JPH0715820B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH0715820B2 JPH0715820B2 JP63111951A JP11195188A JPH0715820B2 JP H0715820 B2 JPH0715820 B2 JP H0715820B2 JP 63111951 A JP63111951 A JP 63111951A JP 11195188 A JP11195188 A JP 11195188A JP H0715820 B2 JPH0715820 B2 JP H0715820B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- low
- vol
- aqueous 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.)
- 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the 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)
- Primary Cells (AREA)
Description
【発明の詳細な説明】 （イ）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 (a) Field of Industrial Application The present invention relates to a non-aqueous electrolyte battery, and more particularly to improvement of an electrolyte solution.
（ロ）従来の技術 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
電が少ないという利点がある。(B) Conventional Technology A non-aqueous electrolyte battery using a negative electrode containing lithium or a lithium alloy as an active material has advantages of high energy density and low 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、その一つとして低温
放電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
（LiCF3SO3）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。In recent years, there has been a demand for improvement in battery characteristics with the expansion of application fields of this type of battery, and as one of them, improvement in low temperature discharge characteristics is desired. For this reason, lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) has been proposed as a solute with excellent low-temperature characteristics, but the electrolyte using this solute has a low electrical conductivity, so the discharge voltage at high rate discharge is low. was there.
（ハ）発明が解決しようとする課題 本発明は電解液を改良し、低温放電特性に優れ且つ高率
放電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。(C) Problem to be Solved by the Invention An object of the present invention is to improve an electrolytic solution and provide a non-aqueous electrolytic solution battery having excellent low-temperature discharge characteristics and high-rate discharge characteristics.
（ニ）課題を解決するための手段 本発明は、二酸化マンガンを主体とする正極と、リチウ
ム又はリチウム合金を主体とする負極と、トリフルオロ
メタンスルホン酸リチウムからなる溶質と、エチレンカ
ーボネート、1,2−ブチレンカーボネート及び1,2−ジメ
トキシエタンとの混合溶媒とからなる電解液とを備える
ものであって、前記エチレンカーボネートが５〜30vol
％、前記1,2−ブチレンカーボネートが５〜30vol％含有
されたことを特徴とする。(D) Means for Solving the Problems The present invention is directed to a positive electrode mainly composed of manganese dioxide, a negative electrode mainly composed of lithium or a lithium alloy, a solute composed of lithium trifluoromethanesulfonate, ethylene carbonate, and 1,2. -Butylene carbonate and an electrolytic solution comprising a mixed solvent of 1,2-dimethoxyethane, wherein the ethylene carbonate is 5 to 30 vol.
%, And the content of 1,2-butylene carbonate is 5 to 30 vol%.
（ホ）作用 溶質としてトリフルオロメタンスルホン酸リチウム（Li
CF3SO3）を用いると、この溶質は有機溶媒に対する溶解
度が高く低温放電においても負極上にLiが析出すること
がないため低温放電特性に優れる。(E) Action Lithium trifluoromethanesulfonate (Li
When CF 3 SO 3 ) is used, this solute has a high solubility in an organic solvent and does not deposit Li on the negative electrode even at low temperature discharge, and thus has excellent low temperature discharge characteristics.
一方、溶媒についていえば溶媒には高沸点溶媒と低沸点
溶媒とがあり、高沸点溶媒は一般に電導度は高いが粘度
も高い、これに対して低沸点溶媒は一般に粘度は低いが
電導度も低い。On the other hand, as for the solvent, there are high boiling point solvent and low boiling point solvent, and high boiling point solvent generally has high electric conductivity but high viscosity, whereas low boiling point solvent generally has low viscosity but also electric conductivity. Low.
ところで、高率放電特性向上のための必要条件として
は、電導度が高く、粘度が低いことであるため一般的に
は高沸点溶媒と低沸点溶媒とを組み合わせて用いられて
いる。By the way, as a necessary condition for improving the high rate discharge characteristic, a high boiling point solvent and a low boiling point solvent are generally used in combination because they have high electric conductivity and low viscosity.
高沸点溶媒の中にも電導度、粘度に差があり、エチレン
カーボネート（EC）は電導度は高いものの粘度は比較的
高く、1,2−ブチレンカーボネート（BC）は電導度は比
較的小さいが粘度は低いものである。Even in high boiling solvents, there are differences in electric conductivity and viscosity. Although ethylene carbonate (EC) has a high electric conductivity, it has a relatively high viscosity, and 1,2-butylene carbonate (BC) has a relatively low electric conductivity. The viscosity is low.
