性に優れ且つ高温
保存特性に優れた非水電解液電池を提供することを目的
とする。An object of the present invention is to provide a non-aqueous electrolyte battery that improves the electrolyte and has excellent low-temperature discharge characteristics and high-temperature storage characteristics.

（課題を解決するための手段） 本発明は溶質としてトリフルオロメタンスルホン酸リチ
ウム、溶媒としてエチレンカーボネートと１，２−ブチ
レンカーボネートとテトラヒドロフランとの混合溶媒を
用いることにより、上記の課題を解決するものである。(Means for Solving the Problems) The present invention solves the above problems by using lithium trifluoromethanesulfonate as a solute and a mixed solvent of ethylene carbonate, 1,2-butylene carbonate, and tetrahydrofuran as a solvent. be.

（作　用） ＥＣ及びＢＣの高沸点溶媒にテトラヒドロフラン（ＴＨ
Ｆ）の低沸点溶媒（沸点６６℃）を加えた三成分系の混
合溶媒を用いることにより、低温放電特性に優れ且つ高
温保存特性に優れた電解液が得られる。(Function) Tetrahydrofuran (TH
By using a three-component mixed solvent to which the low boiling point solvent (boiling point 66° C.) of F) is added, an electrolyte solution having excellent low-temperature discharge characteristics and excellent high-temperature storage characteristics can be obtained.

（実施例） 以下、本発明の実施例について詳述する。(Example) Examples of the present invention will be described in detail below.

二酸化マンガンを熱処理したものを活物質とし。The active material is heat-treated manganese dioxide.

この活物質と導電材としてカーボン粉末及び結着剤とし
てのフッ素樹脂粉とを、８５：１０：５の重量比で混合
した混合物を加圧成形し熱処理したものを正極とする。A mixture of this active material, carbon powder as a conductive material, and fluororesin powder as a binder in a weight ratio of 85:10:5 is pressure-molded and heat-treated to form a positive electrode.

負極は、リチウム金属を所定寸法に打ち抜いたものを用
いた。The negative electrode used was a piece of lithium metal punched out to a predetermined size.

そして、電解液は、ＥＣ，ＢＣ及びＴＨＦとの混合溶媒
（混合体積比　ＥＣ：　ＢＣ：　ＴＨＦ＝２　：３：５
）にＬｉＣＦ、　Ｓ　Ｏ，を、　１　＋ｍｏｌ／　Ｑ溶
解したものを用いて径２０．０ｍ＋、厚み２．５ｍ、電
池容量１３０ｍＡｈの本発明電池（Ａ）を作成した。The electrolyte is a mixed solvent of EC, BC, and THF (mixed volume ratio EC: BC: THF=2:3:5
A battery (A) of the present invention having a diameter of 20.0 m+, a thickness of 2.5 m, and a battery capacity of 130 mAh was prepared using 1 + mol/Q of LiCF, SO, dissolved in ).

次に２本発明電池の優位性を調べるために比較電池を作
成した。電解液として、ＥＣ，ＢＣ及びＤＭＥとの混合
溶媒（混合体積比　ＥＣ：ＢＣ：ＤＭＥ＝２　：　３　
：　５）にＬｉＣＦ３５Ｏ，を、１　ｍｏｌ／Ｑ溶解し
たものを用いることを除いては１本発明電池と同様の比
較電池（Ｂ）を作成した。また、電解液として、ＰＣ（
プロピレンカーボネート）。Next, comparative batteries were prepared to examine the superiority of the two inventive batteries. As the electrolyte, a mixed solvent of EC, BC and DME (mixed volume ratio EC:BC:DME=2:3
A comparative battery (B) was prepared which was similar to the battery of the present invention except that LiCF35O was dissolved in 5) at a concentration of 1 mol/Q. In addition, as an electrolyte, PC (
propylene carbonate).

ＤＭＥの混合溶媒（混合体積比ｌ：１）に、ＬｉＣｌＯ
４を１　ｍｏｌ／Ω溶解したものを用いることを除いて
は、本発明電池と同様の比較電池（Ｃ）を作成した。LiClO was added to a mixed solvent of DME (mixed volume ratio 1:1).
A comparison battery (C) similar to the battery of the present invention was prepared except that 1 mol/Ω of No. 4 was used.