そこで、EC及びBCの高沸点溶媒に1,2−ジメトキシエタ
ン（DME）の低沸点溶媒を加えた三成分系の混合溶媒で
あって且つ前記エチレンカーボネートが５〜30vol％、
前記1,2−ブチレンカーボネートが５〜30vol％である特
定の混合溶媒を用いることにより、高率放電に適した電
導度、粘度を持つ電解液が得られることになる。Therefore, a mixed solvent of a three-component system in which a low boiling point solvent of 1,2-dimethoxyethane (DME) is added to a high boiling point solvent of EC and BC, and the ethylene carbonate is 5 to 30 vol%,
By using the specific mixed solvent containing 5 to 30 vol% of 1,2-butylene carbonate, an electrolytic solution having conductivity and viscosity suitable for high rate discharge can be obtained.
（ヘ）実施例 以下本発明の実施例について詳述する。(F) Examples Examples of the present invention will be described in detail below.
二酸化マンガンを350〜430℃で熱処理したものを活物質
とし、この活物質と、導電剤としてのカーボン粉末及び
結着剤としてのフッ素樹脂粉末とを85:10:5の重量比で
混合した混合物を加圧成形し250〜350℃で熱処理したも
のを正極とする。A mixture obtained by mixing manganese dioxide heat-treated at 350 to 430 ° C. as an active material, and mixing the active material with carbon powder as a conductive agent and fluororesin powder as a binder in a weight ratio of 85: 10: 5. Is molded under pressure and heat-treated at 250 to 350 ° C. to obtain a positive electrode.
負極はLi金属を所定寸法に打ち抜いたものを用いた。The negative electrode was made by punching Li metal into a predetermined size.
そして、電解液はEC、BC及びDMEとの混合溶媒（混合比
はEC:BC:DME＝2:1:7）にLiCF3SO3を1mol／1溶解したも
のを用いて径20.0mm、厚み2.5mm、電池容量130mAHの本
発明電池（Ａ）を作成した。The electrolyte used was a mixture of EC, BC and DME (mixing ratio EC: BC: DME = 2: 1: 7) in which LiCF 3 SO 3 was dissolved at 1 mol / 1, and the diameter was 20.0 mm. A battery (A) of the present invention having a thickness of 2.5 mm and a battery capacity of 130 mAH was prepared.
次に、本発明電池の優位性を調べるために種々の比較電
池を作成した。Next, various comparative batteries were prepared in order to investigate the superiority of the battery of the present invention.
比較例１ 電解液としてECとDMEとの混合比（3:7）の混合溶媒にLi
CF3SO3を溶解したものを用いることを除いて他は本発明
電池と同様の比較電池（Ｂ）を作成した。Comparative Example 1 As an electrolytic solution, Li was added to a mixed solvent of EC and DME at a mixing ratio (3: 7).
A comparative battery (B) similar to the battery of the present invention except that CF 3 SO 3 was dissolved was used.
比較例２ 電解液としてBCとDMEとの混合比（3:7）の混合溶媒にLi
CF3SO3を溶解したものを用いることを除いて他は本発明
電池と同様の比較電池（Ｃ）を作成した。Comparative Example 2 As an electrolytic solution, Li was added to a mixed solvent of BC and DME at a mixing ratio (3: 7).
A comparative battery (C) similar to the battery of the present invention except that CF 3 SO 3 was used was prepared.
比較例３ 電解液としてEC、BC及びDMEとの混合比（2:1:7）の混合
溶媒に過塩素酸リチウムを溶解したものを用いることを
除いて他は本発明電池と同様の比較電池（Ｄ）を作成し
た。Comparative Example 3 Comparative battery similar to the battery of the present invention except that lithium perchlorate was dissolved in a mixed solvent having a mixing ratio (2: 1: 7) of EC, BC and DME as the electrolytic solution. (D) was prepared.
第１図及び第２図は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3kΩの定抵抗
で放電したときの低温放電特性、又第２図は25℃におい
て定抵抗で放電したときの高率放電特性を夫々示す。1 and 2 are comparison diagrams of the discharge characteristics of the battery of the present invention and the comparative battery. FIG. 1 is a low temperature discharge characteristic when discharged with a constant resistance of 3 kΩ at −20 ° C., and FIG. The high-rate discharge characteristics when discharged with a constant resistance at 25 ° C are shown respectively.
第１図より溶質にLiCF3SO3を用いた本発明電池（Ａ）及
び比較電池（Ｂ）（Ｃ）は溶質に過塩素酸リチウム（Li
ClO4）を用いた比較電池（Ｄ）に比して低温放電特性が
優れていることがわかる。As shown in FIG. 1, the batteries (A) and comparative batteries (B) and (C) of the present invention using LiCF 3 SO 3 as the solute had lithium perchlorate (Li) as the solute.
It can be seen that the low temperature discharge characteristics are superior to the comparative battery (D) using ClO 4 ).
又第２図より溶媒にEC、BC及びDMEの混合溶媒を用いた
本発明電池（Ａ）及び比較電池（Ｄ）は比較電池（Ｂ）
（Ｃ）に比して放電電圧が高く、放電容量も大きく高率
放電特性が優れていることがわかる。Further, from FIG. 2, the present invention battery (A) and comparative battery (D) using a mixed solvent of EC, BC and DME as the solvent are comparative batteries (B)
It can be seen that the discharge voltage is higher, the discharge capacity is larger, and the high-rate discharge characteristic is superior to that of (C).
第３図乃至第５図はDMEを夫々80vol％、70vol％、60vol
％に固定した時のECとBCとの混合比率と電池の放電容量
との関係を示す図である。これらの図よりEC及びBCは５
〜30vol％の範囲が必要であることがわかる。Figures 3 to 5 show DME as 80 vol%, 70 vol% and 60 vol, respectively.
It is a figure which shows the relationship between the discharge capacity of a battery, and the mixing ratio of EC and BC when fixing to%. From these figures, EC and BC are 5
It can be seen that a range of ~ 30vol% is necessary.
（ト）発明の効果 上述した如く、二酸化マンガンを主体とする正極と、リ
チウム又はリチウム合金を主体とする負極と、トリフル
オロメタンスルホン酸リチウムからなる溶質と、エチレ
ンカーボネート、1,2−ブチレンカーボネート及び1,2−
ジメトキシエタンとの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、前記エチレンカーボネー
トが５〜30vol％、前記1,2−ブチレンカーボネートが５
〜30vol％含有された特定範囲の混合溶媒を用いること
により、低温放電特性及び高率放電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。(G) Effect of the Invention As described above, the positive electrode mainly composed of manganese dioxide, the negative electrode mainly composed of lithium or a lithium alloy, the solute composed of lithium trifluoromethanesulfonate, ethylene carbonate, 1,2-butylene carbonate and 1,2-
In a non-aqueous electrolyte battery comprising an electrolytic solution containing a mixed solvent of dimethoxyethane, the ethylene carbonate content is 5 to 30 vol%, and the 1,2-butylene carbonate content is 5%.
By using a mixed solvent containing a specific range of up to 30 vol%, low-temperature discharge characteristics and high-rate discharge characteristics can be improved, which is extremely large in contributing to the expansion of applications of this type of battery.
第１図は電池の低温放電特性図、第２図は電池の高率放
電特性図、第３図乃至第５図はDMEのvol％を一定とした
時のECとBCとの混合比率と電池の放電容量との関係を示
す図である。Fig. 1 is a low temperature discharge characteristic diagram of the battery, Fig. 2 is a high rate discharge characteristic diagram of the battery, and Figs. 3 to 5 are the mixture ratio of EC and BC and the battery when the vol% of DME is constant. It is a figure which shows the relationship with the discharge capacity of.
Claims (1)
ウム又はリチウム合金を主体とする負極と、トリフルオ
ロメタンスルホン酸リチウムからなる溶質と、エチレン
カーボネート、1,2−ブチレンカーボネート及び1,2−ジ
メトキシエタンとの混合溶媒とからなる電解液とを備え
るものであって、前記エチレンカーボネートが５〜30vo
l％、前記1,2−ブチレンカーボネートが５〜30vol％含
有されたことを特徴とする非水電解液電池。1. A positive electrode mainly composed of manganese dioxide, a negative electrode mainly composed of lithium or a lithium alloy, a solute composed of lithium trifluoromethanesulfonate, ethylene carbonate, 1,2-butylene carbonate and 1,2-dimethoxy. And a mixed solvent of ethane and an electrolytic solution, wherein the ethylene carbonate is 5 to 30 vo
A non-aqueous electrolyte battery containing 1% of the above 1,2-butylene carbonate in an amount of 5 to 30 vol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63111951A JPH0715820B2 (en) | 1988-05-09 | 1988-05-09 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63111951A JPH0715820B2 (en) | 1988-05-09 | 1988-05-09 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01281679A JPH01281679A (en) | 1989-11-13 |
| JPH0715820B2 true JPH0715820B2 (en) | 1995-02-22 |
Family
ID=14574241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63111951A Expired - Lifetime JPH0715820B2 (en) | 1988-05-09 | 1988-05-09 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0715820B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0218863A (en) * | 1988-07-06 | 1990-01-23 | Matsushita Electric Ind Co Ltd | Organic electrolyte battery |
| CN115911570B (en) * | 2022-11-28 | 2023-09-26 | 九江天赐高新材料有限公司 | Use of methyl trifluoroethyl carbonate, electrolyte, method for inhibiting elution of manganese, and battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5693267A (en) * | 1979-12-17 | 1981-07-28 | Esb Int Corp | Nonnaqueous electrolyte and battery using same |
| JPS59134568A (en) * | 1983-01-24 | 1984-08-02 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithium battery |
| JPS63284763A (en) * | 1987-05-15 | 1988-11-22 | Seiko Electronic Components Ltd | organic electrolyte battery |
-
1988
- 1988-05-09 JP JP63111951A patent/JPH0715820B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01281679A (en) | 1989-11-13 |
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