第１図及び第２図は１本発明電池と比較電池との放電特
性比較図であって、第１図は、−２０℃において、３に
Ωの定抵抗で放電した時の低温放電特性、又、第２図は
、電池を８５℃、１力月保存した後５２５℃において、
３にΩの定抵抗で放電した時の低温放電特性を示す。Figures 1 and 2 are diagrams comparing the discharge characteristics of a battery according to the present invention and a comparative battery. In addition, Figure 2 shows that the battery was stored at 85°C for one month and then at 525°C.
Figure 3 shows the low-temperature discharge characteristics when discharged with a constant resistance of Ω.

第１図により、本発明電池（Ａ）は、比較電池（Ｂ）及
び（Ｃ）に比して、低温放電特性が優れていることがわ
かる。第２図より、本発明電池（Ａ）は、比較電池（Ｂ
）及び（Ｃ）に比して、高温保存後の放電特性が優れて
いることがわかる。From FIG. 1, it can be seen that the battery of the present invention (A) has superior low-temperature discharge characteristics as compared to the comparative batteries (B) and (C). From FIG. 2, the battery of the present invention (A) is different from the comparative battery (B
) and (C), it can be seen that the discharge characteristics after high-temperature storage are superior.

また、それぞれの電池を、８５℃に１力月間保存した後
、分解すると比較電池（Ｂ）のみがガス発生しており、
本発明電池（Ａ）では、ガス発生はなかった。ガス分析
及び溶雪の組成比分析の結果から、比較電池（Ｂ）にお
いては、ＥＣあるいはＢＣの分解が生じたものと考えら
れる。In addition, when each battery was stored at 85°C for one month and then disassembled, only the comparison battery (B) generated gas.
In the battery of the present invention (A), no gas was generated. From the results of the gas analysis and the composition ratio analysis of melted snow, it is considered that EC or BC decomposition occurred in the comparative battery (B).

（発明の効果） 上述した如く、正極と負極と少なくとも一つの溶質と溶
媒とからなる電解液を備える非水電解液電池において、
溶質としてトリフルオロメタンスルホン酸リチウム、溶
媒としてエチレンカーボネ−トと１，２−ブチレンカー
ボネートとテトラヒドロフランとの混合溶媒を用いるこ
とにより、低温放電特性及び高温保存特性を改善するこ
とができるものであり、この種電池の用途拡大に資する
ところ極めて大である。(Effects of the Invention) As described above, in a non-aqueous electrolyte battery comprising an electrolyte consisting of a positive electrode, a negative electrode, and at least one solute and solvent,
By using lithium trifluoromethanesulfonate as a solute and a mixed solvent of ethylene carbonate, 1,2-butylene carbonate, and tetrahydrofuran as a solvent, low-temperature discharge characteristics and high-temperature storage characteristics can be improved, This greatly contributes to expanding the uses of this type of battery.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は１本発明の電池及び他の電池の低温放電特性図
、第２図は、同じく高温保存後の電池の放電特性を示す
図である。 特許出願人　松下電器産業株式会社FIG. 1 is a diagram showing the low temperature discharge characteristics of the battery of the present invention and another battery, and FIG. 2 is a diagram showing the discharge characteristics of the battery after storage at a high temperature. Patent applicant Matsushita Electric Industrial Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] 　正極と負極と、一つの溶質と混合溶媒とからなる電解
液とを備える非水電解液電池において、溶質としてトリ
フルオロメタンスルホン酸リチウム、溶媒としてエチレ
ンカーボネートと１、２−ブチレンカーボネートとテト
ラヒドロフランとの混合溶媒を用いることを特徴とする
非水電解液電池。In a nonaqueous electrolyte battery comprising a positive electrode, a negative electrode, and an electrolytic solution consisting of one solute and a mixed solvent, a mixture of lithium trifluoromethanesulfonate as the solute and ethylene carbonate, 1,2-butylene carbonate, and tetrahydrofuran as the solvent A nonaqueous electrolyte battery characterized by using a solvent.
JP2110340A 1990-04-27 1990-04-27 Nonaqueous electrolyte cell Pending JPH0410364A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2110340A JPH0410364A (en) 1990-04-27 1990-04-27 Nonaqueous electrolyte cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2110340A JPH0410364A (en) 1990-04-27 1990-04-27 Nonaqueous electrolyte cell

Publications (1)

Publication Number Publication Date
JPH0410364A true JPH0410364A (en) 1992-01-14

Family

ID=14533275

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2110340A Pending JPH0410364A (en) 1990-04-27 1990-04-27 Nonaqueous electrolyte cell

Country Status (1)

Country Link
JP (1) JPH0410364A (en)

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